CN1743335A - Reaction systems for making n- (phosphonomethyl) glycine compounds - Google Patents

Abstract

This invention generally relates to liquid-phase oxidation processes for making N-(phosphonomethyl)glycine (also known in the agricultural chemical industry as glyphosate) and related compounds. This invention, for example, particularly relates to processes wherein an N-(phosphonomethyl)iminodiacetic acid (NPMIDA) substrate (i.e., N-(phosphonomethyl)iminodiacetic acid, a salt of N-(phosphonomethyl)iminodiacetic acid, or an ester of N-(phosphonomethyl)iminodiacetic acid) is continuously oxidized to form an N-(phosphonomethyl)glycine product (i.e., N-(phosphonomethyl)glycine, a salt of N-(phosphonomethyl)glycine, or an ester of N-(phosphonomethyl)glycine). This invention also, for example, particularly relates to processes wherein an N-(phosphonomethyl)iminodiacetic acid substrate is oxidized to form an N-(phosphonomethyl)glycine product, which, in turn, is crystallized (at least in part) in an adiabatic crystallizer.

Description

The reactive system of preparation N-((phosphonomethyl)) glycine compound

The field of the invention

Generality of the present invention relates to the liquid-phase oxidation of preparation N-((phosphonomethyl)) glycine (also being referred to as glyphosate in agrochemicals industry) and related compound.The present invention for example relates in particular to wherein N-((phosphonomethyl)) iminodiethanoic acid (NPMIDA) substrate (promptly; N-((phosphonomethyl)) iminodiethanoic acid; the ester of the salt of N-((phosphonomethyl)) iminodiethanoic acid or N-((phosphonomethyl)) iminodiethanoic acid) is oxidized to N-((phosphonomethyl)) glycine product continuously (promptly; N-((phosphonomethyl)) glycine; the salt of N-((phosphonomethyl)) glycine, or the ester of N-((phosphonomethyl)) glycine) method.The present invention for example also is particularly related to wherein, and N-((phosphonomethyl)) iminodiethanoic acid substrate is oxidized to N-((phosphonomethyl)) glycine product, the method for this product and then crystallization in adiabatic crystallizer (to small part).

Background of the present invention

Franz has described N-((phosphonomethyl)) glycine in the U.S. patent No. 3,799,758.N-((phosphonomethyl)) glycine and its salt suit to use as the back weedicide that germinates in aqua.It is highly effective and industrial important broad-spectrum herbicide, can be used for killing or controlling the growth of each kind of plant, comprises seeds germinated, the rice shoot that breaks ground, the woody and herbaceous plant of maturation and field planting, and waterplant.

One of more generally accepted method of preparation N-((phosphonomethyl)) glycine compound comprises by the oxidation of N-((phosphonomethyl)) iminodiethanoic acid substrate cuts off the carboxymethyl substituting group.In the past few years, disclose the whole bag of tricks and be used to carry out this oxidation.Generally consult people such as Franz, Glyphosate:A Unique Global Herbicide (ACS Monograph 189,1997), 233-62 page or leaf (and quoting) here as reference; Franz (the U.S. patent No. 3,950,402); Hershman (the U.S. patent No. 3,969,398); Chou (the U.S. patent No. 4,624,937); Chou (the U.S. patent No. 4,696,772); People such as Ramon (the U.S. patent No. 5,179,228); Felthouse (the U.S. patent No. 4,582,650); People such as Siebenhaar (PCT/EP99/04587); With people (International Publication No. WO 99/43430) such as Ebner.Though the many suitable yields that obtained various N-((phosphonomethyl)) glycine product in these methods, but still need improving one's methods of oxidation N-((phosphonomethyl)) iminodiethanoic acid substrate.Desirable improvement comprises increase output; reduce the cost of per unit N-((phosphonomethyl)) glycine product and reduce undesirable by product (formaldehyde for example; formic acid, N-methyl-N-((phosphonomethyl)) glycine (NMG) and aminomethyl phosphonic acids (AMPA)) concentration.

General introduction of the present invention

The present invention partly provides the iminodiethanoic acid with N-((phosphonomethyl)); the ester of the salt of N-((phosphonomethyl)) iminodiethanoic acid and N-((phosphonomethyl)) iminodiethanoic acid is oxidized to N-((phosphonomethyl)) glycine, the economic means of the ester of the salt of N-((phosphonomethyl)) glycine and N-((phosphonomethyl)) glycine.The present invention also provides the effective ways that are used for purifying and/or are concentrated in N-((phosphonomethyl)) the glycine product that oxidation mixtures obtains.

In brief, therefore, the present invention relates to prepare the method for N-((phosphonomethyl)) glycine product.This method comprises that the water-containing material stream that will comprise N-((phosphonomethyl)) iminodiethanoic acid substrate is incorporated into oxidation reactor system; in this system; the oxidation in the presence of oxide catalyst of N-((phosphonomethyl)) iminodiethanoic acid substrate generates the reaction product solution that comprises N-((phosphonomethyl)) glycine product.Reaction product solution is divided into a plurality of fractions that comprise elementary fraction and secondary fraction.From elementary fraction, be settled out N-((phosphonomethyl)) glycine product crystal; formation comprises the elementary product slurry of sedimentary N-((phosphonomethyl)) glycine product crystal and elementary mother liquor; be settled out N-((phosphonomethyl)) glycine product crystal simultaneously in the moisture secondary crystallization raw mix of the N-that also from be included in the secondary fraction, contains ((phosphonomethyl)) glycine product, form the secondary products slurry that comprises sedimentary N-((phosphonomethyl)) glycine product crystal and secondary mother liquor.

In another embodiment; the method for preparing N-((phosphonomethyl)) glycine product comprises that the water-containing material stream that will contain N-((phosphonomethyl)) iminodiethanoic acid substrate is incorporated into oxidation reactor system; and in this oxidation reactor system; in the presence of oxide catalyst,, generate the reaction product solution that contains N-((phosphonomethyl)) glycine product with the oxidation of N-((phosphonomethyl)) iminodiethanoic acid substrate.N-((phosphonomethyl)) glycine product crystal is precipitated out from reaction product solution, forms the elementary product slurry that comprises sedimentary N-((phosphonomethyl)) glycine product crystal and elementary mother liquor.Vaporize water from elementary mother liquor then, thus make other N-((phosphonomethyl)) glycine product crystal settling and generate the secondary mother liquor.

In another embodiment, the method for preparing N-((phosphonomethyl)) glycine product comprises that the water-containing material stream that will contain N-((phosphonomethyl)) iminodiethanoic acid substrate is incorporated into the primary oxidation reactor system that comprises one or more oxidation reaction zones.The oxidation in the primary oxidation reactor system of N-((phosphonomethyl)) iminodiethanoic acid substrate generates the reaction product solution that comprises N-((phosphonomethyl)) glycine product and unreacted N-((phosphonomethyl)) iminodiethanoic acid substrate.Reaction product solution is divided into a plurality of fractions that comprise elementary fraction and secondary oxidation reactor feedstocks fraction.N-((phosphonomethyl)) glycine product crystal is precipitated out from elementary fraction, forms the elementary product slurry that comprises sedimentary N-((phosphonomethyl)) glycine product crystal and elementary mother liquor.Secondary oxidation reactor feedstocks fraction is incorporated into the secondary oxidation reactor assembly that comprises one or more oxidation reaction zones.The oxidation in the secondary oxidation reactor assembly of N-((phosphonomethyl)) iminodiethanoic acid substrate generates the secondary oxidation reactor effluent that comprises N-((phosphonomethyl)) glycine product.After this, N-((phosphonomethyl)) glycine product crystal is precipitated out from the secondary oxidation reactor effluent, generates the secondary products slurry that comprises sedimentary N-((phosphonomethyl)) glycine product crystal and secondary mother liquor.

The invention still further relates to the method for preparing N-((phosphonomethyl)) glycine product by oxidation N-((phosphonomethyl)) iminodiethanoic acid substrate.This method comprises N-((phosphonomethyl)) iminodiethanoic acid substrate is incorporated in the liquid reaction medium that contains N-((phosphonomethyl)) glycine product in the oxidation reaction zone.The liquid phase of oxidation reaction zone is back mixing basically, and contains the catalyst for oxidation reaction that contacts with liquid reaction medium.Also oxygenant is incorporated into oxidation reaction zone, wherein N-((phosphonomethyl)) iminodiethanoic acid substrate is formed N-((phosphonomethyl)) glycine product by oxidation continuously.Discharge the reaction mixture that comprises N-((phosphonomethyl)) glycine product continuously from oxidation reaction zone and flow out thing.

In another embodiment, described method comprises N-((phosphonomethyl)) iminodiethanoic acid substrate is incorporated in the liquid reaction medium in the oxidation reaction zone.Liquid reaction medium comprises N-((phosphonomethyl)) glycine product and has the particle heterogeneous catalyst that is used for oxidizing reaction that is suspended in wherein.Also oxygenant is incorporated into oxidation reaction zone, wherein N-((phosphonomethyl)) iminodiethanoic acid substrate by oxidation continuously, forms N-((phosphonomethyl)) glycine product in liquid reaction medium.Discharge the reaction mixture that comprises N-((phosphonomethyl)) glycine product continuously from described oxidation reaction zone and flow out thing.Flow out continuous separating particles catalyzer the thing from reaction mixture, obtain to comprise the catalyst recycle materials flow of isolating catalyzer.At least a portion beaded catalyst that contains in the catalyst recycle materials flow is introduced in described oxidation reaction zone.

The invention still further relates to the continuation method for preparing N-((phosphonomethyl)) glycine product by oxidation N-((phosphonomethyl)) iminodiethanoic acid substrate in reactor assembly.This method comprises that water-containing material stream and the oxygenant that will contain N-((phosphonomethyl)) iminodiethanoic acid substrate are incorporated into first oxidation reaction zone.N-((phosphonomethyl)) iminodiethanoic acid substrate by oxidation continuously, forms N-((phosphonomethyl)) glycine product in first oxidation reaction zone.The intermediate reaction mixture that comprises N-((phosphonomethyl)) glycine product and unreacted N-((phosphonomethyl)) iminodiethanoic acid substrate flows out thing discharges continuously from first oxidation reaction zone.Flow and be incorporated into second oxidation reaction zone continuously being included in middle water-containing material that the intermediate reaction mixture flows out N-((phosphonomethyl)) the glycine product that obtains in the thing and unreacted N-((phosphonomethyl)) iminodiethanoic acid substrate with oxygenant; in this oxidation zone; N-((phosphonomethyl)) iminodiethanoic acid substrate is formed other N-((phosphonomethyl)) glycine product by oxidation continuously.From second oxidation reaction zone, discharge the reaction mixture that comprises N-((phosphonomethyl)) glycine product continuously and flow out thing.

The invention still further relates to the method that concentrates and reclaim N-((phosphonomethyl)) glycine product.In one embodiment, provide from the initial aqueous solution that comprises N-((phosphonomethyl)) glycine product except that anhydrating and making N-((phosphonomethyl)) glycine product crystalline method.This method comprises that the moisture evaporation raw mix that will contain the initial aqueous solution is incorporated into evaporating area.In the presence of solid particulate N-((phosphonomethyl)) glycine product; in evaporating area, water is evaporated from raw mix; thereby form the vapour phase that comprises water vapour; from aqueous liquid phase, be settled out N-((phosphonomethyl)) glycine product, and generation comprises N-((phosphonomethyl)) glycine product solid and N-((phosphonomethyl)) glycine product is saturated substantially or the evaporate of oversaturated mother liquor.The ratio that keeps particle N-((phosphonomethyl)) glycine product solid and mother liquor in evaporating area is greater than N-((phosphonomethyl)) glycine product solid that is increased progressively generation by evaporative effect and the ratio that increases progressively the mother liquor of generation thus.

In further embodiment, described method comprises that the evaporation raw mix that will contain the initial aqueous solution is incorporated into vapour/liquid disengaging zone, and pressure is under the vapour pressure of mixture in this district.This comes out water flash distillation from the evaporation raw mix, produced the vapour phase that comprises water vapour, and the concentration that will remain N-((phosphonomethyl)) the glycine product in the liquid phase is increased to the concentration above N-((phosphonomethyl)) glycine product solubleness.As a result, N-((phosphonomethyl)) glycine product is precipitated out from liquid phase, has produced first slurry flow of particle N-((phosphonomethyl)) the glycine product that is included in saturated or the supersaturation mother liquor.Vapour phase is separated with first slurry flow, and first slurry flow is incorporated into the decantation district, will comprise that at this upper strata liquid of mother liquor fraction separates with second slurry flow that comprises sedimentary N-((phosphonomethyl)) glycine product and mother liquor.The decantation district has the import of first slurry, is positioned at the decanting liq outlet of the upper strata liquid on this import, and vertically is positioned on this import but the outlet of second slurry under the outlet of upper strata liquid.Maintenance is incorporated into the decantation district with first slurry; the speed of relative movement that second slurry is discharged by second slurry outlet and upper strata liquid is discharged by the decanting liq outlet; the upward flow speed in the lower region in the decantation district under second slurry outlet that makes is enough to keep sedimentary N-((phosphonomethyl)) glycine product to suspend (promptly; carry secretly) in liquid phase, and the upward flow speed in the upper area in the decantation district on second slurry outlet is in lower region at least under the settling velocity of the N-of 80wt% ((phosphonomethyl)) glycine product particle.

In another embodiment, described method comprises that the moisture evaporation raw mix that will contain the initial aqueous solution is incorporated into evaporating area.In the presence of solid particulate N-((phosphonomethyl)) glycine product; water is evaporated from raw mix in evaporating area; thereby formed the vapour phase that comprises water vapour; N-((phosphonomethyl)) glycine product is precipitated out from aqueous liquid phase, and generation comprises N-((phosphonomethyl)) glycine product solid and N-((phosphonomethyl)) glycine product is saturated substantially or the evaporate of oversaturated mother liquor.Evaporate is divided into N-((phosphonomethyl)) the glycine product solid fraction of the relative dilution of mother liquor and the mother liquor fraction of the relative dilution of N-((phosphonomethyl)) glycine product solid.The ratio that keeps particle N-((phosphonomethyl)) glycine product solid and mother liquor in evaporating area is greater than N-((phosphonomethyl)) glycine product solid that is increased progressively generation by evaporative effect and the ratio that increases progressively the mother liquor of generation thus.

The invention still further relates to the integrated approach that preparation comprises the oxidation mixtures effluent of N-((phosphonomethyl)) glycine product and after this concentrates and reclaim product.In one embodiment; this method comprise the water-containing material mixture that will contain N-((phosphonomethyl)) iminodiethanoic acid substrate be incorporated in the liquid reaction medium and in liquid, aqueous reaction medium catalyzed oxidation N-((phosphonomethyl)) iminodiethanoic acid substrate, thereby produce the oxidation mixtures comprise N-((phosphonomethyl)) glycine product.Cooling is included in the primary crystallization raw mix of N-((phosphonomethyl)) the glycine product that produces in the reaction mixture, thereby is settled out N-((phosphonomethyl)) glycine product and produces the elementary mother liquor that comprises N-((phosphonomethyl)) glycine product.After the N-of precipitation separation from elementary mother liquor ((phosphonomethyl)) glycine product; with elementary mother liquor recirculation be incorporated in the liquid reaction medium, be oxidized to N-((phosphonomethyl)) glycine product at this N-((phosphonomethyl)) iminodiethanoic acid substrate.

In further embodiment of the present invention, described method comprises that the water-containing material mixture that will contain N-((phosphonomethyl)) iminodiethanoic acid substrate is incorporated into the catalytic reactor system that comprises one or more catalytic reaction zones.N-((phosphonomethyl)) iminodiethanoic acid substrate is N-((phosphonomethyl)) glycine product by catalyzed oxidation in catalytic reactor system, produces product mixtures, and this reaction mixture is divided into elementary fraction and secondary fraction.To obtain solid N-((phosphonomethyl)) glycine product fraction and elementary mother liquor from N-((phosphonomethyl)) the glycine product crystallization of elementary fraction.With elementary mother liquor recirculation, in the preparation of the raw mix that is incorporated into catalytic reactor system, use as the water source.

The invention still further relates to that to be used for N-((phosphonomethyl)) iminodiethanoic acid substrate catalyzed oxidation be the continuation method of N-((phosphonomethyl)) glycine product.In one embodiment; this method comprises liquid phase feed stream is incorporated into the primary oxidation reactor district; this liquid phase feed stream comprises the water-containing material stream that contains N-((phosphonomethyl)) iminodiethanoic acid substrate, and the primary oxidation reactor district comprises the primary fixed bed that contains oxide catalyst.Oxygenant is incorporated into the primary oxidation reactor district; be oxidized to N-((phosphonomethyl)) glycine product continuously at this N-((phosphonomethyl)) iminodiethanoic acid substrate, thereby produced the primary reaction mixture that comprises N-((phosphonomethyl)) glycine product and unreacted N-((phosphonomethyl)) iminodiethanoic acid substrate.Discharge the primary reaction mixture from the primary oxidation reactor district.The water-containing material that the difference of the unit weight sensible heat content between reaction mixture and water-containing material stream keeps below per unit weight flows the thermopositive reaction heat that produces in reaction zone.

In another embodiment, described continuation method comprises that the water-containing material stream that will contain N-((phosphonomethyl)) iminodiethanoic acid substrate is incorporated into first of serial oxidation reaction zone, and each of this series oxidation reaction zone all contains oxide catalyst.N-((phosphonomethyl)) iminodiethanoic acid substrate is oxidized in first oxidation reaction zone, produces the intermediate oxidation reaction product.This intermediate oxidation reaction product is incorporated into second oxidation reaction zone that comprises the fixed bed that contains precious metal/C catalyst, and in this district, by product formaldehyde and/or formic acid are oxidized.

In further embodiment, this continuation method comprises that the first component raw material stream that will contain N-((phosphonomethyl)) iminodiethanoic acid substrate is incorporated into first of serial continuous reaction zone, and each of this serial reaction district all contains oxide catalyst.Oxygenant is incorporated into first of this serial reaction district, by catalyzed oxidation, generates the intermediate reaction mixture flow that contains N-((phosphonomethyl)) glycine product at this substrate.To transfer to second of this serial reaction district from the intermediate reaction mixture that first reaction zone is discharged, at this substrate by catalyzed oxidation.Discharge the intermediate reaction mixture from each reaction zone, be incorporated into again in each follow-up reaction zone.Other component raw material stream is incorporated in each of one or more reaction zones after in this series first reaction zone, each other feedstream comprises N-((phosphonomethyl)) iminodiethanoic acid substrate.Oxygenant is incorporated in one or more reaction zones after in this series first reaction zone.From last of this serial reaction district, discharge final reaction product.

In another embodiment, this continuation method comprises that the water-containing material stream that will contain N-((phosphonomethyl)) iminodiethanoic acid substrate is incorporated in the oxidation reaction zone that comprises the fixed bed that contains oxide catalyst.To contain O ₂Gas is incorporated into oxidation reaction zone, is continuously oxidized to N-((phosphonomethyl)) glycine product at this N-((phosphonomethyl)) iminodiethanoic acid substrate, thereby produces the oxidation mixtures that comprises N-((phosphonomethyl)) glycine product.The mass velocity of the liquid phase in fixed bed is about 20～about 800 with the mass velocity of gas phase ratio.

In further embodiment, this continuation method comprises that the water-containing material stream that will contain N-((phosphonomethyl)) iminodiethanoic acid substrate is incorporated in the oxidation reaction zone that comprises the fixed bed that contains oxide catalyst.To contain O ₂Gas is incorporated into oxidation reaction zone, is continuously oxidized to N-((phosphonomethyl)) glycine product at this N-((phosphonomethyl)) iminodiethanoic acid substrate, thereby produces the oxidation mixtures that comprises N-((phosphonomethyl)) glycine product.Liquid phase residual amount in the fixed bed is about 0.1～0.5 with the volume ratio of total bed volume.

In another embodiment, this continuation method comprises that the water-containing material stream that will contain N-((phosphonomethyl)) iminodiethanoic acid substrate is incorporated into the oxidation reaction zone that comprises the fixed bed that contains oxide catalyst.To contain O ₂Gas is incorporated into oxidation reaction zone, is continuously oxidized to N-((phosphonomethyl)) glycine product at this N-((phosphonomethyl)) iminodiethanoic acid substrate, thereby produces the oxidation mixtures that comprises N-((phosphonomethyl)) glycine product.Oxygen partial pressure at the liquid outlet of fixed bed is not higher than about 100psia.

In another embodiment, this continuation method comprises that the water-containing material stream that will contain N-((phosphonomethyl)) iminodiethanoic acid substrate is incorporated into the oxidation reaction zone that comprises the fixed bed that contains oxide catalyst.To contain O ₂Gas is incorporated into oxidation reaction zone, is continuously oxidized to N-((phosphonomethyl)) glycine product at this N-((phosphonomethyl)) iminodiethanoic acid substrate, thereby produces the oxidation mixtures that comprises N-((phosphonomethyl)) glycine product.In the optional position of fixed bed, the dividing potential drop of oxygen is not higher than about 50psia, and wherein the concentration of N-((phosphonomethyl)) iminodiethanoic acid substrate in liquid phase is lower than about 0.1ppm.

In another embodiment, this continuation method comprises that the water-containing material stream that will contain N-((phosphonomethyl)) iminodiethanoic acid substrate is incorporated into the oxidation reaction zone that comprises the fixed bed that contains oxide catalyst.Catalyst surface area is about 100～about 6000m with the ratio that is retained in the liquid in the fixed bed ²/ cm ³Oxygenant is incorporated into oxidation reaction zone, is continuously oxidized to N-((phosphonomethyl)) glycine product, thereby produce the oxidation mixtures that comprises N-((phosphonomethyl)) glycine product at this N-((phosphonomethyl)) iminodiethanoic acid substrate.

In another embodiment, this continuation method comprises that the water-containing material stream that will contain N-((phosphonomethyl)) iminodiethanoic acid substrate is incorporated into the oxidation reaction zone that comprises the fixed bed that contains oxide catalyst.To contain O ₂Gas is incorporated into oxidation reaction zone, is continuously oxidized to N-((phosphonomethyl)) glycine product at this N-((phosphonomethyl)) iminodiethanoic acid substrate, thereby produces the oxidation mixtures that comprises N-((phosphonomethyl)) glycine product.Population mean oxygen partial pressure along the liquid-flow approach in fixed bed is at least about 50psia, and the population mean temperature of the liquid phase in the fixed bed is about 80 ℃～130 ℃.

In another embodiment; this continuation method comprises that the water-containing material stream that will contain N-((phosphonomethyl)) iminodiethanoic acid substrate is incorporated into oxidation reaction zone, and this oxidation reaction zone comprises the fixed bed that contains the oxide catalyst body and be used to promote other measure of gas/liquid mass transfer.To contain O ₂Gas is incorporated into oxidation reaction zone, is continuously oxidized to N-((phosphonomethyl)) glycine product at this N-((phosphonomethyl)) iminodiethanoic acid substrate, thereby produces the oxidation mixtures that comprises N-((phosphonomethyl)) glycine product.

In going back an embodiment; this continuation method comprises liquid phase feed stream is incorporated into the primary oxidation reactor district that comprises the fixed bed that contains oxide catalyst that described liquid phase feed stream comprises the water-containing material mixture that contains N-((phosphonomethyl)) iminodiethanoic acid substrate.Oxygenant is incorporated into the primary oxidation reactor district; be continuously oxidized to N-((phosphonomethyl)) glycine product at this N-((phosphonomethyl)) iminodiethanoic acid substrate, thereby produce the liquid phase discharging current that comprises the primary reaction mixture that contains N-((phosphonomethyl)) glycine product and unreacted N-((phosphonomethyl)) iminodiethanoic acid substrate.Draw the liquid phase discharging current from the primary oxidation reactor district.The speed of introducing liquid phase feed stream and drawing the liquid phase discharging current should make the liquid phase space-time speed in the fixed bed be about 0.5hr ^-1～about 20hr ^-1, based on total bed volume.

Further feature of the present invention partly is obvious, and part will be pointed out hereinafter.

The accompanying drawing summary

Fig. 1 has shown the example in the cross section of honeycomb catalyst carrier.

Fig. 2 is the block diagram that is used for N-((phosphonomethyl)) iminodiethanoic acid substrate is oxidized to the continuous oxidation reaction device system of N-((phosphonomethyl)) glycine product.This reactor assembly comprises the back mixing oxidation reaction zone, the heterogeneous beaded catalyst slurry of this reaction zone utilization round-robin in the loop that is independent of the heat transfer cycle loop.

Fig. 2 A is the block diagram that is used for N-((phosphonomethyl)) iminodiethanoic acid substrate is oxidized to the continuous oxidation reaction device system of N-((phosphonomethyl)) glycine product.This reactor assembly comprises the back mixing oxidation reaction zone, the heterogeneous beaded catalyst slurry of this reaction zone utilization round-robin in the loop that is independent of the heat transfer cycle loop, and comprise flash tank and catalyst recycle jar.

Fig. 2 B is the block diagram that is used for N-((phosphonomethyl)) iminodiethanoic acid substrate is oxidized to the continuous oxidation reaction device system of N-((phosphonomethyl)) glycine product.This reactor assembly comprises the back mixing oxidation reaction zone, and this reaction zone utilization is by the heterogeneous beaded catalyst slurry of heat transfer cycle loop recirculation.

Fig. 3 is the block diagram that is used for N-((phosphonomethyl)) iminodiethanoic acid substrate is oxidized to the continuous oxidation reaction device system of N-((phosphonomethyl)) glycine product.This reactor assembly comprises series connection fractionated two back mixing oxidation reaction zones, and this reaction zone utilization flows to second reaction zone and is recycled to the heterogeneous beaded catalyst slurry of first reaction zone from first reaction zone.

Fig. 4 is the block diagram that is used for N-((phosphonomethyl)) iminodiethanoic acid substrate is oxidized to the continuous oxidation reaction device system of N-((phosphonomethyl)) glycine product.This reactor assembly comprises series connection fractionated two back mixing oxidation reaction zones, and this reaction zone utilization flows to second reaction zone and is recycled to the heterogeneous beaded catalyst slurry of two reaction zones from first reaction zone.

Fig. 5 is the block diagram that is used for N-((phosphonomethyl)) iminodiethanoic acid substrate is oxidized to the continuous oxidation reaction device system of N-((phosphonomethyl)) glycine product.This reactor assembly comprises two back mixing oxidation reaction zones of series connection fractionated, described reaction zone utilizes two kinds of independently heterogeneous beaded catalyst slurry materials, make from the catalyst recycle of first reaction zone to first reaction zone and from the catalyst recycle of second reaction zone to second reaction zone.

Fig. 6 is the block diagram that is used for N-((phosphonomethyl)) iminodiethanoic acid substrate is oxidized to the continuous oxidation reaction device system of N-((phosphonomethyl)) glycine product.This reactor assembly comprises two the back mixing oxidation reaction zones of series connection fractionated that utilize heterogeneous beaded catalyst slurry, and described catalyst slurry is recycled to first reaction zone and is recycled to two reaction zones from second reaction zone from first reaction zone.

Fig. 7 is the synoptic diagram that is used for N-((phosphonomethyl)) iminodiethanoic acid substrate is oxidized to the ejector nozzle loop reactor of N-((phosphonomethyl)) glycine product that can use in continuous oxidation reaction device of the present invention system.

Fig. 8 is the synoptic diagram that is used for N-((phosphonomethyl)) iminodiethanoic acid substrate is oxidized to the fixed-bed reactor of N-((phosphonomethyl)) glycine product that can use in continuous oxidation reaction device of the present invention system.

Fig. 9 is the synoptic diagram that is used for N-((phosphonomethyl)) iminodiethanoic acid substrate is oxidized to the circulating fluid bed reactor of N-((phosphonomethyl)) glycine product that can use in continuous oxidation reaction device of the present invention system.

Figure 10 is the block diagram that is used for N-((phosphonomethyl)) iminodiethanoic acid substrate is oxidized to the continuous distribution formula reactor assembly of N-((phosphonomethyl)) glycine product.This reactor assembly comprises a plurality of reactors, and wherein reaction mixture advances to follow-up reactor this series from each reactor continuously.

Figure 11 is used at reactor assembly N-((phosphonomethyl)) iminodiethanoic acid substrate being oxidized to the oxidation mixtures that comprises N-((phosphonomethyl)) glycine product, and uses nonadiabatic heat to drive evaporative crystallizer reclaims the integrated approach of N-((phosphonomethyl)) glycine product from this oxidation mixtures block diagram.

Figure 12 is used at reactor assembly N-((phosphonomethyl)) iminodiethanoic acid substrate being oxidized to the oxidation mixtures that comprises N-((phosphonomethyl)) glycine product, and uses adiabatic crystallizer to reclaim the block diagram of the integrated approach of N-((phosphonomethyl)) glycine product from this oxidation mixtures.

Figure 12 A is the block diagram that is used for reclaiming from oxidation mixtures the adiabatic crystallizer system of N-((phosphonomethyl)) glycine product.

Figure 13 is used at reactor assembly N-((phosphonomethyl)) iminodiethanoic acid substrate being oxidized to the oxidation mixtures that comprises N-((phosphonomethyl)) glycine product, and uses the adiabatic crystallizer of serial operation and the integrated approach of N-((phosphonomethyl)) glycine product is reclaimed in the nonadiabatic hot combination that drives evaporative crystallizer from this oxidation mixtures block diagram.

Figure 14 is used at reactor assembly N-((phosphonomethyl)) iminodiethanoic acid substrate being oxidized to the oxidation mixtures that comprises N-((phosphonomethyl)) glycine product, and uses the adiabatic crystallizer of mid-shunt operation and the integrated approach of N-((phosphonomethyl)) glycine product is reclaimed in the nonadiabatic hot combination that drives evaporative crystallizer from this oxidation mixtures block diagram.

Figure 14 A is used at reactor assembly N-((phosphonomethyl)) iminodiethanoic acid substrate being oxidized to N-((phosphonomethyl)) glycine product, and uses the block diagram of the integrated approach of the adiabatic crystallizer of mid-shunt operation and combination recovery N-((phosphonomethyl)) the glycine product that nonadiabatic heat drives evaporative crystallizer.N-((phosphonomethyl)) iminodiethanoic acid substrate is oxidized to the oxidation mixtures that comprises N-((phosphonomethyl)) glycine product and unreacted N-((phosphonomethyl)) iminodiethanoic acid substrate in the primary reactor system.To be incorporated in the adiabatic crystallizer from the elementary fraction of the oxidation mixtures of primary reactor system; and unreacted N-((phosphonomethyl)) the iminodiethanoic acid substrate in the secondary oxidation reactor feedstocks fraction of oxidation mixtures is oxidized entering nonadiabatic crystallizer in the second reactor system before, forms other N-((phosphonomethyl)) glycine product.

Figure 15 has shown the influence to the distribution of formic acid by-product concentration by causing in the direct disposable N-of being incorporated into ((phosphonomethyl)) the iminodiethanoic acid oxidation mixtures of bismuth oxide in the circulation of 20 batch reactions.Here, the catalyst concn in the reaction mixture is 0.5wt%, and this catalyzer contains the platinum of 5wt% and the iron of 0.5wt%.

Figure 16 has shown the influence to the distribution of formic acid by-product concentration by the disposable N-of being introduced directly into of bismuth oxide ((phosphonomethyl)) iminodiethanoic acid oxidation mixtures is caused in the circulation of 30 batch reactions.Here, the catalyst concn in the reaction mixture is 0.75wt%, and catalyzer contains the platinum of 5wt% and the tin of 1wt%.

Figure 17 has shown the influence that distributes by the PARA FORMALDEHYDE PRILLS(91,95) by-product concentration that the disposable N-of being introduced directly into of bismuth oxide ((phosphonomethyl)) iminodiethanoic acid oxidation mixtures is caused in the circulation of 30 batch reactions.Here, the catalyst concn in the reaction mixture is 0.75wt%, and catalyzer contains the platinum of 5wt% and the tin of 1wt%.

The influence that N-methyl-N-((phosphonomethyl)) glycine (NMG) by-product concentration is distributed that Figure 18 has caused in having shown in 30 batch reactions circulations by the disposable N-of being introduced directly into ((phosphonomethyl)) the iminodiethanoic acid oxidation mixtures with bismuth oxide.Here, the catalyst concn in reaction mixture is 0.75wt%, and this catalyzer contains the platinum of 5wt% and the tin of 1wt%.

Figure 19 shown in N-((phosphonomethyl)) iminodiethanoic acid oxidation reaction process, mixes the influence to formic acid, formaldehyde and N-methyl-N-((phosphonomethyl)) glycine (NMG) generation that causes by the oxide catalyst that will use in bismuth oxide and formerly 133 crowdes of N-((phosphonomethyl)) iminodiethanoic acid oxidizing reaction circulation.Here, catalyzer comprises the platinum that loads on the 5wt% on the carbon support and the iron of 0.5wt%.

Figure 20 shown in N-((phosphonomethyl)) iminodiethanoic acid oxidation reaction process, mixes the influence to formic acid, formaldehyde and N-methyl-N-((phosphonomethyl)) glycine (NMG) generation that causes by the oxide catalyst that will use in bismuth oxide and formerly 30 crowdes of N-((phosphonomethyl)) iminodiethanoic acid oxidizing reaction circulation.Here, catalyzer comprises the platinum that loads on the 5wt% on the carbon support and the tin of 1wt%.

Figure 21 has shown in 107 batch reactions circulations by mixing the influence to the distribution of formic acid by-product concentration that causes with bismuth oxide and the catalyzer that contains 5wt% platinum and 1wt% tin are disposable.

Figure 22 has shown in 107 batch reactions circulations by with the disposable influence that mixes the PARA FORMALDEHYDE PRILLS(91,95) by-product concentration distribution that causes of bismuth oxide and the catalyzer that contains 5wt% platinum and 1wt% tin.

Figure 23 has shown in 107 batch reactions circulations by mixing the influence to the distribution of N-methyl-N-((phosphonomethyl)) glycine (NMG) by-product concentration that causes with bismuth oxide and the catalyzer that contains 5wt% platinum and 1wt% tin are disposable.

Figure 24 has shown formaldehyde and the distribution of formic acid in the product liquid of embodiment 21.

Figure 25 has shown glyphosate and the distribution of N-((phosphonomethyl)) iminodiethanoic acid in the product liquid of embodiment 22.

Figure 26 has shown glyphosate and the distribution of N-((phosphonomethyl)) iminodiethanoic acid in the product liquid of embodiment 23.

Figure 27 is the process block diagram of the flow reactor system of use in embodiment 24.

Figure 28 is the process block diagram of the flow reactor system of use in embodiment 25.

Figure 29 is the process block diagram of the flow reactor system of use in embodiment 28.

Figure 30 is the process block diagram of the flow reactor system of use in embodiment 35.

Figure 31 is the process block diagram of the flow reactor system of use in embodiment 36.

Detailed description of the preferred embodiments

Generally speaking; method of the present invention comprises that (1) is oxidized to N-((phosphonomethyl)) glycine product with N-((phosphonomethyl)) iminodiethanoic acid substrate in one or more oxidation reaction zones, and/or (2) concentrate and/or purifying N-((phosphonomethyl)) glycine product.Below concise and to the point several further features of describing these steps and more preferred.

By being incorporated into the reactor assembly that comprises the one or more oxidation reaction zones that contain oxide catalyst, N-((phosphonomethyl)) iminodiethanoic acid substrate and oxygenant (being oxygen source) come this substrate of oxidation.Oxidizing reaction is generally carried out according to following equation:

R wherein ¹, R ², R ³And R ⁴Independently be hydrogen separately, agronomically acceptable positively charged ion, the alkyl of alkyl or replacement.

Alkyl is any group of only being made up of carbon and hydrogen.Alkyl can be branching or non-branching, can be saturated or undersaturated, and can comprise one or more rings.The alkyl that is fit to comprises alkyl, thiazolinyl, alkynyl and aryl.They also comprise by alkyl, thiazolinyl, alkynyl and the aryl of other aliphatic series or cyclic hydrocarbon group replacement, as alkaryl, alkene aryl and alkynes aryl.

The alkyl that replaces is that wherein at least one hydrogen atom or (b) is contained any alkyl that the atomic group of at least one non-hydrogen atom replaces by (a) non-hydrogen atom.For example, hydrogen atom can be replaced as chlorine or fluorine atom by halogen atom.Perhaps hydrogen atom can be replaced to form for example hydroxyl, ether, ester, acid anhydrides, aldehyde, ketone or carboxylic acid by Sauerstoffatom or the group that contains Sauerstoffatom.Hydrogen atom can also be by the group displacement of nitrogen atom to form for example acid amides or nitro.In addition, hydrogen atom can be contained the group replacement of sulphur atom for example to form-SO ₃H.

Agronomically acceptable positively charged ion is that the agricultural and the effective anionic positively charged ion of N-((phosphonomethyl)) glycine of weeding activity economically can be provided.This positively charged ion can be an alkali metal cation (for example sodium or potassium ion) for example, ammonium ion, sec.-propyl ammonium ion, tetraalkyl ammonium ion, trialkyl sulfonium cation, protonated primary amine, protonated secondary amine or protonated tertiary amine.

In particularly preferred embodiments, R ¹, R ², R ³And R ⁴Be hydrogen or agronomically acceptable positively charged ion independently of one another, wherein hydrogen is normally most preferred.

Can use various oxygenants according to the present invention.They for example comprise superoxide (H for example ₂O ₂, benzoyl peroxide), hydroperoxide, peracid contains O ₂Gas and the liquid that comprises dissolved oxygen.Generally contain O ₂Gas is particularly preferred.Term used herein contains O ₂Gas is to comprise O ₂With the arbitrary gas mixture of one or more thinners of choosing wantonly, described thinner does not react with oxygen or with substrate or product under reaction conditions.The example of such gas is an air; Pure O ₂Or with He, Ar, N ₂And/or the O of other non-oxidized gas dilution ₂Oxygen source most preferably is to contain at least about 95mol%O ₂, more preferably at least about the O that contains of 98mol% ₂Gas, residuum are one or more non-oxidized gas (N especially ₂And/or Ar).

Preferred oxide catalyst

Can use various oxide catalysts according to the present invention.They comprise two kinds of homogeneous phase or heterogeneous catalysts.

For example, can use various water-soluble tungsten salt to come catalyzing N-((phosphonomethyl)) iminodiethanoic acid substrate H ₂O ₂Oxidation.N-((phosphonomethyl)) iminodiethanoic acid can also be used H ₂O ₂At acid (H for example ₂SO ₄) and heat existence under be oxidized to the N-oxide intermediate.This N-oxide intermediate and then can in the presence of heat and various water-soluble ferrous, cuprous, tungsten, molybdenum and vanadic salts catalyzer, decompose formation N-((phosphonomethyl)) glycine.About using these homogeneous catalysts that the general argumentation that N-((phosphonomethyl)) iminodiethanoic acid is converted into N-((phosphonomethyl)) glycine can be seen for example people such as Franz, Glyphosate:A Unique Global Herbicide(ACS Monograph 189,1997), the 240-41 page or leaf.

Generally more preferably use heterogeneous catalyst.This preferably to small part owing to easy, because heterogeneous catalyst can be separated from reaction mixture after oxidation usually.Many suitable heterogeneous catalysts are disclosed in the document.

Franz discloses one of heterogeneous catalyst the earliest of the oxidation scission that is used for catalyzing N-((phosphonomethyl)) iminodiethanoic acid in the U.S. patent No. 3,950,402.Franz discloses can be by in the presence of the catalyzer that comprises the precious metal that is deposited on the carried by active carbon surface, N-((phosphonomethyl)) iminodiethanoic acid O ₂Liquid-phase oxidation is ruptured and is prepared N-((phosphonomethyl)) glycine product.

Even the method for Franz has generally obtained the acceptable yield and the purity of N-((phosphonomethyl)) glycine, it also exists many problems:

1, the precious metal of the costliness in the catalyzer of Franz often is lost to (being lixiviate) in the reaction soln.This precious metal lixiviate is the result of at least two factors: (a) under the oxidizing condition of reaction, some precious metals are oxidized to more soluble form; (b) N-((phosphonomethyl)) iminodiethanoic acid substrate and N-((phosphonomethyl)) glycine product the two all work to add the part of soluble noble metal.

2, the frequent oxidation of N-((phosphonomethyl)) glycine product forms aminomethylphosphonic acid (AMPA), especially when the density loss of N-((phosphonomethyl)) iminodiethanoic acid substrate.This has obviously reduced the yield of required N-((phosphonomethyl)) glycine product.

In the U.S. patent No. 3,969,398, Hershman discloses the oxidation scission that independent gac (need not have precious metal) can be used to carry out N-((phosphonomethyl)) iminodiethanoic acid, to form N-((phosphonomethyl)) glycine.In the U.S. patent No. 4,624,937, Chou is further open, removes oxide compound by the surface from C catalyst before being used for oxidizing reaction, can increase the activity of the disclosed C catalyst of Hershman.The U.S. patent No. 4,696,772 (providing about increasing the active independent argumentation of C catalyst by remove oxide compound from the C catalyst surface by Chou) also can be provided.Though these methods obviously do not have the leaching problem of precious metal, when being used to carry out the oxidation scission of N-((phosphonomethyl)) iminodiethanoic acid, they often produce the formaldehyde and the formic acid by product of greater concn.

When being easy to act as most N-((phosphonomethyl)) iminodiethanoic acid substrate and being oxidized to N-((phosphonomethyl)) glycine, formaldehyde and formic acid are oxidized to carbonic acid gas and water simultaneously, have obtained following reaction like this:

Comprise that the catalyzer that loads on the precious metal on the carbon support concentrated the many attentions of people because of at least two reasons.Use these catalyzer, the carbon component is mainly carried out the oxidation of N-((phosphonomethyl)) iminodiethanoic acid, and with formation N-((phosphonomethyl)) glycine and formaldehyde, and noble metal component is mainly carried out the oxidation of formaldehyde and formic acid, to form carbonic acid gas and water.Noble metal component also often reduces the speed of deactivating of carbon.More particularly, when independent use gac, it often deactivates with nearly 10%/circulation or 10%/above speed of circulation.Be not bound by any particular theory, but it is believed that deactivating of independent gac is because surface oxidation under reaction conditions of carbon support causes.Consult Chou, the U.S. patent No. 4,624,937.Also consult Chou, the U.S. patent No. 4,696,772 (the independent argumentation that provides relevant gac to be deactivated) by the oxidation of carbon surface.Yet in the presence of precious metal, the speed of deactivating of gac descends.It is believed that precious metal and oxygenant with the reaction of specific activity carbon surface faster speed, therefore, before a large amount of generations of the oxidation of carbon surface, from solution, preferentially remove oxygenant.In addition, do not resemble at activated carbon surface and form and need pyroprocessing to come reductive many oxide-based, be present in reaction mixture or be added to reductive agent in the reaction mixture (Duan Lie amine fragment for example, formaldehyde oxide-based general easily what precious metal surface formed, formic acid, H ₂Deng) reduction, therefore precious metal surface is returned to reduced state.Like this, this catalyzer has advantageously showed the obviously longer life-span, as long as precious metal does not lose because of lixiviate, or by such as dissolving and the process deposition or the precious metal gathering and sintering (form that promptly is unfavorable thick-layer or piece) again.

People such as Ramon (the U.S. patent No. 5,179,228) disclose and have used the example that is deposited on the lip-deep precious metal of carbon support.For the problem that reduces lixiviate people's reports such as (can up to 30% precious metal losses/circulation) Ramon, people such as Ramon disclose after oxidizing reaction is finished and used N under pressure ₂Purge reaction mixture, so that precious metal deposits on the surface of carbon support again.According to people such as Ramon, N ₂Purging reduces to precious metal losses and is lower than 1%.

Felthouse (the U.S. patent No. 4; 582; 650) disclose and used 2 kinds of catalyzer: (i) N-((phosphonomethyl)) iminodiethanoic acid has been oxidized to the gac of N-((phosphonomethyl)) glycine and (ii) simultaneously with the promotor of oxidation of formaldehyde as carbonic acid gas and water.Promotor is the aluminosilicate carrier that has precious metal in its hole.Select the size in these holes, so that repel N-((phosphonomethyl)) thereby glycine and prevent that the precious metal of promotor from being poisoned by N-((phosphonomethyl)) glycine.According to Felthouse, these two kinds of catalyzer use together and can simultaneously N-((phosphonomethyl)) iminodiethanoic acid are oxidized to N-((phosphonomethyl)) glycine and oxidation of formaldehyde is carbonic acid gas and water.

People such as Ebner, International Publication No. WO 99/43430 (its whole disclosures are combined in this by reference) disclose the method for using drastic reduction catalyst oxidation N-((phosphonomethyl)) the iminodiethanoic acid substrate that comprises the precious metal that loads on the carbon support.The destruction that this catalyzer has often showed improved leachability of anti-precious metal the and undesirable by product (for example formaldehyde) increases.The advantage of such catalyzer makes that they are particularly preferred.Therefore, following many argumentations will concentrate on these catalyzer.Even so, should be realized that feature of the present invention can use above-mentioned various homogeneous phases and heterogeneous catalyst to use usually.

At the lip-deep oxygen-containing functional group of carbon support (carboxylic-acid for example; ethers, alcohols, aldehydes; lactone; ketone, ester class, amine oxide class and amides) often increased the precious metal leaching; and increased precious metal sintering in the liquid phase oxidation reaction process potentially; therefore, reduced the ability of catalyst oxidation oxidable substrate, especially formaldehyde and formic acid in N-((phosphonomethyl)) iminodiethanoic acid oxidation reaction process.If term oxygen-containing functional group used herein is incorporated on the atom of carbon support, is surface so, and can interacts with chemistry or physics mode with component in the reaction mixture or with the atoms metal that is deposited on the carbon support at carbon support.

When described catalyzer under the high temperature (for example 900 ℃) in inert atmosphere (for example helium or argon gas) when heating, anti-leachability of many reduction precious metals and coking property and the oxygen-containing functional group that reduces catalyst activity are as carbon monoxide desorb from the carbon support.Therefore, measuring live catalyst (catalyzer that be not used for liquid phase oxidation reaction promptly) CO desorption quantity at high temperature, is to be used for a kind of method of analysis of catalyst surface with prediction precious metal retention rate and catalytic activity conservation rate.A kind of method of measure CO desorb is to use the thermogravimetry that adopts online mass spectroscopy (TGA-MS).Preferably, when dry, fresh catalyst sample experience in helium-atmosphere with 10 ℃/minute and rise to 900 ℃ from 20 ℃, when being held constant at 900 ℃ temperature then and assigning 30 minutes, every gram catalyzer has the desorb from the catalyzer of the carbon monoxide that is not higher than about 1.2mmol.More preferably, every under these conditions gram live catalyst has the carbon monoxide desorb that is not higher than about 0.7mmol, also more preferably every gram live catalyst has the carbon monoxide desorb that is not higher than about 0.5mmol, and most preferably every gram live catalyst has the carbon monoxide desorb that is not higher than about 0.3mmol.When catalyzer had the moisture content that is lower than 1wt%, catalyzer was considered to exsiccant.Usually, can be by catalyzer be put into N ₂Came dry catalyst in the vacuum of 25 inches Hg posts that purge and under 120 ℃ temperature in 16 hours.

The number of the Sauerstoffatom of measurement on the live catalyst carrier surface is to be used for the other method of analysis of catalyst with prediction precious metal retention rate and catalytic activity conservation rate.For example use the x-ray photoelectron spectroscopy method, analyze the top layer of the carrier of the about 50_ of thickness.The present obtainable equipment that is used for the x-ray photoelectron spectroscopy method generally is accurate to ± 20% scope in.Usually, (carbon atom: surface carbon atom Sauerstoffatom) and the ratio of Sauerstoffatom (by being used for the present obtainable measuring apparatus of x-ray photoelectron spectroscopy method) were fit at least about 20: 1.Yet preferably, this ratio is at least about 30: 1, more preferably at least about 40: 1, also more preferably at least about 50: 1 with most preferably at least about 60: 1.In addition, at the Sauerstoffatom on surface and the ratio of atoms metal (also the being) (Sauerstoffatom: atoms metal) that preferably is lower than about 8: 1 by being used for the present obtainable measuring apparatus of x-ray photoelectron spectroscopy method.More preferably this ratio is lower than 7: 1, also is more preferably less than about 6: 1 and most preferably is lower than about 5: 1.

Usually, the carbon support that uses in the present invention is known in the art.Active, non-graphitized carbon support is preferred.These carriers are characterised in that the high absorbent capacity and relative high specific surface area to gas, steam and colloidal solids.Carrier can be suitably by mode as known in the art, for example pass through the carbon that timber, peat, brown coal, coal, nutshell, bone, plant or other destructive distillation natural or synthetic carbonaceous material produce, charcoal or charcoal, but preferably be activated with further raising absorbing power.Activation is usually by with steam or be heated to high temperature (800-900 ℃) with carbonic acid gas and realize that this will cause the porous particle structure and increase specific surface area.In some cases, before destructive distillation or activation, add hygroscopic material, as zinc chloride and/or phosphoric acid or sodium sulfate, to improve receptivity.The carbon content of preferred carbon support is in about 10% (bone black) arrives about 98% (some charcoals) and the scope near 100% (from organic polymer deutero-gac).Non-carbon species in commercially available absorbent charcoal material changes according to the factor such as precursor source, processing and activation method usually.Many commercially available carbon supports contain a spot of metal.The carbon support that has minimum oxygen-containing functional group on the surface is most preferred.

The form of the carrier that uses in fixed-bed reactor can considerable change.For example, carbon support can be the form of integral carriers.The integral carriers that is fit to can have different shape.Integral carriers for example can exist with the form of reactor impeller.Also more preferably, this carrier can also be for example to have the screen cloth of parallel channels (raw mix is by this passage) or the form of honeycomb.Fig. 1 has shown the example in the cross section of honeycomb substrate.Though the cross section of the passage in the honeycomb substrate of Fig. 1 is a sexangle, Ding Yi honeycomb substrate can also (or in addition) comprises have other cross-sectional shape passage of (for example, annular, ellipse, square, trilateral, rectangle etc.) here.The passage of honeycomb substrate is preferably straight, and/or has enough big cross section, makes the slurry that they are not contained solid N-((phosphonomethyl)) iminodiethanoic acid substrate stop up.Perhaps, the flow passage in the integral carriers can be irregular and not have uniform flow direction (random network of the flow passage that for example interconnects).

In particularly preferred embodiments, carrier exists with the particulate form.Because particulate vector is particularly preferred, so following most of the argumentation concentrates on the embodiment of using particulate vector.Yet, should be realized that, the invention is not restricted to use particulate vector.

The particulate vector that is fit to can have various shapes.For example, these carriers can be pill, particulate and form of powder.The pill carrier generally has the granularity of about 1mm to about 10mm.Preferred vector is a form of powder.These particulate vectors can use as free particle in reactor assembly, maybe can be incorporated into the structure in the reactor assembly, on screen cloth or impeller.

Usually, the carrier of particle form comprises the particle of wide distribution of sizes.For powder, preferably the overall dimension at least about 95% particle is about 2 to about 300 μ m, more preferably the overall dimension at least about 98% particle is about 2 to about 200 μ m, and most preferably from about the overall dimension of 99% particle is that about 2 overall dimensions to the particle of about 150 μ m and about 95% are about 3 to arrive about 100 μ m.Overall dimension often is broken for ultrafine particle (that is, overall dimension is less than 2 μ m) greater than the particle of about 200 μ m, thereby is difficult to reclaim.

Use N ₂The specific surface area preferably about 10 of the carbon support of measuring by BET (Brunauer-Emmett-Teller) method is to about 3,000m ²/ g (surface-area of carbon support/g carbon support), more preferably about 500 to about 2,100m ²/ g and also more preferably about 750 to about 2,100m ²/ g.In some embodiments, most preferred specific surface area is about 750 to about 1,750m ²/ g.

The pore volume of carrier can alter a great deal.Use is in the measuring method described in the embodiment 1, and pore volume preferably about 0.1 to about 2.5ml/g (pore volume/g catalyzer) is more preferably about 0.2 to about 2.0ml/g, most preferably is about 0.4 to about 1.7ml/g.Comprise that pore volume is often broken easily greater than the catalyzer of the carrier of about 2.5ml/g.On the other hand, comprise that pore volume often has little surface-area and therefore has low activity less than the catalyzer of the carrier of 0.1ml/g.

Being used for carbon support of the present invention can be purchased from many sources.Below be the inventory of the more operable gacs of the present invention: Darco G-60 Spec and Darco X (ICI-America, Wilmington, DE); Norit SG Extra, Norit EN4, Norit EXW, NoritA, Norit Ultra-C, Norit ACX and Norit 4 X 14 orders (Amer.Norit Co., Inc., Jacksonville, FL); Gl-96 15, VG-8408, and VG-8590, NB-9377, XZ, NW and JV (Barnebey-Cheney, Columbus, OH); BL Pulv., PWA Pulv., Calgon C 450 and PCB Fines (Pittsburgh Activated Carbon, Div.OfCalgon Corporation, Pittsburgh, PA); P-100 (No.Amer.Carbon, Inc., Columbus, OH); Nuchar CN, Nuchar C-1000N, Nuchar C-190A, Nuchar C-115A and Nuchar SA-30 (Westvaco Corp., CarbonDepartment, Covington, Virginia); Code 1551 (Baker and Adamson, Division of Allied Amer.Norit Co., Inc., Jacksonville, FL); Grade 235, and Grade 337, and Grade 517 and Grade 256 (Witco Chemical Corp., Activated Carbon Div., New York, NY); With Columbia SXAC (UnionCarbide New York, NY).

Carbon support preferably has one or more precious metals in its surface.Preferred precious metal is selected from platinum (Pt), palladium (Pd), ruthenium (Ru), rhodium (Rh), iridium (Ir), silver (Ag), osmium (Os) and gold (Au).Usually, platinum and palladium are preferred, and platinum is most preferred.Because platinum is most preferred precious metal at present, so following argumentation will relate generally to the embodiment of using platinum.Yet, be noted that identical argumentation generally is applicable to other precious metal and their combination.Should also be understood that term precious metal used herein is meant the precious metal of elementary state and with any precious metal that exists of its various states of oxidation.

The concentration that is deposited on the lip-deep precious metal of carbon support can change in wide region.Preferred this concentration is about 0.5 to about 20wt%, more preferably from about 2.5 arrives about 10wt%, most preferably from about 3 arrives about 7.5wt% ([total mass of the quality ÷ catalyzer of precious metal] * 100%).If in N-((phosphonomethyl)) iminodiethanoic acid oxidation reaction process, use the concentration that is lower than 0.5wt%; often oxidation of formaldehyde reduces; and therefore produce more substantial N-methyl-N-((phosphonomethyl)) glycine, thereby reduced N-((phosphonomethyl)) glycine yield.On the other hand, be higher than under the concentration of about 20wt%, trending towards forming the layer and the piece of precious metal.Therefore, employed unit precious metal total amount has surperficial precious metal atom still less.This has often reduced activity of such catalysts, and has used expensive precious metal wastefully.

It is about 10 to about 400 μ mol/g (μ mol surface precious metal atoms/g catalyzer) that precious metal preferably should make the concentration of surperficial precious metal atom in the lip-deep dispersion of carbon support, more preferably from about 10 to about 150 μ mol/g and most preferably from about 15 arrives about 100 μ mol/g.This for example can by use Micromeritics ASAP 2010C (Micromeritics, Norcross, GA) or Altamira AMI100 (Zeton Altamira, Pittsburgh PA) measure H ₂Or the chemisorption of CO is measured.

Preferred precious metal is that form with metallics is on the surface of carbon support.In the overall dimension preferably about 0.5 to about 35nm of the lip-deep noble metal at least about 90% (number density) of carbon support, more preferably overall dimension be about 1 to about 20nm and most preferably overall dimension be about 1.5 to arrive about 10nm.In particularly preferred embodiments, be about 1 to about 15nm in the lip-deep overall dimension of carbon support at least about 80% noble metal, more preferably overall dimension be about 1.5 to about 10nm and most preferably overall dimension be about 1.5 to arrive about 7nm.If noble metal is too little, when in catalyzer is being easy to dissolve the environment of precious metal, using,, often increase the leaching amount as in that N-((phosphonomethyl)) iminodiethanoic acid is oxidized under the situation of N-((phosphonomethyl)) glycine.On the other hand, along with the increase of granularity, employed unit precious metal total amount often has precious metal surface atom still less.As mentioned above, this has often reduced activity of such catalysts, and also is to use expensive precious metal wastefully.

Except precious metal, at least a promotor may reside in the surface of carbon support.Here defined promotor being trends towards increasing catalyst selectivity, activity and/or stable metal.Promotor can be reduced precious metal in addition and be leached.Though promotor deposits in the promotor deposition step on the surface of carbon support usually, carbon support itself is also can (or alternatively) natural to contain promotor.Be reduced the promotor that (following) deposits before or self-heating is present in catalyst surface on the carbon support surface at last and be called as catalyst surface promotor here.

Catalyst surface promotor for example can be lip-deep other precious metal at carbon support.For example, depend on application, ruthenium and palladium can play catalyst surface promotor comprising on the catalyzer that be deposited on the lip-deep platinum of carbon support.Catalyst surface promotor for example can be to be selected from tin (Sn) in addition, cadmium (Cd), magnesium (Mg), manganese (Mn), nickel (Ni), aluminium (Al), cobalt (Co), bismuth (Bi), plumbous (Pb), titanium (Ti), antimony (Sb), selenium (Se), iron (Fe), rhenium (Re), zinc (Zn), cerium (Ce), zirconium (Zr), the metal in tellurium (Te) and the germanium (Ge).The preferred catalyst surface promoter is selected from bismuth, iron, tin, tellurium and titanium.In an especially preferred embodiment, catalyst surface promotor is tin.In another particularly preferred embodiment, catalyst surface promotor is iron.In other embodiment preferred, catalyst surface promotor is titanium.In going back a particularly preferred embodiment, catalyzer comprises iron and tin on its surface.The precious metal that iron, tin or the use of the two general (1) have reduced the catalyzer that uses several cycles leaches; (2) when catalyzer is used to carry out the oxidation of N-((phosphonomethyl)) iminodiethanoic acid substrate, often increases and/or kept activity of such catalysts.It generally is most preferred wrapping ferruginous catalyzer, because they often have the highest activity and stable for formaldehyde and formic acid oxidation.

In preferred embodiments, catalyst surface promotor is than the easier oxidation of precious metal (catalyst surface promotor also is under the situation of precious metal therein, and catalyst surface promotor precious metal is preferably than the easier oxidation of non-promotor precious metal).If promotor has the first lower ionizing potential than precious metal, promotor is easier to be oxidized so.First ionizing potential of element is well-known in the art, and can for example see CRC Handbook of Chemistry And Physics(CRC Press, Inc., Boca Raton, Florida).

Depend on for example employed precious metal and catalyst surface promotor, can in wide region, change in the amount of the catalyst surface promotor on carbon support surface (whether no matter with carbon surface itself, metal or their combination are associated mutually).Usually, the weight percentage of catalyst surface promotor is at least about 0.05% ([total mass of the quality ÷ catalyzer of catalyst surface promotor] * 100%).The weight percentage of catalyst surface promotor preferably about 0.05 is to about 10%, and more preferably from about 0.1 to about 10%, and also more preferably from about 0.1 to about 2% and most preferably from about 0.2 to about 1.5%.When catalyst surface promotor was tin, weight percentage most preferably was about 0.5 to about 1.5%.Be lower than 0.05% catalyst surface promotor weight percentage generally can not be in long-time the promotion activity of such catalysts.On the other hand, be higher than about 10% weight percentage and often reduced activity of such catalysts.

According to for example employed precious metal and catalyst surface promotor, the mol ratio of precious metal and catalyst surface promotor (catalyst surface promotor also is under the situation of precious metal therein, the mol ratio of non-promotor precious metal and catalyst surface promotor precious metal) also can alter a great deal.Preferred this ratio is about 1000: 1 to about 0.01: 1; More preferably from about 150: 1 to about 0.05: 1; Also more preferably from about 50: 1 to about 0.05: 1; Most preferably from about 10: 1 to about 0.05: 1.For example, the catalyzer that comprises platinum and iron preferably has about 3: 1 platinum and iron mol ratio.

In a particularly preferred embodiment of the present invention, precious metal (for example Pt) and at least a catalyst surface promotor are (for example, Sn, Fe or the two) become alloy, formation alloyed metal particle (and catalyst surface promotor also is under the situation of precious metal therein, non-promotor precious metal preferably becomes alloy with catalyst surface promotor precious metal).Comprise that to become the catalyzer of the precious metal of alloy often to have with at least a catalyst surface promotor above about described all advantages of the catalyzer that generally comprises catalyst surface promotor.Comprise the catalyzer that becomes the precious metal of alloy with at least a catalyst surface promotor also often showed higher anti-catalyst surface promotor leachability and in addition for formaldehyde and formic acid oxidation each the circulation between stability (consulting for example embodiment 17).

The term alloy comprises any metallics that contains precious metal and at least a catalyst surface promotor, no matter precious metal and the catalyst surface promotor atom accurate mode of arranging in particle how (though general preferred surface at the alloyed metal particle has the part precious metal atom) wherein.This alloy for example can be following any:

1, Intermetallic compoundIntermetallic compound is the compound that comprises precious metal and promotor (Pt for example ₃Sn).

2, Substitutional alloySubstitutional alloy has single external phase, no matter the concentration of precious metal and promotor atom how.Usually, replace alloy and contain precious metal and promotor atom, they are similarly (for example platinum and silver dimensionally; Or platinum and palladium).Substitutional alloy also is called single-phased alloy.

3, Polyphase alloyPolyphase alloy is the alloy that contains at least two kinds of discontinuous phases.This alloy can contain for example Pt in mutually at one ₃Sn, and in a separation mutually, contain the tin that is dissolved in the platinum.

4, Separate alloySeparate alloy and be the metallics that wherein chemistry of particles metering changes with the variation of the distance on distance metallics surface.

5, Caulking metalCaulking metal is a bonded metallics such as precious metal and promotor atom and non-metallic atom such as boron, carbon, silicon, nitrogen, phosphorus wherein.

Preferably the alloyed metal particulate overall dimension at least about 80% (number density) is about 0.5 to about 35nm, and more preferably overall dimension is about 1 to about 20nm, and also more preferably overall dimension is about 1 to about 15nm, and most preferably overall dimension is about 1.5 to about 7nm.

The alloyed metal particle need not have uniform composition; Between each particle, and even the composition within the particle itself can be different.In addition, catalyzer can also comprise separately by precious metal or the independent particle of being made up of catalyst surface promotor.Even so, the composition of preferable alloy particle is being uniform substantially between each particle and within each particle, and the number of the precious metal atom that closely contacts of preferred and catalyst surface promotor atom maximizes.Though dispensable, also preferred most of precious metal atoms become alloy with catalyst surface promotor, more preferably basic all precious metal atoms become alloy with catalyst surface promotor.Though dispensable, further the preferred alloy metallics is evenly distributed on the surface of carbon support.

No matter whether catalyst surface promotor become alloy with precious metal, think at present, if this catalyst exposure in the oxygenant certain hour, catalyst surface promotor is often oxidized.For example, element tin catalyst surface promotor often is oxidized to Sn (II) O, and Sn (II) O often is oxidized to Sn (IV) O ₂For example, if catalyst exposure is about more than 1 hour in air, this oxidation can take place.Though the oxidation of this catalyst surface promotor does not find that precious metal leaching, precious metal sintering, catalyst activity or catalyst stability are had remarkable adverse influence, it makes analysis become more difficult in the concentration of harmful oxygen-containing functional group on carbon support surface.For example, as mentioned above, the concentration of harmful oxygen-containing functional group (that is, reduce anti-leachability of precious metal and sintering resistance, and reduce the oxygen-containing functional group of catalyst activity) can at high temperature be measured from the CO of catalyzer desorb in inert atmosphere by measurement (using for example TGA-MS) and measure.Yet, believe at present, when the catalyst surface promotor of oxidation is present in the surface, the Sauerstoffatom that comes autoxidizable catalyst surface promotor often with carbon atom reaction at high temperature in inert atmosphere of carrier, generate CO, have than the in esse more illusion that is harmful to oxygen-containing functional group thereby produced on the surface of carrier.These Sauerstoffatoms of the catalyst surface promotor of oxidation can also influence the reliable prediction that is obtained precious metal leaching, precious metal sintering and catalyst activity by the Sauerstoffatom single measurement of catalyst surface (for example through the x-ray photoelectron spectroscopy method).

Therefore, when catalyzer comprises at least a catalyst surface promotor of catalytic oxidation agent and oxidized thereby (for example when catalyzer ingress of air about more than 1 hour the time), preferably before the amount of harmful oxygen-containing functional group of attempting to measure the carbon support surface, catalyst surface promotor is at first by basic reduction (thereby removing Sauerstoffatom of the catalyst surface promotor of deoxidation) from catalyst surface.This reduction is preferred by mainly by H ₂In the atmosphere of forming catalyzer being heated to 500 ℃ temperature reaches 1 hour and realizes.The mensuration of harmful oxygen-containing functional group on surface preferred (a) is carried out before the surperficial catalytic oxidation agent after reduction after this reduction and (b).Most preferably after reduction, measure immediately.

The preferred concentration of the metallics on carbon support surface depends on for example size of metallics, the specific surface area of carbon support and the precious metal concentration on catalyzer.Think that at present usually, the preferred concentration of metallics probably is about 3 to about 1,500 particle/μ m ²(that is number of metallics/μ m, ²The carbon support surface), especially wherein: (a) overall dimension at least about the metallics of 80% (number density) is about 1.5 to about 7nm, and (b) carbon support has about 750 and arrives about 2100m ²The specific surface area of/g (is m ²Carbon support surface/g carbon support) and (c) concentration of the precious metal on carbon support surface is about 1 to about 10wt% ([total mass of the quality ÷ catalyzer of precious metal] * 100%).In a more preferred embodiment, need more the metallics concentration and the precious metal concentration of close limit.In such embodiment, the concentration of metallics is about 15 to about 800 particles/μ m ², the concentration of precious metal on the carbon support surface is about 2 to about 10wt%.In more preferred embodiment, the concentration of metallics is about 15 to about 600 particles/μ m ², the concentration of precious metal on the carbon support surface is about 2 to about 7.5wt%.In the most preferred embodiment, the concentration of metallics is about 15 to about 400 particles/μ m ², the concentration of precious metal on the carbon support surface is about 5wt%.Metallics can use methods known in the art to measure in the concentration on carbon support surface.

The surface of carbon support is deoxidation before noble metal loading is to this surface preferably.Preferably should use the high temperature deoxidation to handle deoxidation in the surface.This processing can be a step or a multistep scheme, and under each situation, this processing makes in the whole chemical reductions of the lip-deep oxygen-containing functional group of carbon support.

In two step high temperature deoxidations are handled, carbon support is preferably at first handled with gas or liquid-phase oxidation agent, so that with the oxygen-containing functional group of relative low-oxidation-state (ketone for example, aldehydes and alcohols) be converted into functional group's (for example carboxylic acid) of relative high oxidation state, the latter is easier at high temperature ruptures from catalyst surface.Representational liquid-phase oxidation agent comprises nitric acid, H ₂O ₂, chromic acid and hypochlorite wherein comprise about 10 to about 80g HNO ₃The concentrated nitric acid of/100g the aqueous solution is preferred.Representational gaseous oxidant comprises molecular oxygen, ozone, nitrogen peroxide and nitric acid vapor.Nitric acid vapor is preferred oxygenant.Use liquid oxidizer, about 60 suit to about 90 ℃ temperature, but use gaseous oxidant, advantageously use about 50 usually to about 500 ℃ or even higher temperature.Carbon can change in about 10 hours wide region at about 5 minutes with the time of oxidizer treatment.Preferably, the reaction times is about 30 minutes to about 6 hours.Experimental result shows that the carbon load in first treatment step, temperature, oxidant concentration etc. are not very crucial for the oxidation that obtains required carbon material, therefore can be easily in the wide region inner control.Since the reason of economic aspect, preferred high as far as possible carbon load.

In second step, the carbon support of oxidation is at preferred about 500 to about 1500 ℃ and more preferably from about 600 under about 1,200 ℃ temperature, in nitrogen, argon gas, helium or other non-oxygenated environment (being basic oxygen-free environment) by pyrolysis (promptly being heated), so that remove oxygen-containing functional group from carbon surface.Be higher than under 500 ℃ the temperature, can using to comprise little ammonia and (or in pyrolytic process, can produce NH ₃Any other chemical entity), the environment of steam or carbonic acid gas, they help pyrolysis.Yet when the temperature with carbon support was cooled to be lower than 500 ℃ temperature, the existence of oxygen-containing gas such as steam or carbonic acid gas can cause the formation again of oxide on surface, therefore, preferably avoided existing.Therefore, pyrolysis is preferably carried out in nonoxidizing atmosphere (for example nitrogen, argon gas or helium).In one embodiment, nonoxidizing atmosphere comprises ammonia, compares with the pyrolysis in other atmosphere, and this often produces active higher catalyzer in shorter time.Pyrolysis for example can use rotary kiln, fluidized-bed reactor or common heating furnace to carry out.

The general pyrolysis of carbon support about 5 minutes to about 60 hours, preferred about 10 minutes to about 6 hours time.The shorter time is preferred, often reduces activity of such catalysts under the high temperature because carbon is exposed to for a long time.Be not subjected to the restriction of any particular theory, think at present, the long-term heating under pyrolysis temperature helps the formation of graphite, and this is the not preferred form of carbon support, because it has less surface-area usually.As mentioned above, by using the ammoniated atmosphere of bag generally can in the shorter time, produce active higher catalyzer.

In a preferred embodiment of the invention, the high temperature deoxidation carries out in a step.This step handles the pyrolysis step that can only be handled by above-mentioned two step high temperature deoxidations and forms.Yet more preferably, single step is handled by RESEARCH OF PYROCARBON carrier as mentioned above and is formed, and allows simultaneously comprise N ₂, NH ₃(or in pyrolytic process, can produce NH ₃Any other chemical entity) and the air-flow of steam through carbon.Though it is not a key feature of the present invention, the flow velocity of this air-flow preferably must be enough to obtain the abundant contact between live gas reactant and the carbon surface soon, and must be enough to slowly prevent that the weightless and material of excessive carbon from wasting.Can use non-reactive gas as thinner, to avoid serious carbon weightlessness.

Being used for noble metal loading generally is known to the method on carbon support surface in the art, and (for example comprise liquid phase process such as reactive deposition technology, precious metal chemical complex reduce deposition method and precious metal chemical complex hydrolysis sedimentation), ion exchange technique, excess solution dipping and early stage wetting dipping; Vapor phase process such as physical deposition and electroless plating; Precipitation; Electrochemical deposition and electroless deposition.Generally consult Cameron, D.S., Cooper, S.J., Dogdson, I.L., Harrison, B., and Jenkins, J.W. " Carbons as Supports forPrecious Metal Catalysts, " Catalysis Today, 7,113-137 (1990).The catalyzer that comprises precious metal on the surface of carbon support can also be purchased, AldrichCatalog No.20 for example, and 593-1, the active C of 5%Pt/ (Aldrich Chemical Co., Inc., Milwaukee, WI); Aldrich Catalog No.20,568-0, the active C of 5%Pt/.

Preferred precious metal comprises carbon support is contacted with the solution of the salt that comprises precious metal, then this salt of hydrolysis by the reactive deposition deposition techniques.The example of relatively cheap suitable platinum salt is chloroplatinic acid (H ₂PtCl ₆).In embodiment 3 illustrated use this salt platinum to be deposited on the carbon support by the hydrolysis sedimentation.

In one embodiment of the invention, use comprise be in its more the solution of the salt of the precious metal of one of low-oxidation-state with noble metal loading to the surface of carbon support.For example, use the salt of Pt (II) to replace using the salt (H for example of Pt (IV) ₂PtCl ₆).In another embodiment, use the platinum (for example colloidal platinum) of element state.Use these metal precursors of more going back ortho states to cause the oxidation of carbon support to reduce, and therefore on carrier surface, form oxygen-containing functional group still less, simultaneously with noble metal loading to this surface.An example of Pt (II) salt is K ₂PtCl ₄Another may effective Pt (II) salt be two nitrous acid, two ammino platinum (II).Embodiment 11 shows, uses this salt sedimentation precious metal to obtain than using H ₂PtCl ₆The catalyzer that has higher anti-leachability as the catalyzer of metal precursor preparation.Be not bound by any particular theory, it is believed that this is owing to the following fact: two nitrous acid, two ammino platinum (II) have produced ammonia on the spot in reduction process, this has further promoted the removal of the lip-deep oxygen-containing functional group of carbon support.Yet, should weigh and consider this benefit and use the relevant possible explosion hazard of two nitrous acid, two ammino platinum (II).

Noble metal loading before the carbon support surface, simultaneously or afterwards, catalyst surface promotor can be deposited on the surface of carbon support.Being used for promotor is deposited to the lip-deep method of carbon support generally is known in the art, and comprises the above-mentioned same procedure that is used for depositing noble metal.In one embodiment, use the salts solution that comprises promotor to come the deposited catalyst surface promoter.The acceptable acid addition salts that can be used to deposit bismuth is Bi (NO ₃) ₃5H ₂O, the acceptable acid addition salts that can be used for deposited iron is FeCl ₃6H ₂O, and the acceptable acid addition salts that can be used for deposit tin is SnCl ₂2H ₂O.Should be realized that, more than one catalyst surface promotor can be deposited on the surface of carbon support.Embodiment 13,14,15 and 17 has demonstrated and with the salts solution that comprises promotor promotor has been deposited on the carbon surface.Embodiment 18 has demonstrated to using and has comprised the salts solution of promotor more than one promotor (being iron and tin) is deposited on the carbon surface.

As mentioned above, comprise that to become the catalyzer of the precious metal of alloy with at least a catalyst surface promotor be particularly preferred.Multiple feasible technology of preparing known in the art is arranged, can be used on carrier surface, forming many metal alloys.Consult for example V.Ponec ﹠amp; G.C Bond, Catalysis by metals and Alloys, " Studies in Surface Scienceand Catalysis ", Vol.95 (B.Delmon. ﹠amp; J.T.Yates, advisory eds., Elsevier Science B.V., Amsterdam, Netherlands).

In a preferred embodiment, use reactive deposition to form and contain the metallics that becomes the precious metal of alloy with catalyst surface promotor.

Reactive deposition can comprise for example reduce deposition, and wherein the carbon support surface contacts with the solution that comprises following component: (a) reductive agent; (b) (i) comprises the compound of precious metal and comprises the compound of promotor, or (ii) comprises the compound of precious metal and promotor.Can use various reductive agents, as sodium borohydride, formaldehyde, formic acid, sodium formiate, hydrazine hydrochloride, azanol and ortho phosphorous acid.The compound that comprises precious metal and/or promotor for example comprises:

1, Halogen compoundsThey comprise for example H ₂PtCl ₆, K ₂PtCl ₄, Pt ₂Br ₆ ^2-, K ₂PdCl ₄, AuCl ₄ ^1-, RuCl ₃, RhCl ₃3H ₂O, K ₂RuCl ₆, FeCl ₃6H ₂O, (SnCl ₃) ^1-, SnCl ₄, ReCl ₆, FeCl ₂And TiCl ₄

2, Oxide compound and oxychlorideThey comprise for example RuO ₄ ^2-And M ₂SnO ₄

3, Nitrate compoundThey comprise for example Fe (NO ₃) ₃

4, Amine complexThey for example comprise [Pt (NH ₃) ₄] Cl ₂, [Pd (NH ₃) ₄] Cl ₂, Pt (NH ₃) ₂Cl ₂, [Pt (NH ₃) ₄] PtCl ₄, Pd (NH ₂CH ₂CH ₂NH ₂) Cl ₂, Pt (NH ₂CH ₂CH ₂NH ₂) ₂Cl ₂[Ru (NH ₃) ₅Cl] Cl ₂

5, Phosphine compositionThey comprise for example Pt (P (CH ₃) ₃) ₂Cl ₂IrClCO (PC ₆H ₅) ₃) ₂PtClH (PR ₃) ₂, wherein each R independently is an alkyl, as methyl, and ethyl, propyl group, phenyl etc.

6, Organometallic complexThey comprise for example Pt ₂(C ₃H ₆) ₂Cl ₄Pd ₂(C ₂H ₄) ₂Cl ₄Pt (CH ₃COO) ₂, Pd (CH ₃COO) ₂K[Sn (HCOO) ₃]; Fe (CO) ₅Fe ₃(CO) ₁₂Fe ₄(CO) ₁₆Sn ₃(CH ₃) ₄And Ti (OR) ₄, wherein each R independently is an alkyl, as methyl, and ethyl, propyl group, phenyl etc.

7, Precious metal/promotor title complexThey comprise for example Pt ₃(SnCl ₃) ₂(C ₈H ₁₂) ₃[Pt (SnCl ₃) ₅] ^3-

In particularly preferred embodiments, use hydrolysis reaction to deposit the precious metal that becomes alloy with catalyst surface promotor.In this case, form the part contain precious metal and promotor, hydrolysis then forms well-mixed metal oxide and metal hydroxides bunch on the carbon support surface.These parts for example can contain the compound of precious metal and contain the compound of promotor with comprising (a) in the surface by making carrier, or the solution that (b) contains the compound of precious metal and promotor contacts and forms.More than enumerated the suitable combination thing that contains precious metal and/or promotor with regard to reduce deposition.The hydrolysis of part for example can realize by heating (for example heating under at least about 60 ℃ temperature) mixture.The embodiment 17 use hydrolysis reaction of further having demonstrated deposits the precious metal (being platinum) that becomes alloy with catalyst surface promotor (being iron).

Except above-mentioned reactive deposition technology, also have many other technology can be used to form alloy.They for example comprise:

1,, metallic compound (it can be simple compounds or mixture, and can be covalency or ionic compound) is incorporated on the surface of carrier and forms alloy by dipping, solution absorbs and/or ion-exchange.

2, be co-deposited to by the metal vapors vacuum that will contain precious metal and promotor and form alloy on the surface.

3, by for example electrolysis plating or electroless plating, one or more metal deposition are formed alloy to the metal that belongs to the periodic table of elements 8,9 or 10 families (being Fe, Co, Ni, Ru, Rh, Pd, Os, Ir and Pt) of pre-deposition.

4, form alloy through the following steps: (a) deposition contains the metal complexes (for example the carbonyl of precious metal and promotor, π-allyl group or cyclopentadienyl complex compound) of 0 valence state metal on the surface of carbon support; (b) for example by heating or also removing part originally to form alloy particle on the surface.

5, contact with the metal hydride of the pre-deposition of 8, the 9 or 10 family's metals that contain the periodic table of elements by solution and form alloy containing metal compound (for example metal chloride or metal alkyls).

6, by on the surface of carbon support simultaneously or successively the codeposition metal complexes (form in advance or form on the spot) that contains precious metal and promotor form alloy.

7, by forming as colloid or aerocolloidal alloy particle in advance, this preformed alloy particle of deposition forms alloy on the surface of carbon support then.Illustrate, the colloidal particle that contains platinum and iron can be easily by boiling H ₂PtCl ₆And SnCl ₂2H ₂Dilute solution and the sodium citrate solution of O form.Can use protective material (for example carbohydrate, polymkeric substance, lipophilic quaternary nitrogen salt) effectively to control the metal alloy particle growth.This technology is therefore through being used to form the alloy particle granularity of narrow distribution.

Should be realized that the above-mentioned technology that is used to form alloy is exemplary, rather than exhaustive.Use instruction of this specification sheets and the general knowledge of this area, those of ordinary skill in the art can determine any specific end use that is suitable for of many alloy technologies of preparing known in the art routinely.

No matter it is any being used to form the technology of alloy, after on the surface of metal deposition at carbon support, preferred usually for example subatmospheric non-oxygenated environment (the preferred N that uses ₂, rare gas element or the two) and come drying support.The reductive occasion is come by heating this surface subsequently in surface at carrier, and the use of drying step is particularly preferred (and be the occasion of in non-oxygenated environment carrying out in heating, be preferred).Preferred drying support reduces to the moisture content with carrier and is lower than about 5wt%.

Should be realized that the reduction on the carbon support surface after precious metal and catalyst surface promotor deposition has generally increased precious metal becomes alloy with catalyst surface promotor degree.This reduction has also increased the number of the particle in the preferred size scope usually.

At carbon support with precious metal (with catalyst surface promotor, if any) after the dipping, preferably with the surface reduction of catalyzer.For example can come the surface of reducing catalyst aptly by heating surface under at least about 400 ℃ temperature.Especially preferably in non-oxygenated environment (for example nitrogen, argon gas or helium), carry out this heating.Also more preferably this temperature is higher than about 500 ℃.More more preferably this temperature is about 550 to about 1,200 ℃, most preferably from about 550 to about 900 ℃.The temperature that is lower than 400 ℃ is not satisfied often for removing oxygen-containing functional group from the surface of carbon support.On the other hand, the temperature that is higher than 1,200 ℃ has often reduced activity of such catalysts.Only have carbon atom and Sauerstoffatom ratio, just preferably use about 400 to about 500 ℃ temperature at least about 20: 1 on noble metal loading carbon support surface before the surface.

In especially preferred embodiment, reduce by comprising the method that allows this surface be exposed to reducing environment on the surface of catalyzer.For example, before heating, catalyst sample can be used the liquid-phase reduction agent, as formaldehyde or formic acid pre-treatment.Even more preferably, (method of heatable catalyst is sometimes referred to as the high temperature vapour phase reduction in the presence of the vapour phase reduction agent) carried out in this heating in the presence of the vapour phase reduction agent.In heat-processed, can use various vapour phase reduction agent, include but not limited to H ₂, ammonia and carbon monoxide.Hydrogen is most preferred, because the molecular dimension of hydrogen is little, can be penetrated into better in the darkest carbon support hole.The residuum of preferred gas is substantially by non-oxidized gas, and as nitrogen, argon gas or helium are formed.This gas can comprise the H of any limited concentration ₂Though, be lower than 1.0% H ₂Concentration is disadvantageous, because required time of reduction carrier surface is often very long.Preferred this gas comprises about 5 to about 50 volume % H ₂, most preferably from about 5 to the H of about 25 volume % ₂

The preferred time on heatable catalyst surface is depended on the mass transfer of reductive agent to catalyst surface.When reductive agent is to comprise about 10 to about 20 volume %H ₂Non-oxidized gas the time, this surface is preferably about 550 to about 900 ℃ of down heating about 15 minutes to about 24 hours, wherein air speed be about 1 arrive about 5,000hr ^-1More preferably air speed is about 10 to about 2,500hr ^-1And even more preferably from about 50 arrive about 750hr ^-1In the most preferred embodiment, thermal treatment carries out about 1 to about 10hr under above preferred temperature and air speed.Be lower than 1hr ^-1Air speed under heating surface be disadvantageous because the oxygen-containing functional group on carbon support surface is not fully destroyed.On the other hand, be higher than 5,000hr ^-1Air speed under the heating be uneconomic.

For obtaining enough precious metal dispersiveness and retention rate, the oxygen-containing functional group that is pre-existing on the carbon support surface generally is unnecessary, perhaps or even undesirable.Be not subjected to the restriction of any particular theory, it is believed that the oxygen-containing functional group of this heating steps by removing the carbon support surface (comprising because those that noble metal loading is formed to this surface) strengthened the platinum-carbon interaction on catalyzer.It is believed that these oxygen-containing functional groups are unstable set sites of precious metal, because they often are subjected to potential stronger interactional influence of π between precious metal and the carbon support.Thereby simple heating can be decomposed and be removed the lip-deep many oxygen-containing functional groups of carbon support.Yet, by at reductive agent (H for example ₂) following this surface of heating of existence, can eliminate more oxygen-containing functional group.

If before noble metal loading is to the carrier surface, be lower than about 20: 1 at lip-deep carbon atom of carbon support and Sauerstoffatom ratio, this surface preferably uses above-mentioned high temperature vapour phase reduction to handle to reduce being higher than under 500 ℃ the temperature, though should the surface is optional can handle with other reducing environment except that the high temperature vapour phase reduction.On the other hand, if having carbon atom and Sauerstoffatom ratio on noble metal loading surface of carbon support before the surface, can use various alternate reducing environments to replace the high temperature vapour phase reduction so at least about 20: 1.

The surface of catalyzer can be at least in part by with amine such as urea, comprise the solution of ammonium ion (for example ammonium formiate or ammonium oxalate) or ammonia and handle and reduce, wherein ammonia or the solution that comprises ammonium ion are most preferred.Except other reduction is handled, preferably use this amine to handle, and most preferably before the high temperature vapour phase reduction, use.In such embodiment, by with comprising the noble metal precursor solution treat surface of ammonium ion, with this noble metal loading to the surface.Perhaps, with noble metal loading after carrier surface, carrier can perhaps contact with the ammoniated gas of bag with the solution washing that comprises ammonium ion.Most preferably after depositing noble metal, catalyst surface washs with weak ammonia.In this case, catalyzer is added in the pure water, stirred several hours, with the surface of wetting catalyzer.Secondly, when continuing to stir this catalyst slurry, the solution that will comprise ammonium ion joins in the catalyst slurry, and its add-on should be enough to produce the pH greater than 7, more preferably from about 8 to about 12 and most preferably from about 9.5 to about 11.0 pH.Because temperature and pressure is not crucial, this step is preferably carried out under room temperature and normal atmosphere.Embodiment 10 further illustrates this reduction and handles.

Can also use sodium borohydride (NaBH ₄) come the surface of reducing catalyst.With the same, except other reduction is handled, preferably use this processing, and most preferably before the high temperature vapour phase reduction, use with the amine processing.Preferably with noble metal loading after carrier surface, in the presence of NaOH,, use NaBH about 8 under about 14 the pH ₄Solution washing carrier about 15 by about 180 minutes.NaBH ₄Consumption preferably be enough to reduce all precious metals.Because temperature and pressure is not crucial, this step is preferably carried out under room temperature and normal atmosphere.Embodiment 12 further illustrates this reduction and handles.

Should be realized that any processing that more than can be used for the reducing catalyst surface also can be used for noble metal loading was made carbon support surface deoxidation before the surface.

In many methods, when wishing that catalyzer contains promotor, by for example above-mentioned promotor deposition technique (this deposition step is undertaken by the manufacturer of catalyzer usually), with the promotor pre-deposition to catalyst surface.Yet this promotor deposition step has often increased the cost of method for preparing catalyst.For fear of these fringe costs, the interests (for example selectivity of Zeng Jiaing, activity and/or catalyst stability) that have been found that promotor can only obtain by promotor (being supplemental promoter) is directly mixed with the catalyzer that contains precious metal (especially with above-mentioned reductive catalyzer) of carbon load.This mixing for example can directly be carried out in the oxidation reaction zone of oxidation N-((phosphonomethyl)) iminodiethanoic acid substrate.Perhaps, for example, this mixing can be independent of oxidizing reaction to be carried out, as carrying out in the catalyst stores jar.

Especially, have been found that some metal and/or metallic compound play supplemental promoter in N-((phosphonomethyl)) the iminodiethanoic acid substrate oxidation with the catalyst that contains precious metal of carbon load.Have been found that these supplemental promoters can effectively improve the ability that precious metal/C catalyst is oxidized to N-((phosphonomethyl)) iminodiethanoic acid substrate N-((phosphonomethyl)) glycine product; wherein they can effectively improve the required conversion to N-((phosphonomethyl)) glycine, the katalysis of by product formaldehyde to the oxidation of formic acid and by product formic acid to the oxidation of carbonic acid gas.

Depend on application, supplemental promoter can be for example tin, cadmium, magnesium, manganese, ruthenium, nickel, copper, aluminium, cobalt, bismuth, lead, titanium, antimony, selenium, iron, rhenium, zinc, cerium, zirconium, tellurium, sodium, potassium, vanadium, gallium, tantalum, niobium, rubidium, caesium, lanthanum and/or germanium.Usually more preferably supplemental promoter is a bismuth, lead, germanium, tellurium, titanium, copper and/or nickel.

In an especially preferred embodiment, supplemental promoter is a bismuth.Have been found that according to the present invention; the oxidation that is used for catalyzing N-((phosphonomethyl)) iminodiethanoic acid substrate when catalyzer is when forming N-((phosphonomethyl)) glycine product, and the existence of bismuth is effective especially for the selectivity of the catalyzer that contains precious metal (especially above-mentioned reductive catalyzer) that improves the carbon load.More particularly, the existence that has been found that bismuth has caused by the increase of the formic acid amount of by-products of catalyzed oxidation.(especially in the occasion of catalyst pack stanniferous as catalyst surface promotor) in some instances finds that also the existence of bismuth has caused by the increase of the formaldehyde amount of by-products of catalyzed oxidation.This destruction that one or both these by products are increased and then make formed N-methyl-N-((phosphonomethyl)) glycine by product reduce (it is believed that this formation owing to per molecule N-methyl-N-((phosphonomethyl)) glycine by product needs (a) two formaldehyde molecules, or (b) fact of a formic acid molecule and a formaldehyde molecule).In addition; have been found that; (especially using the occasion of more than one supplemental promoters) in some cases, the existence of bismuth can also reduce in the oxidising process of N-((phosphonomethyl)) iminodiethanoic acid substrate the noble metal amount that leaches from the carbon support of catalyzer.

In another preferred embodiment of the present invention, use tellurium promotor as a supplement.As introduce bismuth as a supplement in the above embodiment of promotor; the oxidation that is used for catalyzing N-((phosphonomethyl)) iminodiethanoic acid substrate when catalyzer finds that the existence of tellurium also can effectively improve the selectivity of the catalyzer that contains precious metal (especially above-mentioned reductive catalyzer) of carbon load when forming N-((phosphonomethyl)) glycine product.More particularly, find that also tellurium can be increased in the activity of such catalysts in the oxidation of N-((phosphonomethyl)) iminodiethanoic acid substrate.In addition, also find, be present in (especially when also having bismuth) in the reaction medium, can reduce in the oxidising process of N-((phosphonomethyl)) iminodiethanoic acid substrate the amount of the precious metal that leaches from the carbon support of catalyzer by making tellurium.

In the most preferred embodiment, use the two promotor as a supplement of bismuth and tellurium.

The mixing of supplemental promoter and catalyzer is preferably carried out in liquid medium.As mentioned above, this mixing for example can directly be carried out in the oxidized liquid reaction medium of N-((phosphonomethyl)) iminodiethanoic acid substrate.Therefore yet in the occasion that oxidizing reaction is carried out under pressure, reaction vessel is sealed usually, and more preferably mixed catalyst and supplemental promoter outside reaction vessel usually are as mixing in catalyst stores jar or recirculation tank.

Usually, supplemental promoter is incorporated in the mixing liquid with the form of the inorganic or organic compound that contains supplemental promoter.The compound that contains promotor can dissolve in liquid or be insoluble, but the most common solvable to small part.The functional group that is connected in the supplemental promoter atom generally is not crucial (though its preferably agriculture acceptable functional group).Usually, for example, the compound that is fit to comprises oxide compound, oxyhydroxide, the salt of inorganic hydracid, the salt of inorganic oxacid, aliphatic series or aromatics organic acid salt and phenates.

The bismuth-containing compound that is fit to for example comprises inorganic or organic compound, and wherein bismuth atom is in greater than 0 (for example 2,3,4 or 5), most preferably 3 oxidation level.The example of the bismuth compound that these are fit to comprises:

1, bismuth oxide compound.They for example comprise, BiO, Bi ₂O ₃, Bi ₂O ₄, Bi ₂O ₅Deng.

2, bismuth oxyhydroxide.They comprise for example Bi (OH) ₃Deng.

3, the bismuth salt of inorganic hydracid.They for example comprise bismuth muriate (BiCl for example ₃), bismuth bromide (BiBr for example ₃), bismuth iodide (BiI for example ₃), bismuth telluride (Bi for example ₂Te ₃) etc.Bismuth halogenide generally is not preferred, because their etching process equipment often.

4, the bismuth salt of inorganic oxacid.They for example comprise bismuth sulphite (Bi for example ₂(SO ₃) ₃Bi ₂O ₃5H ₂O), bismuth vitriol (Bi for example ₂(SO ₄) ₃), oxygen bismuth vitriol ((BiO) HSO for example ₄), oxygen bismuth nitrite ((BiO) NO for example ₂0.5H ₂O), bismuth nitrate (Bi (NO for example ₃) ₃5H ₂O also is called the Bismuth trinitrate pentahydrate), oxygen bismuth nitrate ((BiO) NO for example ₃, also be called Vikaline, oxidation Bismuth trinitrate and nitric acid oxidation bismuth), two nitrate of bismuth and magnesium (2Bi (NO for example ₃) ₃3Mg (NO ₃) ₂24H ₂O), bismuth phosphite (Bi for example ₂(PO ₃H) ₃3H ₂O), bismuth phosphoric acid salt (BiPO for example ₄), bismuth pyrophosphate salt (Bi for example ₄(P ₂O ₇) ₃), oxygen bismuth carbonate (for example (BiO) ₂CO ₃, also be referred to as Bismuth Subcarbonate), bismuth perchlorate (Bi (ClO for example ₄) ₃5H ₂O), bismuth stibnate (BiSbO for example ₄), bismuth arsenate (Bi (AsO for example ₄) ₃), bismuth selenate (Bi for example ₂(SeO ₂) ₃), bismuth titanate (Bi for example ₂O ₃2TiO ₂) etc.These salt also comprise from the bismuth salt of transition metal deutero-oxygen acid, for example comprise bismuth vanadate (BiVO for example ₄), bismuth niobate (BiNbO for example ₄), bismuth tantalate (BiTaO ₄), bismuth chromic salt (Bi ₂(CrO ₄)), oxygen bismuth dichromate (for example (BiO) ₂Cr ₂O ₇), oxygen bismuth chromic salt (H (BiO) CrO for example ₄), two chromic salt of oxygen bismuth and potassium (K (BiO) CrO for example ₄), bismuth molybdate (Bi for example ₂(MoO ₄) ₃), two molybdates of bismuth and sodium (NaBi (MoO for example ₄) ₂), bismuth tungstate (Bi for example ₂(WO ₄) ₃), bismuth permanganate (Bi for example ₂O ₂(OH) MnO ₄), bismuth zirconate (2Bi for example ₂O ₃3ZrO ₂) etc.

5, aliphatic series or aromatics organic acid bismuth salt.They for example comprise bismuth acetate (Bi (C for example ₂H ₃O ₂) ₃), oxygen bismuth propionic salt ((BiO) C for example ₃H ₅O ₂), bismuth benzoate (C for example ₆H ₅CO ₂Bi (OH) ₂), oxygen bismuth salicylate (C for example ₆H ₄CO ₂(BiO) (OH)), bismuth oxalate ((C for example ₂O ₄) ₃Bi ₂), bismuth tartrate (Bi for example ₂(C ₄H ₄O ₆) ₃6H ₂O), bismuth magma hydrochlorate ((C for example ₆H ₉O ₅) OBi7H ₂O), bismuth Citrate trianion (C for example ₆H ₅O ₇Bi) etc.

6, bismuth phenol thing.They for example comprise bismuth gallate (C for example ₇H ₇O ₇Bi), bismuth pyrogallate (C for example ₆H ₃(OH) ₂(OBi) (OH)) etc.

7, various other organic and inorganic bismuth compounds.They comprise for example bismuth phosphide (for example BiP), arsenic bismuth (Bi ₃As ₄), sodium bismuthate (NaBiO for example ₃), bismuth-thiocyanic acid (for example, H ₂(Bi (BNS) ₅) H ₃(Bi (CNS) ₆)), the sodium salt of bismuth-thiocyanic acid, the sylvite of bismuth-thiocyanic acid, trimethylammonium

(Bi (CH for example ₃) ₃), triphenyl

(Bi (C for example ₆H ₅) ₃), pearl white (for example BiOCl), bismuthyl iodide (for example BiOI) etc.

In preferred embodiments, bismuth compound is the bismuth oxide compound, the bismuth salt of bismuth oxyhydroxide or inorganic oxacid.More preferably bismuth compound is bismuth nitrate (Bi (NO for example ₃) ₃5H ₂O), oxygen bismuth carbonate (for example (BiO) ₂CO ₃) or bismuth oxide compound (Bi for example ₂O ₃), wherein bismuth oxide (III) (is Bi ₂O ₃) be most preferred, because it does not conform to the counter ion that can pollute final reacting product.

The tellurium compound that contains that is fit to for example comprises inorganic or organic compound, and wherein tellurium atom is in greater than 0 (for example, 2,3,4,5 or 6), most preferably 4 oxidation level.The example of the tellurium compound that these are fit to comprises:

1, tellurium oxide compound.They comprise for example TeO ₂, Te ₂O ₃, Te ₂O ₅, TeO ₃Deng.

2, the tellurium salt of inorganic hydracid.They for example comprise tellurium tetrachloride (TeCl for example ₄), tellurium tetrabromide (TeBr for example ₄), tellurium tetraiodide (TeI for example ₄) etc.

3, the tellurium salt of inorganic oxacid, they for example comprise tellurous acid (H for example ₂TeO ₃), telluric acid (H for example ₂TeO ₄Or Te (OH) ₆), tellurium nitrate (Te for example ₂O ₄HNO ₃) etc.

4, various other organic and inorganic tellurium compounds, they comprise for example dichloride dimethyl tellurium, oxidation tellurium lead, Virahol tellurium, ammonium tellurate, tellurium thiocarbamide etc.

In preferred embodiments, tellurium compound is the tellurium salt of tellurium oxide compound or inorganic hydracid.More preferably tellurium compound is tellurium dioxide (TeO for example ₂), tellurium tetrachloride (TeCl for example ₄) or telluric acid (Te (OH) for example ₆), wherein tellurium tetrachloride is most preferred.

The preferred amounts that is incorporated into the supplemental promoter in the reaction zone depends on the quality of the catalyzer that contains precious metal of for example carbon load (being the total mass of any other component of carbon support, precious metal and catalyzer); The concentration of the quality of total reaction raw mix and N-((phosphonomethyl)) iminodiethanoic acid substrate.

Usually, be added to the ratio of quality of the catalyzer that contains precious metal of the quality of the supplemental promoter in the reactor and carbon load preferably at least about 1: 15000; More preferably at least about 1: 5000; Also more preferably at least about 1: 2500; Most preferably at least about 1: 1000.Though when the ratio of the quality of the catalyzer that contains precious metal of the quality of supplemental promoter and carbon load up to about 1: 750; about 1: 500; about 1: 300; and even be higher than about 1: 50 or can implement the present invention at 1: 40 o'clock; and without detriment to oxidizing reaction; but have been found that above-mentioned preferred low ratio uses for great majority, especially the oxidation for N-((phosphonomethyl)) iminodiethanoic acid substrate is effective.

The ratio that is added to the quality of the supplemental promoter in the reactor and total reactant quality is preferably at least about 1: 1, and 000,000; More preferably at least about 1: 100,000; Also more preferably at least about 1,40,000; Most preferably from about 1: 40,000 to about 1: 15,000.Be higher than 1: 8000 ratio though can use usually, and without detriment to oxidizing reaction, usually preferred this ratio was less than 1: 8000 (especially being the occasion of supplemental promoter at bismuth).

The ratio of quality that is added to the quality of the supplemental promoter in the reactor and N-((phosphonomethyl)) iminodiethanoic acid substrate is preferably at least about 1: 100, and 000; More preferably 1: 10,000; Also more preferably at least about 1: 4000; Most preferably from about 1: 4000 to about 1: 2000.Be higher than 1: 1000 ratio though can use usually, and without detriment to oxidizing reaction, usually preferred this ratio was less than 1: 1000 (especially being the occasion of supplemental promoter at bismuth).

When particle precious metal/C catalyst is used for oxidation N-((phosphonomethyl)) iminodiethanoic acid substrate, can the two joins in the water-containing reacting medium that contains N-((phosphonomethyl)) iminodiethanoic acid substrate and oxygen with catalyzer and supplemental promoter.Supplemental promoter can be with at least about 1: 15, and 000, preferably at least about 1: 5000, more preferably at least about 1: 2500 with most preferably at least about 1: 1000 supplemental promoter: the reinforced mass ratio of catalyzer adds.Carrying out along with the oxidation of N-((phosphonomethyl)) iminodiethanoic acid substrate produced formaldehyde and formic acid by product.This catalyzer is the effectively oxidation of catalyzing N-((phosphonomethyl)) iminodiethanoic acid substrate not only, and formaldehyde further is oxidized to formic acid and is carbonic acid gas with formic acid oxidation.The existence of supplemental promoter can effectively improve the catalyzed oxidation of these by products, especially formic acid is converted into CO ₂

The occasion of carrying out in the stirred-tank reactor of catalyzer slurryization in reaction medium therein in oxidizing reaction; catalyzer preferably separates from reaction mixture by filtering; and be recycled in the reactor, be used for the oxidation of N-((phosphonomethyl)) iminodiethanoic acid substrate and above-mentioned by product once more.This stirred-tank reactor system can be with intermittently or the continuous mode operation.Perhaps, can use fixing or fluid catalyst beds.In continuation method; in reaction zone continuously or intermittent entry comprise the water-containing reacting medium of N-((phosphonomethyl)) iminodiethanoic acid substrate; and discharge the reaction mixture that comprises N-((phosphonomethyl)) glycine product continuously or intermittently; supplemental promoter is incorporated into this reaction zone continuously or intermittently, and N-((phosphonomethyl)) iminodiethanoic acid substrate, formaldehyde and formic acid is all oxidations of quilt in continuous reaction zone.

Find, with the discontinuous continuously batch reactions round-robin in first of series that joins of supplemental promoter, the catalyst activity of whole serial reaction round-robin oxidation of formaldehyde and formic acid can be effectively improved, the supplemental promoter of any external source need not be further added.Find that in addition supplemental promoter is present in the catalyst recycle, obviously is deposited on the catalyzer by being adsorbed onto on precious metal and/or the carbon support.After a plurality of circulations, on catalyzer, only can find to join the part supplemental promoter of this series in first.Yet, when being incorporated into first in above-mentioned amount supplemental promoter, the part that is retained on the catalyzer obviously enough promotes all serial batch the formaldehyde and the oxidation of formic acid, and wherein the catalyzer by preceding a collection of recirculation is to be used for series unique source of batch reactions round-robin supplemental promoter continuously substantially.Find that with about 1: 2500 supplemental promoter: the quality of catalyzer is added supplemental promoter than single, can effectively promote more than 20 batches or 20 batches, and is general more than 50 batches or 50 batches, the by product oxidation of more general 100 batches of above reaction cycle series.After this, can choose wantonly another part supplemental promoter feed is joined in the reaction medium, make this follow-up batch to constitute first of another serial batch oxidation reaction cycle, wherein become unique source of the continuous batch reactions round-robin promotor that is used for this another serial batch reactions basically from last batch catalyst recycle of this another series.

Similarly, under the situation in the reaction medium that supplemental promoter is joined continuous stirred tank reactor, single supplemental promoter that adds in batches can effectively improve in a plurality of reactors turnovers of whole successive reaction round-robin catalyzer for the effectiveness of formaldehyde and formic acid oxidation.Till beginning, second reaction cycle need not add supplemental promoter in addition.For this reason, reaction cycle is once added in the supplemental promoter to formaldehyde and the formic acid oxidation cycle in the reaction zone interpolation supplemental promoter formed next time to reaction zone by any, and can be by 50 or more, general 100 or the turnover of more a plurality of reactor working volumes form.

Such as described, at serial batch reactions round-robin after a plurality of cycles, or after the successive reaction round-robin repeatedly has enough to meet the need, only some is added to the supplemental promoter of round-robin in first and is retained on the catalyzer.Yet; comprising when this substrate and oxygenant in the reaction zone of liquid reaction medium and contacting; and wherein supplemental promoter and catalyzer are at least about 1: 200 at the mass ratio of this reaction zone, 000, preferably at least about 1: 70; 000; more preferably at least about 1: 30,000, most preferably at least about 1: 15; 000 o'clock, this supplemental promoter still can effectively improve the oxidation of N-((phosphonomethyl)) iminodiethanoic acid substrate, formaldehyde and formic acid.Because unique source of the supplemental promoter of reactor is catalyst recycle substantially, so further preferred addition promotor is with identical mass ratio, promptly at least about 1: 200,000, preferably at least about 1: 70,000, more preferably at least about 1: 30,000, most preferably at least about 1: 15,000 is present on the catalyst recycle or is present in the catalyst recycle.

The supplemental promoter content of reaction zone can also recently be represented with the quality of the noble metal component of supplemental promoter and catalyzer.For example, for 5% precious metal/C catalyst, the ratio of supplemental promoter and precious metal should be at least about 1: 10, and 000, more preferably 1: 3500, also more preferably 1: 1800, most preferably 1: 700.These are preferred general effective for the whole bullion content scope of precious metal/C catalyst, and described catalyzer generally contains 0.5 to about 20% the precious metal of having an appointment.Yet high relatively in bullion content, for example near 20% occasion, supplemental promoter is at low relatively and mass ratio noble metal component, even is low to moderate 1: 40, also can be effective under 000 the situation.

Begin at serial batch reactions round-robin at supplemental promoter, or in successive reaction round-robin initial stage of above definition, occasion with discontinuous feed-type interpolation, it is with at least about 1: 750, preferably at least about 1: 250, more preferably, most preferably add at least about 1: 50 the supplemental promoter and the noble metal component mass ratio of catalyzer at least about 1: 125.As mentioned above, the preferred ratio of supplemental promoter and precious metal can change with the variation of the bullion content of catalyzer.Therefore, for example, when the bullion content of catalyzer during near 20wt%, supplemental promoter is with 1: 3000 or higher, and more preferably at least about 1: 1000, it just can be effective that the supplemental promoter of 1: 500 or 1: 200 and precious metal mass ratio add.

Regular discontinuous interpolation supplemental promoter may be favourable, because in the maximized while of the effectiveness of the catalyzer that is used in oxidation of formaldehyde and formic acid, the supplemental promoter of crossing ratio may delay the oxidation of N-((phosphonomethyl)) iminodiethanoic acid substrate.By only regularly adding supplemental promoter; be deposited on the catalyzer and can decay to residual quasi-steady state scope quite apace with the ratio that is present in the supplemental promoter of reaction zone; wherein supplemental promoter still can effectively improve the catalytic activity of oxidation of formaldehyde or formic acid, and can obviously not hinder the speed or the degree of the oxidation of N-((phosphonomethyl)) iminodiethanoic acid substrate.Therefore; in the oxidation reaction zone that is used for oxidation N-((phosphonomethyl)) iminodiethanoic acid substrate and the best supplemental promoter content that is being used on the catalyst recycle of this reaction can be lower than 1: 15,000, for example; at 1: 65, in 000 to 1: 25000 the scope.

Supplemental promoter is deposited on the formation of the new catalyst mixture that has caused comprising catalyzer and promotor on precious metal/C catalyst surface in the reaction medium.The catalyst component of catalyst complex may further include surface promoter, and this surface promoter comprises the metal that is different from supplemental promoter, or contains identical metal in some cases.Supplemental promoter it is believed that by adsorbing from reaction medium and deposits, and keeps getting off from the catalyst surface desorb, enters catalyst media.Though effective fraction opposing desorb of residual supplemental promoter, so that (or in the long-term operation at continuous reaction system) keeps being attached to catalyzer in above-described a plurality of reaction times, but supplemental promoter is general than the easier desorb of the surface promoter of using in method for preparing catalyst.

As mentioned above, by precious metal and optional surface promoter being deposited on the carbon support to form catalyst precursor, the reducing catalyst precursor at first prepares catalyzer to produce catalysts then.(generally by being adsorbed onto on carbon or the precious metal surface) forms the new catalyst mixture on the oxide catalyst by subsequently supplemental promoter being deposited on.Advantageously, supplemental promoter mixes in reaction medium with oxide catalyst, makes promotor deposit on the catalyst surface from reaction medium.Yet, be noted that in replacement scheme, supplemental promoter can with oxide catalyst premix in another liquid medium, form catalyst complex, after this, this catalyst complex can be incorporated in the reaction medium, is used to carry out oxidizing reaction.

Should be realized that, depend on required effect, can use more than one supplemental promoter.In addition, each supplemental promoter can be from more than one source.In addition, the catalyzer that contains precious metal of carbon load can contain a certain amount of metal identical with supplemental promoter in its surface, for example produce in the mode of this metal that has catalyst surface promotor effect in its surface at (a) catalyzer, or (b) catalyzer be from exist this metal (for example promotor) as a supplement before the occasion of the used catalyst that reclaims the reaction mixture.

In particularly preferred embodiments, as mentioned above, the catalyst themselves that contains precious metal of carbon load also comprises one or more catalyst surface promotor in its surface.Be used for the oxidation of N-((phosphonomethyl)) iminodiethanoic acid substrate and the occasion that supplemental promoter is bismuth at catalyzer; especially preferred this catalyzer contains tin and/or iron (except the oxidation that increases the formic acid by product, the existence of tin is effective especially often for the oxidation that increases the formaldehyde by product).

In many cases, after the catalyzer that contains precious metal of supplemental promoter (especially bismuth) and carbon load merges, deposit to the carbon support and/or the precious metal surface of catalyzer to the small part supplemental promoter, and therefore kept by this catalyzer.Because this catalyzer keeps promotor, so this catalyzer generally can recirculation, for use in the oxidation of the oxidation substrates of the follow-up amount of catalysis (for example, this catalyzer can be used for the oxidation substrates of other batch of oxidation, maybe can be used for continuous oxidation process), also kept the benefit of supplemental promoter simultaneously.When the effect of supplemental promoter reduced with the prolongation of duration of service, the fresh supplemented promotor of additional amount can be regularly and this catalyst mix, so that recovery effects and/or obtain other required result (for example, the formic acid level of reduction).For example, the occasion of in many batches of rhythmic reactions, using at catalyzer, this for example regularly add can be after catalyzer be used at least about 20 batches of oxidizing reactions (more preferably after catalyzer has been used at least about 30 batches of oxidizing reactions and most preferably after catalyzer has been used at least about the oxidizing reaction more than 100 or 100 batches) carry out.In the occasion of the fresh supplemental promoter of catalyzer regular supply, the mixing that is used for supply can be carried out at oxidation reaction zone or outside oxidation reaction zone.

In particularly preferred embodiments, supplemental promoter and used catalyst (promptly used catalyst in the previous oxidizing reaction of one or many) mix.Usually, activity of such catalysts and/or required selectivity reduce along with use.Therefore; for example; use along with catalyzer; the activity of such catalysts that contains precious metal of carbon load that is used for the by product (for example formaldehyde and/or formic acid) of oxidation N-((phosphonomethyl)) iminodiethanoic acid substrate oxidation trends towards reducing usually; thereby make still less formaldehyde and/or formic acid destroyed, and therefore form a large amount of N-methyl-N-((phosphonomethyl)) glycine.At last; in fact; therefore this activity is reduced to formaldehyde and/or the not oxidized level of formic acid that unacceptable amount is wherein arranged, and usually causes that N-methyl-N-((phosphonomethyl)) glycine compound of unacceptable amount generates (selectivity of catalyst that promptly is used for being prepared by N-((phosphonomethyl)) iminodiethanoic acid substrate N-((phosphonomethyl)) glycine compound is reduced to unacceptable level).Traditionally, when the catalyst activity of oxidized byproduct reached at this, this catalyzer was considered to and can not uses, and therefore came recirculation (i.e. regeneration) by consuming time and common expensive method, perhaps abandoned together.Yet; according to the present invention, have been found that this catalyzer can be by with this catalyzer and supplemental promoter; especially bismuth or tellurium mix and regenerate (that is the selectivity of catalyst that, is used to prepare N-((phosphonomethyl)) glycine product can be increased to acceptable level).In other words, supplemental promoter can be used in the work-ing life that changes catalyst performance and prolong catalyzer.

Find that supplemental promoter (especially bismuth) can cause the slight reduction of N-((phosphonomethyl)) iminodiethanoic acid substrate oxidation rate.In this case, oxidation rate generally can be by increasing supply to the oxygen amount of reaction mixture, keeps high relatively oxygen flow speed in reaction process long-time, and/or pressure boost and increase at least in part.Yet,, preferably be not increased to and cause the catalyst surface snperoxiaized unfriendly degree that becomes in the occasion that oxygen flow speed increases.Therefore, the oxygen delivery rate of increase preferably remains on the level that oxygen is utilized that feeds that makes at least about 40% (more preferably at least about 60%, also more preferably at least about 80% with most preferably at least about 90%).

Preferred oxidation reactor system

Oxidation reaction zone can comprise various reactor configuration, comprises having in liquid phase and choosing those of in gas phase back mixing characteristic wantonly, and has the piston flow characteristic those.Suitable reactor configuration with back mixing characteristic comprises for example stirred-tank reactor, ejector nozzle loop reactor (also being called loop reactor in civilian Qiu) and fluidized-bed reactor.The reactor configuration that is fit to piston flow characteristic comprises those with filling or stationary catalyst bed (for example trickle-bed reactor and filling bubble-column reactor) and bubble-cap slurry tower reactor.Fluidized-bed reactor can also be operated in the mode of performance piston flow characteristic.

In a broad sense, oxidizing reaction can be according to the present invention in the temperature of wide region with under the pressure from the sub-atmospheric pressure to the super-atmospheric pressure, carry out.Use gentle condition (for example room temperature and normal atmosphere) to have commercial benefit, because can in reactor assembly, use cheap equipment.Yet; operating the mass transfer that has often improved between the liquid and gas (for example oxygen source) under higher temperature and the super-atmospheric pressure; increased N-((phosphonomethyl)) iminodiethanoic acid oxidizing reaction speed and increased N-((phosphonomethyl)) glycine product solvability, separated with the precipitation and the required water yield of recovery product thereby reduced.Therefore, use oxidizing condition more initiatively in fact can reduce the total cost of factory and the running cost of minimizing production unit N-((phosphonomethyl)) glycine product.Preferably, N-((phosphonomethyl)) iminodiethanoic acid oxidizing reaction is at about 20 ℃ to about 180 ℃, more preferably from about 50 ℃ to about 140 ℃, also more preferably from about 80 ℃ to about 110 ℃ and more more preferably from about 95 ℃ under about 105 ℃ temperature, carry out.Be higher than under about 180 ℃ temperature, raw material trends towards slow decomposition.And, when oxidizing reaction temperature is on about 90 ℃, required N-((phosphonomethyl)) glycine product selectivity is trended towards worsening.For example, temperature of reaction 10 ℃ of every increases on 90 ℃, the generation of undesirable by product N-methyl-N-((phosphonomethyl)) glycine (NMG) often increase about 2-4 doubly.Lower temperature (promptly being lower than about 95 ℃ temperature) usually is disadvantageous, because the solubleness of some N-((phosphonomethyl)) iminodiethanoic acid substrate and N-((phosphonomethyl)) glycine product descends under such temperature.The total pressure that keeps in oxidation reaction zone generally depends on employed temperature and reactor configuration.Total pressure at each oxidation reaction zone preferably equals normal atmosphere at least and is enough to prevent that the liquid reaction medium in oxidation zone from seething with excitement.At the following preferred oxidation reaction condition of discussing the particular reactor system in more detail.

In a preferred embodiment, the oxidation of N-((phosphonomethyl)) iminodiethanoic acid substrate is carried out in one or more continuous oxidation reactions district, and wherein substrate is formed N-((phosphonomethyl)) glycine product by oxidation continuously.Continuously oxidation provides and has obtained the higher process yields and the chance of lower production cost more.And, because the oxidation of N-((phosphonomethyl)) iminodiethanoic acid substrate is heat release, after continuous oxidation reaction device system begins, generally do not need to keep required oxidizing reaction temperature to the water-containing material stream heat supply of introducing oxidation zone.

Can suitably use various reactor configuration the continuous oxidation reaction district is provided.According to an embodiment preferred; the continuous oxidation of N-((phosphonomethyl)) iminodiethanoic acid substrate is in the oxidation reaction zone of one or more basic back mixing (i.e. back mixing in liquid phase at least); utilize the heterogeneous beaded catalyst of suspension that contacts with liquid reaction medium, the precious metal of preferred above-mentioned drastic reduction/carbon granule catalyzer carries out.It should be understood, however, that enforcement of the present invention is not limited to use the catalyzer of this drastic reduction, also is not limited to the catalyzer of particle form.And, it should be understood that the catalyzer that uses can comprise the mixture of different catalysts in reactor assembly of the present invention, and/or an oxidation reaction zone in reactor assembly can be different to next oxidation reaction zone catalyzer.

Fig. 2 has shown the example of the reactor assembly that can be used for carrying out continuous oxidizing process of the present invention.System shown in Fig. 2 comprises continuous stirred tank reactor 3, and the mechanical stirring of the liquid reaction medium that wherein contains generally is provided with rotary blade.Stirred-tank reactor is the interior liquid phase of back mixing reaction zone suitably, and design is simple relatively, and operation can be adjusted to required working ability.Can use various impeller designs, comprise system with a plurality of blades that on common axle, rotate.Such as known to those skilled in the art, reactor vessel can comprise Internal baffle and/or drainage tube, to change mixed characteristic and the eddy flow that prevents liquid reaction medium.

Though the reactor assembly shown in Fig. 2 comprises single continuous stirred tank reactor, in many cases, as following in greater detail, the reactor assembly that comprises the placed in-line two or more back mixing oxidation reaction zones of classification is preferred.The back mixing oxidation reaction zone can be suitably reactor configuration (for example ejector nozzle loop reactor and fluidized-bed reactor) by discontinuous stirred-tank reactor provide.And different reactor configuration can make up in comprising the reactor assembly of a plurality of oxidation reaction zones.For example, the one or more reactors with back mixing characteristic can make up with reactor configuration with piston flow characteristic such as fixed catalyst bed reactors.

The water-containing material stream 1 that will comprise N-((phosphonomethyl)) iminodiethanoic acid substrate is incorporated in the liquid reaction medium within the stirred-tank reactor 3 continuously or intermittently with oxygen source.Heterogeneous beaded catalyst also is present in the oxidation reaction zone, contacts with liquid reaction medium, is used for the oxidation of N-((phosphonomethyl)) the iminodiethanoic acid substrate of catalysis water-containing material.Carry out the CO that comprises that emitted with oxidizing reaction ₂Steam head space on the reaction mixture from stirred-tank reactor 3 discharge.The reaction mixture that contains N-((phosphonomethyl)) glycine product and heterogeneous beaded catalyst flows out thing 7 discharges continuously or intermittently from stirred-tank reactor 3, and transfer to catalyst filter 9, there, basically all catalyzer separate from reaction mixture, form: (1) comprises the catalyst recycle materials flow 11 of N-((phosphonomethyl)) the glycine product of all catalyzer and residual quantity basically; (2) contain the filtrate 13 of most of N-((phosphonomethyl)) glycine product.Catalyst recycle materials flow 11 is incorporated in the stirred-tank reactor 3 again, and filtrate 13 is sent to and concentrated and purifying N-((phosphonomethyl)) glycine product simultaneously.

The interior temperature of oxidation reaction zone preferably keeps fully high according to N-((phosphonomethyl)) glycine production concentration, makes that basic all N-((phosphonomethyl)) glycine product in the reaction mixture outflow thing 7 of discharging from stirred-tank reactor 3 is dissolved.Therefore; for example; when N-((phosphonomethyl)) glycine product is that concentration is when being about N-of 7 to about 15wt% ((phosphonomethyl)) glycine free acid; the temperature that the reaction mixture of discharging from stirred-tank reactor 3 flows out thing is preferably maintained in the range of from about 80 ℃ to about 180 ℃; more preferably from about 90 ℃ to about 150 ℃; also more preferably from about 90 ℃ to about 135 ℃, more more preferably from about 95 ℃ to about 125 ℃, also further preferred about 95 ℃ to about 105 ℃.It should be understood, however, that N-((phosphonomethyl)) glycine product precipitation in reaction mixture outflow thing 7 is tolerable, and still can obtain gratifying result.Sedimentary N-((phosphonomethyl)) glycine product can separate (for example filtering altogether) with beaded catalyst with its excess that reaction mixture flows out thing 7.

In when beginning, reaction mixture and/or water-containing material stream 1 in can heated oxide reaction zone 3 be to obtain required oxidizing reaction temperature.Heat supply if desired, all or at least a portion heat energy can provide various feedstreams being pumped into the residuum of stirred-tank reactor 3 neutralizations by reactor assembly, making not to need independent conventional feed preheater.Because this oxidizing reaction is heat release, in case oxidizing reaction begins to emit a large amount of heat, need from reaction mixture, remove heat energy usually, so that keep temperature required in the oxidation zone.As shown in FIG. 2, excessive reaction heat can be by allowing reaction mixture take out from stirred-tank reactor 3 interior reaction mixtures through the external heat exchange cycles loop 15 that comprises heat exchanger 16, and wherein heat is from the reaction mixture indirect branch to heat-eliminating medium (for example water coolant).Temperature of reaction is for example controlled from the chilled(cooling) water supply (CWS) of the signal control heat exchanger 16 of temperature regulator by basis.Reaction heat can also pass through other mode easily, as coming to remove from oxidation reaction zone with the spiral coil cooling tube or the reactor vessel chuck (by this spiral coil cooling tube or chuck circulating cooling medium) that are immersed in the reaction mixture.

Total pressure in the stirred-tank reactor 3 generally is about 0 to about 500psig, and the preferred fully height that keeps seethes with excitement therein so that prevent liquid reaction medium.Usually, the total pressure in the stirred-tank reactor 3 is about 30 to about 500psig.When oxidation reaction zone when in about 105 ℃ particularly preferred temperature range, operating for about 95 ℃, the total pressure preferably about 30 to about 130psig and more preferably from about 90 that keeps in stirred-tank reactor 3 arrives about 110psig.

In water-containing material stream 1, can adopt N-((phosphonomethyl)) the iminodiethanoic acid concentration of substrate of wide region.Water-containing material stream 1 comprises the catalyst recycle materials flow 11 that is incorporated in the stirred-tank reactor 3 and from any other recycle streams of this method other parts.At slurry-phase reactor, in the stirred-tank reactor as shown in Figure 2, preferably, make that all required N-((phosphonomethyl)) glycine products are dissolved basically according to the concentration of substrate in the temperature selection water-containing material stream 1 of reaction mixture outflow thing 7.As mentioned above, can also use formation is contained concentration of substrate above the reaction mixture of N-((phosphonomethyl)) the glycine product of the concentration of the solubility limit of product, but generally be not preferred.With respect to the commercial run of many common implementations, the present invention allows to use higher temperature and N-((phosphonomethyl)) iminodiethanoic acid concentration of substrate to prepare N-((phosphonomethyl)) glycine, by product is formed minimize.Using only is in the commercial run of common implementation of catalyzer of carbon, usually preferably operates under low concentration of substrate and temperature economically, so that the formation of N-methyl-N-((phosphonomethyl)) glycine by product is minimized.With those methods and catalyzer, generally use about 60 ℃ to 90 ℃ temperature to obtain the effective yield of cost and the generation of waste material is minimized.Under this temperature, N-((phosphonomethyl)) glycine maxima solubility generally is lower than 6.5% ([the quality ÷ total reactant quality of N-((phosphonomethyl)) iminodiethanoic acid substrate] * 100%).But with preferred oxide catalyst of the present invention and reaction process, it is minimum that the precious metal losses of catalyzer and catalyst deactivation are reduced to, and formaldehyde is more effectively oxidized, thereby allow temperature of reaction up to 180 ℃ (or higher).More the use of high oxidation temperature of reaction and reactor feedstocks concentration increases reactor output, reduced every pound of N-((phosphonomethyl)) glycine product of being produced the water yield that must remove and the cost that has reduced production N-((phosphonomethyl)) glycine.Compare with the commercial run of many common implementations, therefore the present invention provides economic interests.

The preferred upper limit of N-((phosphonomethyl)) iminodiethanoic acid concentration of substrate depends on employed specific substrates.For example, under the situation of N-((phosphonomethyl)) Iminodiacetate (for example sylvite), can use concentration up to about 70wt%.Yet usually, the N-of about 50wt% ((phosphonomethyl)) iminodiethanoic acid concentration of substrate is preferred (especially arriving under about 180 ℃ temperature of reaction about 20) at the most.More preferably use the N-of about 25wt% ((phosphonomethyl)) iminodiethanoic acid concentration of substrate (especially arriving under about 150 ℃ temperature of reaction) at the most about 60.More more preferably use about 3 to about 20wt% N-((phosphonomethyl)) iminodiethanoic acid concentration of substrate (especially arriving under about 130 ℃ temperature of reaction) about 100.Arrive under about 105 ℃ preferable reaction temperature about 95, N-((phosphonomethyl)) iminodiethanoic acid concentration of substrate preferably about 7 to about 15wt% more preferably from about 7 arrives about 12wt%, more more preferably from about 9 arrives about 10wt%.

In some cases, N-((phosphonomethyl)) the iminodiethanoic acid substrate source that is fed in this technology with water-containing material 1 form that flows is contained from the synthetic chlorion (Cl that inherits of substrate ^-1).In the occasion of the precious metal of catalyst pack carbon containing load, chlorion often interacts with catalyzer, has increased the leaching of precious metal and has suppressed the oxidation of formic acid by product.And, chloride level each logistics therein (for example, concentrating and/or purification step) recirculation as described below and be incorporated in the reactor assembly of oxidation reaction zone and trend towards rising from the product of present method.Preferably, in oxidation reaction zone with liquid phase reaction medium that catalyzer contacts in chlorine ion concentration remain on and be not higher than about 500ppm (weight), more preferably no higher than about 300ppm (weight), more more preferably no higher than 100ppm (weight).Advantageously, the control of chloride level realizes by N-((phosphonomethyl)) the iminodiethanoic acid substrate source formation water-containing material stream 1 that use has relative low chlorine ion content in oxidation reaction zone.Preferably; chlorine ion concentration in the N-of streamed charging present method with water-containing material ((phosphonomethyl)) iminodiethanoic acid substrate source is lower than about 5000ppm (weight); more preferably less than about 3000ppm (weight); more more preferably less than about 2000ppm (weight); especially be lower than about 1000ppm (weight), by dry basis.For example can pass through in U.S. patent 4,724,103 and 4,775, the method described in 498 is produced and is satisfied these standard N-((phosphonomethyl)) iminodiethanoic acid substrate source, and these patents are here quoted specially as a reference.In addition, can advantageously utilize drastic reduction precious metal (for example the platinum)/C catalyst of above-mentioned interpolation ruthenium modification, catalysis should reaction in continuous oxidation reaction device system.The catalyzer of this ruthenium modification can provide the enhanced anti-chlorine ion the aggressive and leachability of anti-the precious metal, and uses in the continuous oxidation reaction device system that raises owing to various recirculation stream of the chloride level that is particularly suitable for oxidation reaction zone therein.

Can oxygen source be incorporated in the reaction mixture in the stirred-tank reactor 3 by making any usual manner that dissolved oxygen concentration in reaction mixture remains on desired level.Preferably, oxygen source is to contain O ₂Gas, as air, pure O ₂Or with one or more non-oxidized gas (for example He, Ar and N ₂) dilution O ₂More preferably, oxygen source is to comprise at least about 95mol%O ₂, about usually 98mol%O ₂Contain O ₂Gas.So that contain O ₂Gas is incorporated into this gas in the reaction mixture with the mode that reaction mixture closely contacts.For example, contain O ₂Gas can be introduced by the distribution conduit or the similar dispenser that are positioned under stirred-tank reactor 3 bottom impeller, makes when containing O ₂When gas rises by liquid reaction medium, the turbulent flow thorough mixing that causes by rotary blade and distribute it.Contain O ₂The distribution of gas in reaction mixture can be by feeding this gas scatterer such as sintered glass filter or by well known to a person skilled in the art that alternate manner further strengthens.Perhaps, contain O ₂Gas can be incorporated in the stirred-tank reactor 3 in the head space on the reaction mixture.

If the dissolved oxygen concentration in the reaction mixture is too high, catalyst surface is easily by oxidation nocuously, this so that cause easily leaching and increase and the active reduction of formaldehyde (this and then cause producing more N-methyl-N-((phosphonomethyl)) glycine again).For fear of this problem, the oxygen delivery rate that general preferred use is such makes at least about 40%, more preferably at least about 60%, more more preferably at least about 80% with also more preferably be utilized at least about 90% oxygen.Here employed oxygen utilizes percentage ratio to equal: (total oxygen consumption rate ÷ oxygen delivery rate) * 100%.The total oxygen consumption rate of term is meant that (i) N-((phosphonomethyl)) iminodiethanoic acid substrate generates the oxygen consumption rate (R of the oxidizing reaction of N-((phosphonomethyl)) glycine product and formaldehyde _i), (ii) formaldehyde generates the oxygen consumption rate (R of the oxidizing reaction of formic acid _Ii) and (iii) formic acid generate the oxygen consumption rate (R of the oxidizing reaction of carbonic acid gas and water _Iii) summation.

Oxygen partial pressure can change in the different zones of oxidation reaction zone.Preferably, the aerial oxygen partial pressure in top is about 0.1 to about 35psia on the liquid reaction mixture in stirred-tank reactor, more preferably from about 1 arrives about 10psia.

When oxidizing reaction was carried out in single continuous stirred tank reactor system, according to employed concrete catalyzer and oxidation reaction condition, the residence time in reactor 3 can alter a great deal.Usually, the residence time is about 3 to about 120 minutes, more preferably from about 5 to about 90 minutes, also more preferably from about 5 arrives about 60 minutes and more more preferably from about 15 to about 60 minutes.The residence time is that benchmark is determined with the flow velocity of filtrate 13 and the working volume of stirred-tank reactor 3.

The beaded catalyst that utilizes in the continuous oxidation reaction system can comprise the carrier of powder type, and this carrier has foregoing size-grade distribution.Preferably, the mean particle size of beaded catalyst is about 15 to about 40 μ m, more preferably from about 25 μ m.The concentration preferably about 0.1 to about 10wt% ([the quality ÷ total reactant quality of catalyzer] * 100%) of beaded catalyst in stirred-tank reactor 3 reaction mixture.More preferably, catalyst concn is about 0.5 to about 5wt%, more more preferably from about 1 arrives about 3wt% and 2wt% more preferably from about also.The concentration that is higher than about 10wt% is difficult to separate from N-((phosphonomethyl)) glycine product.On the other hand, the concentration that is lower than about 0.1wt% has often produced unacceptable low reaction speed.

Be used for preferably being applicable to the strainer of continuous separating catalyst from reaction mixture from the catalyst filter 9 of the reaction mixture 7 separating particles catalyzer of stirred-tank reactor 3 discharges.That is to say, the continuous logistics that catalyst filter 9 can acceptable response mixture 7 and form filtrate 13 and catalyst recycle logistics 11 continuously, and needn't interrupt being incorporated into the flow of reaction mixture in this strainer.According to a particularly preferred embodiment, catalyst filter 9 is continuous cross-flow filter or continuous back-flushing filter.In carrying out continuous oxidation style shown in Figure 2, back-flushing filter is generally preferred than cross-flow filter, because commercially available back-flushing filter generally can form the catalyst recycle logistics 11 that contains the greater concn catalyzer at present, catalyst concn is than at least 5 times of at present commercially available cross-flow filter height usually.

Fig. 2 A is and the block diagram of similar flow reactor shown in Figure 2 system that it especially is fit to use continuous back-flushing filter as catalyst filter 9.When the operation overall pressure ratio normal atmosphere in oxidation reaction zone is much higher (this is preferred), in order to concentrate and purifying N-((phosphonomethyl)) glycine product, the reaction mixture that general reduction is discharged by stirred-tank reactor 3 flows out the pressure in the thing 7.At least a portion that this pressure descends can be carried out in catalyst filter 9 upstream flash tanks 17.Flash tank 17 is reduced to the pressure of reaction mixture 7 to a certain degree, makes dissolved CO ₂Flash distillation is come out and is discharged from flash tank as steam from mixture.Flash tank 17 has reduced the running pressure of continuous recoil catalyst filter 9, thereby has reduced the complicacy of capital cost and filter system.Oxygen source (for example can be contained O ₂Gas) introduce (for example spraying) to flash tank 17; with not oxidized N-((phosphonomethyl)) the iminodiethanoic acid substrate in stirred-tank reactor 3 in the further oxidation mixtures 7, and further oxidation is present in formaldehyde and formic acid by product in the reaction mixture.By this way, flash tank 17 can play a part and stirred-tank reactor 3 placed in-line additional oxidation reaction zones.

The back-flushing filter system comprises filter element continuously, and preferred adiabatic operation, but can have heating or cooling power.Preferably, being used for the back-flushing filter element is the part of filtrate 13 with the liquid of removing isolating catalyzer.Filtrate 13 is sent to be concentrated and purifying N-((phosphonomethyl)) glycine product; catalyst recycle logistics 11 is simultaneously discharged from catalyst filter 9 continuously, and can be transferred to optional catalyst stores jar 5 (being also referred to as catalyst recycle jar or catalyst slurry jar) before this catalyzer is incorporated in the stirred-tank reactor 3 again.

Though the preferably continuous back-flushing filter of the catalyst filter 9 in the oxidation reactor system shown in Fig. 2 and the 2A should be realized that cross-flow filter is preferred in some cases continuously.Be similar in the system shown in Fig. 2 and the 2A in the system class shown in Fig. 2 B, just catalyst filter 9 is placed in the external heat exchange cycles loop 15, rather than in independent catalyst recirculation loop.In this embodiment, the preferably continuous cross-flow filter of catalyst filter 9.Usually, the flash tank before the strainer is not united use with cross-flow filter.In addition, because the catalyst recycle logistics 11 of relative large volume flows out the general same omission of catalyst stores jar from continuous cross-flow filter.

Except cross-stream and back-flushing filter, the catalyst filter 9 that uses in continuous oxidation reaction device system can be that vacuum filter maybe can comprise row's leaf filter in addition, is used for handling the Continuous Flow that flows out thing 7 at the reaction mixture of staggered filtration cycle.As another yes-no decision, stirred-tank reactor 3 can comprise inner catalyst strainer (for example sintered glass filter), its stops beaded catalyst to flow out thing 7 with reaction mixture to discharge, and makes this catalyzer be retained in the oxidation reaction zone substantially and reaction mixture flows out thing and do not contain beaded catalyst substantially.And, should be realized that, can use other catalyst separating mode to replace (or being additional to) catalyst filter 9.For example, can use whizzer separating catalyst from the oxidation mixtures effluent.

When catalyzer with the prolongation of using during inactivation, it can be continuously or off and on to the small part reactivate.Reactivate can be included in and reduce the surface of this catalyzer after the catalyzer heavy oxidation.In this case, for example can washing surface to remove organism, use above-mentioned reduction to handle then and reduce.This reduction is handled and for example can be comprised reductive agent is incorporated into reactor assembly continuously or intermittently.For example, reductive agent can comprise formaldehyde and/or formic acid and can advantageously be obtained by various recirculation stream described herein usually.Reactivate can also be by for example with supplemental promoter, and especially bismuth oxide is incorporated into above-mentioned reactor assembly and realizes.According to the preferred embodiments of the invention, with supplemental promoter (Bi for example ₂O ₃) be incorporated into the flow reactor system continuously or intermittently, make the formic acid concn that flows out in the thing at the reaction mixture of discharging remain below about 6000ppm by last oxidation reaction zone, more preferably from about 1000ppm is to about 3000ppm.According to particularly preferred practice of the present invention, the formic acid concn of monitoring in the reaction mixture outflow thing of discharging by last oxidation reaction zone.In case the concentration that records surpasses about 6000ppm, 3000ppm more preferably from about, 2000ppm more more preferably from about, beginning is introduced supplemental promoter continuously or intermittently to reactor assembly, and lasts till till being begun to descend by the formic acid concn in the reaction mixture outflow thing of last oxidation reaction zone discharge.Preferably, the speed of adding supplemental promoter to reactor assembly should make in beginning that after this system adds supplemental promoter the formic acid concn in the reaction mixture outflow thing of being discharged by last oxidation reaction zone continues to raise and reaches certain hour.With Bi ₂O ₃Promotor is added under the situation of reactor assembly as a supplement, is fed to the Bi of this system ₂O ₃With the weight ratio of N-((phosphonomethyl)) iminodiethanoic acid substrate be about 1: 20,000,00 by about 1: 200,000.

Though choose wantonly in the continuous oxidation reaction device system shown in Fig. 2 A, when using the beaded catalyst of drastic reduction, catalyst stores jar 5 can be favourable, because it provides catalyst substance by the place of even reactivate.As shown in Fig. 2 A, reductive agent 18 and/or supplemental promoter 19 can be incorporated in the catalyst stores jar 5 that contains catalyst recycle.Perhaps reductive agent and/or supplemental promoter can directly join oxidation reaction zone or be incorporated into reactor assembly elsewhere.It should further be appreciated that, only allow catalyst recycle and residual reaction mixture be in the catalyst stores jar 5 also advantageously reducing catalyst surface (catalyzer that especially comprises the precious metal of carbon load).Preferably, the catalyst stores jar does not contain O substantially ₂With other oxidizing gas.Therefore, can advantageously nitrogen or other non-oxidizing gas be introduced (for example spraying) in jar 5, to help to remove O ₂Before being incorporated into oxidation reaction zone again, allow the slurry of beaded catalyst and residual slurry not have O substantially ₂Environment under, outside oxidation reaction zone, keep certain hour, it is believed that surface that can reducing catalyst and realize reactivate to a certain degree and prolong work-ing life of catalyzer.Catalyst stores jar or catalyst slurry jar 5 can have various structures, but generally be stirring tank, the catalyst slurry that wherein comprises beaded catalyst and residual reaction mixture stirs with rotary blade, so that by preventing that catalyst sedimentation from improving the homogeneity of catalyst slurry and promoting the even reactivate of catalyzer to jars 5 bottom.By regulate the volume of catalyst stores jar inner catalyst slurry with respect to the working volume of oxidation reaction zone internal reaction medium, can regulate the residence time of catalyzer in catalyst stores jar 5.The long catalyzer residence time in catalyst stores jar 5 generally is of value to catalyst performance.Yet, because the long residence time requires the catalyst inventory in reactor assembly bigger, must consider that than the benefit of long residence time especially under the situation of the precious metal of catalyst pack carbon containing load, this becomes very important with the catalyzer cost balance that increases.Preferably, the residence time of catalyst recycle in the catalyst stores jar is at least about 2 minutes, more preferably at least about 5 minutes, and more more preferably from about 5 to about 40 minutes.

Keep or be incorporated in the reaction soln if will sacrifice reductive agent, can find that in the present invention the loss of precious metal reduces.The reductive agent that is fit to comprises formaldehyde, formic acid and acetaldehyde.Most preferably, use formic acid, formaldehyde or their mixture (for example obtaining) by various recirculation stream described here.

Can also remove stream 20 by catalyzer and from continuous oxidation reaction device system, remove catalyzer (for example have the active of reduction and/or optionally catalyzer) continuously or intermittently, and replace through live catalyst feedstream 21 usefulness live catalysts.When intermittently removing catalyzer, the catalyst substance (this generally is preferred method) that can clear all from this technology simultaneously perhaps can be removed the part catalyst substance under different time increments.In other words, intermittently removing comprises any repetition and the removing of discontinuous catalyzer.

According to preferred embodiment of the present invention; the continuous oxidation of N-((phosphonomethyl)) iminodiethanoic acid substrate is in the presence of particle heterogeneous catalyst slurry; classification is carried out in the oxidation reaction zone of the two or more basic back mixing of serial operation (that is back mixing in liquid phase at least).The combination of placed in-line two or more back mixing oxidation reaction zones is favourable, because this reactor assembly often shows to such an extent that more resemble plug flow reactor, forms the yield of less by product and improvement N-((phosphonomethyl)) glycine product.And the combination of two or more reaction zones provides the ability that changes reaction conditions in the different steps of oxidizing reaction according to principal reaction kinetics.

For concentration of substrate; the oxidation of N-((phosphonomethyl)) iminodiethanoic acid substrate shows as proximate zeroth order reaction; be reduced to up to N-((phosphonomethyl)) iminodiethanoic acid concentration of substrate and be not higher than about 4.5wt%; more generally be not higher than about 2.7wt%; more about 0.4wt% is to about 1.8wt%; also more generally about 0.4wt% arrives about 1.3wt%, and also more generally is not higher than about 1wt%.For example the concentration of substrate in the water-containing material that is fed to first reaction zone is the occasion of about 9wt%, with regard to substrate, reaction often shows as proximate zeroth order reaction, up at least about 50%, more generally at least about 70%, more more generally about 80% to about 95% and also more generally about 85% to about 95% substrate be consumed.At this moment, oxidation rate become concentration of substrate than majorant (promptly with regard to concentration of substrate, oxidation is near first order reaction), therefore and trend towards further reducing with concentration of substrate.When oxidation rate become N-((phosphonomethyl)) iminodiethanoic acid concentration of substrate than majorant the time, the oxidation of substrate is often slower than the simultaneous oxidation of formaldehyde and formic acid by product reaction.

The continuous oxidation reaction device system that comprises placed in-line two or more oxidation reaction zones by utilization, can be controlled at the residence time and/or oxygen feed in first reaction zone, make the reacting phase in first reaction zone show as zeroth order reaction basically (promptly for concentration of substrate, can control the residence time in first reactor, make substrate conversion in first reactor be enough to form concentration of substrate and be not higher than about 4.5wt%, more preferably no higher than about 2.7wt%, more more preferably from about 0.4 arrive about 1.8wt%, also more preferably from about 0.4 to about 1.3wt% and the further reaction mixture of 1wt% more preferably from about).This reaction mixture can transfer to then second and any subsequent reaction zone in, this reaction shows as first order reaction substantially with regard to concentration of substrate in these reaction zones.By this way, can be independently in each reaction zone accurate controlling reactor configuration and/or reaction conditions (catalyst type for example, average catalyst duration of service, catalyst concn, oxygen concn, temperature, pressure etc.), to optimize the oxidation of each section of reaction and formaldehyde and formic acid by product.

Fig. 3 has shown the preferred continuous oxidation reaction device system that comprises series connection fractionated two back mixing oxidation reaction zones according to of the present invention.The back mixing oxidation reaction zone preferably provides by two continuous stirred tank reactors 3 and 40.Contain the water-containing material stream 1 and the oxygen source of N-((phosphonomethyl)) iminodiethanoic acid substrate, preferably contain O ₂Gas is incorporated in first stirred-tank reactor 3 together continuously or intermittently.N-((phosphonomethyl)) iminodiethanoic acid substrate is in the presence of heterogeneous beaded catalyst; quilt oxidation continuously in first stirred-tank reactor 3; formation comprises the middle aqueous reaction mixture 41 of N-((phosphonomethyl)) glycine product and unreacted N-((phosphonomethyl)) iminodiethanoic acid substrate, and it is discharged from first stirred-tank reactor 3 continuously or intermittently.Comprise (a) N-((phosphonomethyl)) glycine product from middle aqueous reaction mixture 41; (b) middle the water-containing material of unreacted N-((phosphonomethyl)) iminodiethanoic acid substrate (also come to small part in the middle of aqueous reaction mixture 41) flows 42 and is incorporated into second stirred-tank reactor 40 then.Usually, also other oxygen is incorporated into second stirred-tank reactor 40, preferably also to contain O ₂The form of gas.In second stirred-tank reactor 40, other N-((phosphonomethyl)) iminodiethanoic acid substrate by oxidation continuously, forms the final reacting mixture effluent 45 that comprises N-((phosphonomethyl)) glycine product in the presence of heterogeneous beaded catalyst.Head space on emptying stirred-tank reactor 3 and 40 reaction mixture when carrying out with convenient oxidizing reaction, is removed from oxidation reaction zone and is comprised CO ₂Steam.

Though water-containing material stream 42 comprises whole middle aqueous reaction mixture 41 in the middle of the demonstration in Fig. 3, should be realized that in some embodiments of the present invention, middle water-containing material stream 42 is less than whole middle aqueous reaction mixture 41.For example, as following (Fig. 5 and 6), the particle heterogeneous catalyst can partly or entirely be removed from middle aqueous reaction mixture 41.In addition, should be appreciated that first and second oxidation reaction zones needn't be included in the independent stirring tank reaction vessel 3 and 40 as shown in Figure 3.A plurality of oxidation reaction zones can connect classification and be included in be divided into a plurality of compartments have the baffle plate that is used to separate each reaction zone or the single reaction vessel of other measure in.

In the embodiment shown in Fig. 3, the reaction zone of beaded catalyst from first stirred-tank reactor 3 flows in the reaction zone in second stirred-tank reactor 40.Preferably, beaded catalyst is the oxide catalyst of above-mentioned drastic reduction.This catalyzer is incorporated in first stirred-tank reactor 3 continuously or intermittently through catalysagen materials flow 39.As shown in Figure 3, catalysagen materials flow 39 is the parts that contain the water-containing material of N-((phosphonomethyl)) iminodiethanoic acid substrate stream 1.This catalyzer is discharged from first stirred-tank reactor 3 continuously or intermittently as the part of middle aqueous reaction mixture 41, is incorporated in second stirred-tank reactor 40 continuously or intermittently and discharges from second stirred-tank reactor 40 continuously or intermittently as the part of final reacting mixture effluent 45 at last as the part of middle water-containing material stream 42.Final reacting mixture effluent 45 is chosen decompression in flash tank 17 wantonly, transfers in the catalyst filter 9 again.In catalyst filter 9, basically all beaded catalysts separate from final reacting mixture effluent 45, and formation (1) comprises the catalyst recycle logistics 11 from N-((phosphonomethyl)) the glycine product of all catalyzer basically of final reacting mixture 45 and residual volume; (2) comprise filtrate 13 from most of N-((phosphonomethyl)) glycine product of final reacting mixture 45.In the embodiment depicted in fig. 3, catalyst filter 9 is continuous back-flushing filter system preferably, so that catalyst recycle logistics volume is minimized and keep grading effect in the reactor assembly.Catalyst recycle logistics 11 is imported in the catalyst stores jar 5, be incorporated in first stirred-tank reactor 3 through catalysagen materials flow 39 again, filtrate 13 is sent to and is concentrated and purifying N-((phosphonomethyl)) glycine product simultaneously.When catalyzer with the prolongation of using during inactivation, as mentioned above, by making this beaded catalyst and reductive agent 18 (for example in catalyst stores jar 5) continuously or Intermittent Contact and/or supplemental promoter 19 is incorporated in this technology (for example be incorporated in the catalyst stores jar 5 and/or be introduced directly in first and/or second stirred-tank reactor 3 and 40), it can be to the small part reactivate.Catalyzer can be removed logistics 20 by catalyzer and remove continuously or intermittently from system, and by catalysagen materials flow 21 fresh makeup catalyst.

In the starting process of the reactor assembly in Fig. 3, can heat the catalysagen materials flow 39 and/or the water-containing material stream 1 that are incorporated into first stirred-tank reactor 3, so that in oxidation reaction zone, obtain required temperature.In stable state or quasi-steady state operating process, thermopositive reaction heat enough allows raw material reach required temperature of reaction usually, and removes in the liquid reaction medium of the heat exchanger 16 of excessive reaction heat in external heat exchange cycles loop 15 from first reactor 3.For example by coming control reaction temperature according to the water coolant of supplying from the signal control heat exchanger 15 of temperature regulator.Similarly, the temperature of the liquid reaction medium in second oxidation reaction zone of reactor 40 can be removed hot speed by the heat exchanger 48 in the external heat exchange cycles loop 47 that links to each other with second reactor and be controlled.Yet second oxidation reaction zone can not have heat exchange loop 47 or be used to remove operation (being adiabatic operation) under the situation of other measure of reaction heat.For example; in some cases; the conversion of the increase of N-((phosphonomethyl)) iminodiethanoic acid substrate and the existing oxidation of formaldehyde and formic acid are so limited in second stirred-tank reactor 40, so that do not need reaction mixture to remove the heat of being emitted by oxidizing reaction.Be higher than the occasion of finishing reaction under the temperature of leading temperature of first reactor 3 at hope second reactor 40, the spontaneous reaction heat in second reactor can contribute the temperature of rising water-containing material stream 42 and remain on first reactor and second reactor between the necessary all or part of heat of temperature head of wishing.

The temperature of the reaction medium within second stirred-tank reactor 40; preferably keep enough high, make that basic all N-((phosphonomethyl)) the glycine products in the final reacting mixture effluent 45 of being discharged by second reactor keep dissolving with respect to N-((phosphonomethyl)) glycine production concentration.Randomly, sedimentary N-((phosphonomethyl)) glycine product can separate with beaded catalyst in final reacting mixture effluent 45, as the part of catalyst recycle logistics 11.Should be realized that the temperature of the reaction mixture in stirred-tank reactor 3 and 40 can differ from one another.For example; because middle aqueous reaction mixture 41 is not filtered and also contains N-((phosphonomethyl)) the glycine product that concentration is lower than final reacting mixture effluent 45, generally can be lower than the preferred operations temperature of the reaction mixture in second stirred-tank reactor 40 slightly in the temperature of the reaction mixture within first stirred-tank reactor 3.Preferably, first stirred-tank reactor 3 is at about 80 ℃ to about 120 ℃, more preferably from about 85 ℃ to about 110 ℃ and also more preferably from about 95 ℃ under about 100 ℃ temperature, operate, and second stirred-tank reactor 40 is preferably at about 80 ℃ to about 120 ℃, more preferably from about 85 ℃ to about 110 ℃ and also more preferably from about 100 ℃ under about 105 ℃ temperature, operate.Operate the speed that first stirred-tank reactor, 3 common favourable reduction N-methyl-N-((phosphonomethyl)) glycine form at a lower temperature, this by product increases under comparatively high temps.

Total pressure in first and second stirred- tank reactors 3 and 40 preferably keeps enough height, so that prevent the liquid reaction medium boiling in the oxidation reaction zone, and generally is about 0 to about 500psig.Typically, the total pressure in stirred- tank reactor 3 and 40 is about 30 to about 500psig.The temperature of the reaction mixture in keeping first and second oxidation reaction zones is in above-mentioned preferred range the time, and the total pressure preferably about 30 to about 130psig and more preferably from about 90 that keeps first and second stirred- tank reactors 3 and 40 in arrives about 110psig.

Oxygen partial pressure can change in the different zones of oxidation reaction zone.Preferably, the aerial oxygen partial pressure in top is about 0.1 to about 35psia on the liquid reaction medium in stirred- tank reactor 3 and 40, more preferably from about 1 arrives about 10psia.

Particularly the concentration of N-((phosphonomethyl)) iminodiethanoic acid substrate is about 7 to about 12wt% the time in water-containing material stream 1 (it comprise catalyst recycle logistics 11 and from any other recirculation stream of this method other parts); during more especially about 9wt%; it is at least about 50% to the transformation efficiency of N-((phosphonomethyl)) glycine product that the general preferred residence time in first stirred-tank reactor 3 should make N-in the oxidation reaction zone of winning ((phosphonomethyl)) iminodiethanoic acid substrate; more preferably at least about 70%; more more preferably from about 80% to about 95%; also more more preferably from about 85% to about 95% and most preferably from about 90%.Obtaining the necessary residence time of required transformation efficiency will change with the variation of the oxidation reaction condition that uses in first stirred-tank reactor 3.Usually, the residence time in first stirred-tank reactor 3 is about 5 to about 50 minutes, preferred about 10 to about 30 minutes, and more preferably from about 14 to about 24 minutes and more more preferably from about 20 minutes.The residence time in second stirred-tank reactor 40 generally is about 1 by about 50 minutes, preferred about 1 to about 30 minutes, and more preferably from about 3 to about 20 minutes, also more preferably from about 6 to about 20 minutes, also more more preferably from about 6 to about 12 minutes and also further preferred about 8 minutes.The residence time in first stirred-tank reactor 3 is that benchmark defines with the flow velocity of intermediate reaction mixture 41 and the working volume of reactor.The residence time in second stirred-tank reactor 40 is that benchmark defines with the flow velocity of final reacting mixture effluent 45 and the working volume of reactor.Along with catalyst activity reduces with the prolongation of using, the transformation efficiency that obtains under the given residence time often reduces, and needs to pass through reactivate or adds live catalyst or increase O in system ₂Delivery rate is strengthened catalyst activity.

Preferably, the ratio of the working volume of the working volume of the liquid reaction medium in first stirred-tank reactor 3 and the liquid reaction medium in second stirred-tank reactor 40 is greater than 1, more preferably greater than 1 to about 10 at the most, also more preferably from about 1.1 to about 5 and also more more preferably from about 1.1 to about 2.5.

Usually when the flow reactor system comprises placed in-line two stirred-tank reactors; adjusting be incorporated in the flow reactor system total oxygen raw material (promptly; be given to the total oxygen raw material in two stirred-tank reactors 3 and 40) and total oxygen product distribution to the amount of each stirred-tank reactor, so that influence the yield and the quality of N-((phosphonomethyl)) glycine product.In one embodiment; change N-((phosphonomethyl)) the iminodiethanoic acid substrate of total oxygen/mole in being incorporated into the water-containing material stream 1 of first stirred-tank reactor 3 that is incorporated in the flow reactor system, so that the concentration of control N-((phosphonomethyl)) iminodiethanoic acid substrate in the final reacting mixture effluent 45 of discharging by second stirred-tank reactor 40.The concentration of unreacted N-((phosphonomethyl)) the iminodiethanoic acid substrate in the final reacting mixture 45 is minimized, so that avoid the over-drastic yield losses.Preferably, the concentration of unreacted N-((phosphonomethyl)) iminodiethanoic acid substrate in the final reacting mixture effluent is not higher than about 2000ppm.Yet the concentration of N-((phosphonomethyl)) iminodiethanoic acid substrate in final reacting mixture effluent 45 should keep enough height, so that suppress the speed that N-((phosphonomethyl)) glycine product is oxidized to aminomethylphosphonic acid.The speed that aminomethylphosphonic acid forms obviously and N-((phosphonomethyl)) iminodiethanoic acid concentration of substrate be inversely proportional to.And, it is believed that the existence of N-((phosphonomethyl)) iminodiethanoic acid substrate can suppress the oxidation of catalyzer and prolong catalyst life.Therefore; the preferred concentration of N-((phosphonomethyl)) iminodiethanoic acid substrate in final reacting mixture effluent 45 is maintained at about 200 to about 2000ppm; more preferably from about 500 to about 1500ppm and most preferably from about 500 in the scope of about 700ppm, by weight.Usually; when for N-((phosphonomethyl)) the iminodiethanoic acid substrate in every mole the water-containing material stream that is being incorporated into first stirred-tank reactor 31; the total oxygen that is incorporated into the flow reactor system is about 0.5 to about 5, and more preferably from about 1 to about 3, also more preferably from about 1.5 to about 2.5 moles of O ₂The time, obtained the suitable concentration of N-((phosphonomethyl)) iminodiethanoic acid substrate in final reacting mixture 45.

In addition, select to be given to the distribution of total oxygen raw material between stirred- tank reactor 3 and 40 of flow reactor system, to reduce the amount of the by product in final reacting mixture effluent 45.Entering the ratio that is incorporated into first stirred-tank reactor 3 in total oxygen raw material of flow reactor system is about 10% to about 95%, more preferably from about 30% to about 95%, also more preferably 50% to about 95%, most preferably from about 70% to about 90%, and the remainder of total oxygen raw material is incorporated into second stirred-tank reactor 40.

In enforcement of the present invention; can measure unreacted N-((phosphonomethyl)) iminodiethanoic acid substrate, N-((phosphonomethyl)) glycine product and/or oxidized byproduct are at the middle aqueous reaction mixture 41 of being discharged by first stirred-tank reactor 3 and/or by the concentration in the final reacting mixture effluent 45 of second stirred-tank reactor, 40 discharges.Based on these measuring results; the total oxygen raw material and/or this distribution of total oxygen raw material between first and second stirred-tank reactors 3 and 40 that enter the flow reactor system be can regulate, thereby the yield and the quality of N-((phosphonomethyl)) glycine product advantageously influenced.Can use high pressure lipuid chromatography (HPLC) (HPLC) or fourier transform infrared spectroscopy (FTIR) the unreacted N-of analyte stream sample determination ((phosphonomethyl)) iminodiethanoic acid substrate, the concentration of N-((phosphonomethyl)) glycine product and/or oxidized byproduct.In addition, can use online FTIR spectrometer, so that the real-time compositional analysis of reactor effluent logistics is provided, and these data are used for regulating the oxygen raw material of flow reactor system.Online use infrared spectroscopy is measured the concentration of the analyte in oxidation mixtures such as those oxidation mixtures prepared in accordance with the present invention, the method that is used for technology controlling and process and end point determination, be described in the title submitted to May 22 calendar year 2001 for the U.S. temporary patent application No. of " Use of InfraredSpectroscopy for On-Line Process Control and EndpointDetection " _ _ _ _ in (Attorney ReferenceMTC 6767; 39-21 (51882)), whole disclosures of this application are specially quoted for referencial use here.

Usually, when the flow reactor system comprised placed in-line two continuous stirred tank reactors 3 and 40, the oxygen delivery rate preferably about 0.5 that is given to first reaction zone was to about 10, and more preferably from about 0.5 to about 5, and also more preferably from about 1.0 to about 4.0mol O ₂N-((phosphonomethyl)) the iminodiethanoic acid substrate that in being incorporated into the water-containing material stream 1 of first reactor 3, contains of/mol.The oxygen delivery rate preferably about 0.5 that is given to second reaction zone is to about 10, and more preferably from about 0.5 to about 5, and also more preferably from about 2 to about 4mol O ₂The N-in the feedstream that is given to second reaction zone ((phosphonomethyl)) the iminodiethanoic acid substrate of/mol.

Use the occasion of placed in-line two stirred-tank reactors in described method; N-((phosphonomethyl)) the iminodiethanoic acid substrate in preferred first reactor of maintenance and the mol ratio of N-((phosphonomethyl)) glycine product; make N-((phosphonomethyl)) iminodiethanoic acid substrate oxidation molar rate be N-((phosphonomethyl)) glycine product oxidation molar rate at least about 10 times; more preferably at least about 20 times; more more preferably at least about 100 times; also more preferably at least about 150 times with most preferably at least about 200 times.

Can use the various replacement schemes of schema shown in Fig. 3, come by the intrasystem back mixing oxidation reaction zone of flow reactor circulating granular heterogeneous catalyst.The case representation of these alternative flow is in Fig. 4-6.In each schema shown in Fig. 3-7, can be by continuously or intermittently be added to live catalyst in the catalyst recycle logistics or directly be added in each reaction zone and remain on desirable scope in age catalyzer or be controlled near the specified level.Can choose wantonly in addition by from the catalyst recycle logistics, removing the part catalyzer continuously or intermittently and control this catalyzer age.Usually, the catalytic amount of being removed equals to be added to the live catalyst amount in this system.Intermittently remove and add catalyzer and comprise any repetition and the removing and the interpolation of discontinuous catalyzer.For example, intermittence removing and interpolation comprises regularly discharges catalyzer from the catalyst recycle logistics, and live catalyst is added in the position in the discharge point downstream in the catalyst recycle loop.Removing at intermittence and interpolation also comprise for example once discharges all catalyzer from the reaction zone that is less than the total overall reaction district, then a collection of fresh catalyzer fully is added in the reaction zone that is less than the total overall reaction district.Intermittently remove and add and for example also comprise simultaneously from the flow reactor system and discharge all catalyzer and add a collection of fresh fully catalyzer (for example, in case by reactor assembly production N-((phosphonomethyl)) in case predetermined target value or catalyst activity that the glycine product reached based on work-ing life of catalyst load have dropped to the degree that can not operate economically) then.Back one method generally is preferred.This is owing to the fact that for example is difficult to stablize this system when only removing with addition portion divided catalyst load at given time usually.Also for example at first do not removing under the situation of all raw catalysts, be difficult to analyze any change (for example newly improving) catalyzer.Should further be pointed out that, in the initial stage of continuous oxidation reaction system, can be advantageously operate this system's certain hour, gradually other catalyzer is added to this system then so that be issued to the catalyst loading of the best in main operational condition with the catalytic amount that significantly is less than design catalyst loading (for example design catalyst loading 75%).

Fig. 4 embodiments shown provides greater flexibility by the catalyst loading that control enters first and second stirred-tank reactors 3 and 40; make in second stirred-tank reactor 40, can keep desirable higher catalyst loading, so that compensation general N-((phosphonomethyl)) iminodiethanoic acid concentration of substrate motivating force reduction that exists at least in part owing to lower concentration of substrate in second reaction zone.Catalyzer is incorporated in first stirred-tank reactor 3 continuously or intermittently through catalysagen materials flow 39.This catalyzer is discharged from first stirred-tank reactor 3 continuously or intermittently as the part of middle aqueous reaction mixture 41 then, part as middle water-containing material stream 42 is incorporated in second stirred-tank reactor 40 continuously or intermittently, and a last part as final aqueous reaction mixture 45 is from second stirred-tank reactor, 40 discontinuous or discharge continuously.Substantially remove catalyzer by catalyst filter 9 from final aqueous reaction mixture 45 then, formation (1) comprises the catalyst recycle logistics 11 from N-((phosphonomethyl)) the glycine product of basic all catalyzer of final aqueous reaction mixture 45 and residual quantity; (2) comprise filtrate 13 from most of N-((phosphonomethyl)) glycine product of final aqueous reaction mixture 45.Catalyst recycle logistics 11 is divided into catalysagen materials flow 39 and middle catalysagen materials flow 50.Catalysagen materials flow 39 is recycled to first stirred-tank reactor 3, and simultaneously middle catalysagen materials flow 50 is recycled to second stirred-tank reactor 40.Preferably remove logistics 53 and from the flow reactor system, remove catalyzer continuously or intermittently by for example catalyzer removing logistics 51 and/or catalyzer, and by for example catalysagen materials flow 55 and/or catalysagen materials flow 57 make-up catalysts.Perhaps or additionally, can from catalyst recycle logistics 11, remove catalyzer, and equally before recirculation stream 11 is divided into catalyst recycle logistics 39 and 50, perhaps or additionally live catalyst is added in the catalyst recycle logistics 11.Can also be by intermittently or be incorporated into the flow reactor system continuously with reductive agent and/or supplemental promoter, reactivating catalyst at least in part as described above especially comprises the occasion of the catalyzer of above-mentioned drastic reduction at catalyzer.For example in catalyst recycle logistics 11,39 and/or 50, introduce reductive agent and/or supplemental promoter.This reactivate is optional can to carry out in one or more catalyst stores jar (not shown)s.

Fig. 5 has shown that wherein each oxidation reaction zone utilizes its embodiment of beaded catalyst material independently separately.In this embodiment; the water-containing material stream 1 that will comprise N-((phosphonomethyl)) iminodiethanoic acid substrate is given to first stirred-tank reactor 3; at this water-containing material stream 1 oxidation continuously in the presence of first kind of catalyst substance, aqueous reaction mixture 41 in the middle of forming.This centre aqueous reaction mixture 41 filters in catalyst filter 9a, isolate basic first kind of all catalyst substances from middle aqueous reaction mixture 41, formation (1) comprises first kind of catalyst recycle logistics 11a from basic all catalyzer of middle aqueous reaction mixture 41; (2) water-containing material stream 60 promptly from the filtrate of strainer 9a, comprises most of N-((phosphonomethyl)) glycine product and unreacted N-((phosphonomethyl)) iminodiethanoic acid from middle aqueous reaction mixture 41 in the middle of.First kind of catalyst recycle logistics 11a gives through catalysagen materials flow 39a and gets back to first stirred-tank reactor 3, simultaneously middle water-containing material stream 60 is incorporated into second stirred-tank reactor 40, at this N-((phosphonomethyl)) iminodiethanoic acid substrate (and C ₁Molecule is as formaldehyde and formic acid) further continuously oxidation in the presence of the second beaded catalyst material, carry out, form final reacting mixture effluent 45.In flash tank 17b, choose wantonly after the decompression, final reacting mixture 45 filters in catalyst filter 9b, isolate second kind of catalyst substance from final aqueous reaction mixture 45, formation (1) comprises the catalyst recycle logistics 11b from basic all catalyzer of final aqueous reaction mixture 45; (2) comprise filtrate 13 from most of N-((phosphonomethyl)) glycine product of final aqueous reaction mixture 45.Through catalysagen materials flow 39b catalyst recycle logistics 11b is returned then and be given to second stirred-tank reactor 40.Preferably, the catalyst substance that utilizes in first stirred-tank reactor 3 is removed logistics 20a by catalyzer and is removed continuously or intermittently, replenishes by catalysagen materials flow 21a again.Equally, the catalyst substance that utilizes in second stirred-tank reactor 40 is preferably removed logistics 20b by catalyzer and is removed continuously or intermittently, replenishes by catalysagen materials flow 21b again.First and second stirred-tank reactors 3 and 40 beaded catalyst material can also be as mentioned above, by reductive agent 18a and 18b and/or supplemental promoter 19a and 19b are incorporated into continuously or intermittently separately catalyst stores jar 5a and other position of 5b or flow reactor system come reactivate at least in part.For example, supplemental promoter can also directly be added in one or two of stirred-tank reactor 3 and 40.

In the catalyst recycle mode shown in Fig. 5 is favourable, because it provides the handiness of catalyst type, catalyzer age and the carrying capacity of independent each reaction zone of control.For example; can design the catalyzer that uses in first stirred-tank reactor 3; so that under the operational condition that first oxidation reaction zone is being selected, obtain the high conversion of N-((phosphonomethyl)) iminodiethanoic acid substrate; can optimize simultaneously the catalyzer that in second stirred-tank reactor 40, uses, with the oxidation that improves formaldehyde and formic acid by product with the peroxidation of N-((phosphonomethyl)) glycine product is minimized.Also have, the dual filter reactor assembly, as shown in FIG. 5 the sort of can allow to use to produce the strainer that concentration is lower than the catalyst recycle logistics of single strainer reactor assembly (system as shown in FIG. 3) desired concn.

In some embodiments, duration of service, the benefit of short catalyzer may be greater than another reaction zone in a reaction zone.For example; in some embodiments; may be harmful like that in the influence of the aging catalyst of first reaction zone (wherein most of N-((phosphonomethyl)) iminodiethanoic acid substrate is oxidized usually) not as influence at the aging catalyst of second reaction zone, and the influence of live catalyst equally may be greater than first reaction zone in second reaction zone.For example most of therein N-((phosphonomethyl)) iminodiethanoic acid substrate is oxidized in first reaction zone, and resulting low concentration of substrate in second reaction zone causes in the embodiment of slower speed of response, may be exactly like this.In this case, usually preferably use flow process reactor assembly as shown in Figure 6.In this embodiment, come the catalyzer of the beaded catalyst material of utilization in comfortable second stirred-tank reactor 40 from catalyst recycle logistics 11b, to remove continuously or intermittently through logistics 65, and be incorporated into first stirred-tank reactor 3 through catalyst recycle logistics 11a, thereby prolonged the work-ing life of catalyzer in whole technology.Comprise expensive material at catalyzer, as the occasion of precious metal, this flow process is particularly advantageous.Usually in this embodiment, live catalyst only is incorporated into second reaction zone by catalysagen materials flow 21b, and catalyzer is only removed from first reaction zone of this technology through catalyzer removing logistics 20a.About 20 to about 65% of average catalyst age of the catalyzer that preferably utilize at first stirred-tank reactor 3 the average catalyst age in second stirred-tank reactor 40 (being the cumulative time that catalyzer is used for catalytic oxidation).The mean vol of N-((phosphonomethyl)) the glycine product that every pound of catalyzer produced in second stirred-tank reactor 40, about 5 to about 30% of N-((phosphonomethyl)) the glycine product mean vol that preferably every pound of catalyzer produced in first stirred-tank reactor 3.

Should be realized that, in some embodiments, more preferably with opposite direction catalyst recycle shown in Figure 6 (being catalyzer and substrate coflow).Under those situations, live catalyst is incorporated into first reaction zone continuously or intermittently, come the catalyzer of the beaded catalyst material of utilization in comfortable first stirred-tank reactor 40 from catalyst recycle logistics 11a, to remove continuously or intermittently, and transfer to second reaction zone continuously or intermittently, and from reactor assembly, remove the catalyzer in second reaction zone continuously or intermittently.In this embodiment, the average catalyst age in first stirred-tank reactor 3 is preferably in second stirred-tank reactor 40 about 33 to about 80% of average catalyst age of catalyzer.About 75 to about 90% of N-((phosphonomethyl)) the glycine product mean vol that every pound of catalyzer that the mean vol of N-((phosphonomethyl)) the glycine product that the every pound of catalyzer that consumes in first stirred-tank reactor 3 is produced preferably consumes in second stirred-tank reactor 40 is produced.

In the embodiment shown in Fig. 5 and 6, external heat exchange cycles loop 15 or 47 can also be the catalyst recycle loop with same way as shown in Fig. 2 B, rather than is independent of respectively outside catalyst recycle logistics 11a or the 11b.For this merging loop, the preferably continuous cross-flow filter of catalyst filter 9a and 9b.

Comprising two oxidation reaction zones of operating series, in especially placed in-line two stirred-tank reactors 3 and 40 the method, wishing to realize the high speed mass transfer at first oxidation reaction zone.Therefore, preferably by just being positioned under the impeller or near sparger will contain O ₂Gas preferably contains at least about 95molO ₂, generally about 98mol%O ₂The reaction mixture neutralization that is introduced directly in first stirred-tank reactor 3 of gas the back mixing of gas is minimized so that make the maximization of oxygen concn motivating force, thereby in first oxidation reaction zone, obtain high mass transfer.For the pressure and the OTR that equate, expection averaged oxygen spatial concentration is higher in the reaction environment with minimum gas phase back mixing.Near sparger, for example, the oxygen partial pressure in the gas dissolved is not usually above other zone of reactor, as the near interface between liquid reaction medium and head space.Yet in second reaction zone, N-((phosphonomethyl)) iminodiethanoic acid concentration of substrate is generally much lower, to the demand of mass transfer and obviously littler to the demand of hyperoxia concentration motivating force.Therefore, easier back mixing of allowing gas in second oxidation reaction zone, and be preferred in some cases.Preferred drastic reduction precious metal/C catalyst in enforcement of the present invention; be easier to peroxidation in having the reaction environment of the high keto sectional pressure air pocket of gas dissolved not; especially under low N-((phosphonomethyl)) iminodiethanoic acid concentration of substrate, those as running at second oxidation reaction zone.By the gas phase in the liquid reaction medium in back mixing second oxidation reaction zone, averaged oxygen spatial concentration and the stability that has improved this catalyzer have been reduced.

Can use various reactor modification, so that in the reaction mixture that second reaction zone contains, keep the more uniform low oxygen partial pressure in the gas dissolved not.A kind of preferred replacement scheme is that the impeller system of selecting to be suitable for making gas enter reaction mixture fast from the head space interface is used for second stirred-tank reactor 40, as available from Lightnin (Rochester, New York, A340 U.S.A) go up pump shaft stream impeller system.This impeller system is drawn into gas the liquid reaction mixture from head space, make the difference between the oxygen partial pressure of the oxygen partial pressure be drawn into the gas in the liquid reaction medium and head space gas reduce, thereby reduced the averaged oxygen spatial concentration in the not gas dissolved of reaction mixture.In addition, can change second stirred-tank reactor 40, make to contain O ₂Gas is sent in the head space on the reaction mixture, rather than directly is distributed in the liquid reaction mixture.This will further reduce the formation of hyperoxia concentration air pocket.Perhaps, the averaged oxygen spatial concentration can reduce by with impeller the head space gas in second stirred-tank reactor 40 being incorporated in the liquid reaction mixture.The commercially available example that comprises this impeller system of the quill shaft that is used for gas transport is the DISPERSIMAX system, and (Nogent-sur-OiseCedex France) sells by Autoclave France.Another possibility is to reduce the O that contains that is incorporated into second stirred-tank reactor 40 ₂O in the gas ₂Concentration (for example, air can be used as the oxygen source that supplies to second oxidation reaction zone).

In another modification, second continuous stirred tank reactor 40 is substituted by the ejector nozzle loop reactor.The flow chart of this reactor is shown among Fig. 7.Here, the water-containing material stream 901 that will comprise at least a portion of the middle aqueous reaction mixture 41 of being discharged by first oxidation reaction zone is pumped into import 903, is ejected into mixing section 909 by nozzle 907 again, also contains O through import 911 to wherein introducing ₂Gas (is about to contain O ₂Gas is incorporated in the venturi of nozzle 907 in civilian Qiu).This has produced high mass transfer coefficient, so that oxygen is delivered in the water-containing material 901.Because this high oxygen mass transfer coefficients and the height stirring within reaction vessel 913 that is caused by nozzle 907, the averaged oxygen spatial concentration in the not gas dissolved of liquid reaction mixture 915 is low.Reaction mixture flows out thing 917 discharges near the outlet reaction vessel 913 bottoms 919, cooling in heat exchanger 921, and again by catalyst filter 922, preferred cross-flow filter filters.Use pump 925, will flow out the thing 917 isolating catalyzer from reaction mixture and get back in the reactor 913 through catalyst recycle logistics 923 recirculation.The filtrate 927 of containing most of N-((phosphonomethyl)) glycine product is delivered to and is carried out purifying in other step and/or concentrate.People such as VanDierendonck at " Loop Venturi Reactor-A Feasible Alternativeto Stirred Tank Reactions? ", Ind. Eng. Chem. Res.37, the operation and the design of ejector nozzle loop reactor have been described among the 734-738 (1998), its whole disclosures are combined in here by reference.The commercially available example of ejector nozzle loop reactor is by Kvaerner Buss CPS (Pratteln, Switzerland) the BUSS loop reactor of Xiao Shouing.Should be appreciated that, except in comprising the flow reactor system of placed in-line a plurality of oxidation reaction zones, provide second or the subsequent oxidation reaction zone, the ejector nozzle loop reactor is fit to provide first oxidation reaction zone equally.The oxidation reaction condition of ejector nozzle loop reactor and operating parameters be similar to above for the oxidation reaction zone that provides by stirred-tank reactor described those.

The discussion great majority of front concentrate on the flow reactor system that utilizes heterogeneous beaded catalyst slurry and comprise placed in-line at least two stirred-tank reactors (oxidation reaction zone of basic back mixing in liquid phase at least is provided).Yet, should be realized that the reactor configuration except that stirred-tank reactor can be more suitable in one or more oxidation reaction zones equally or than stirred-tank reactor, or can be used in combination with a plurality of stirred-tank reactor sections.And many this selective reactor configuration are suitable for comprising the flow reactor system of single oxidation reaction zone equally.Utilizing one of the shortcoming of the flow reactor system that comprises one or more stirred-tank reactors of beaded catalyst slurry is capital and the running cost relevant with catalyst recycle mechanism, comprises reclaiming N-((phosphonomethyl)) the necessary catalyst filter of glycine product or other catalyst separation device.Therefore, wherein the catalyzer reactor configuration that can be retained in oxidation reaction zone can provide economical advantage in some applications.Two examples of such reactor configuration are fixed catalyst bed reactors and fluidized-bed reactor.Another advantage of fixed-bed reactor and fluidized-bed reactor is that they can be operated in the mode of performance piston flow characteristic; this often forms undesirable by product (for example N-methyl-N-((phosphonomethyl)) glycine) and so higher N-((phosphonomethyl)) glycine product yield of low concentration.

Fig. 8 has shown the example according to the fixed-bed reactor 500 of one embodiment of the invention.Being arranged within the reactor 500 is the primary oxidation reactor district, and it comprises contains oxide catalyst, the primary fixed bed 501 of the catalyzer of especially above-mentioned drastic reduction.Fixed bed upholder 502 is preferably placed in the reactor 500, with on the fixed bed 501 and under chamber 503 and following chamber 504 are provided respectively.The water-containing material stream 505 that comprises N-((phosphonomethyl)) iminodiethanoic acid substrate is incorporated into chamber 503 continuously or intermittently by nozzle 506 or other appropriate liquid distribution system, and is distributed in the fixed bed 501.Contain O ₂Gas is incorporated in the chamber 503 equally.When containing O ₂The downstream concurrent of gas and liquid reaction mixture is when fixed bed 501, and N-((phosphonomethyl)) iminodiethanoic acid substrate is by oxidation continuously.Comprise the primary reactor effluent 507 of N-((phosphonomethyl)) glycine product and comprise CO ₂Steam flow from discharging together the chamber 504 down.

Though in Fig. 8, show the liquid reaction mixture of process fixed bed 501 and contain O ₂The downward coflow of gas, but it should be understood that various mobile combinations are possible.For example, water-containing material stream 505 and contain O ₂Gas can be incorporated into the following chamber 504 of reactor 500, and in the same way, up stream is through fixed bed 501.Perhaps, liquid reaction mixture and contain O ₂Gas can reverse flow through fixed bed 501, wherein contain O ₂Gas is introduced in down chamber 504 and water-containing material stream 505 is introduced in chamber 503, perhaps just in time in contrast.

Temperature in the oxidation reaction zone of fixed-bed reactor 500 more preferably from about 60 to about 140 ℃, also more preferably from about 80 arrives about 130 ℃, and goes back further preferred about 90 in about 120 ℃ scope preferably at about 20 to about 180 ℃.Though reactive system can be chosen adiabatic operation wantonly, but in the primary oxidation reactor district, be about to most of unconverted substrate and be incorporated into the excessive temperature that is run in the adiabatic operation in wherein the reaction zone, may cause the disadvantageous effect of catalyzer or the excessive formation of by product.At substrate is the occasion of acid, and the limited solubility of substrate is defined in Reactor inlet and keeps the temperature of temperature of saturation at least, to prevent that the substrate deposition of solids is in bed.Yet, require top temperature to remain in the above-mentioned scope to the influence of by product formation and catalyst degradation.In fact, this substrate conversion degree that will can obtain in insulation fix bed is restricted to and is not higher than about 10wt%, preferably is not higher than approximately 7%, is more typically in about 3% in about 5% scope, press the calculating of total reaction mixture benchmark.At substrate is the occasion of salt, and transformation efficiency is not subjected to the restriction of the solubleness of substrate, but still is limited in the above-mentioned scope because of the influence to catalyzer and by product formation.In order in single fixed bed, to obtain bigger transformation efficiency, must remove thermopositive reaction heat from reactive system.Though reaction zone in the same old way can adiabatic operation, but must reduce phlegm and internal heat from some local removing of reactive system, make unit weight sensible heat content difference between reaction mixture and water-containing material stream, remain below the value of the thermopositive reaction heat that per unit weight water-containing material stream produces in reaction zone.As described below, the measure of removing reaction heat can comprise the cooling reaction zone, or introduces the refrigerative recirculation stream with the water-containing material mixture.By cooling off by this way, the transformation efficiency of representing with the difference between reaction mixture composition and the raw material composition can be increased to more than 10%, and even more than 15%.At substrate and product is the occasion of water-soluble salt, and transformation efficiency can be increased to 20%, 30%, and even 50%.

Compare with the temperature control of back mixing reactor assembly, the temperature in the control fixed-bed reactor oxidation reaction zone is generally more difficult.As shown in Figure 8, primary reactor effluent 507 can be divided into elementary product fraction 508 and recirculation fraction 509, and the latter turns back to the import of reactor again in the exterior cooling of reaction zone.Usually, the primary reactor effluent 507 of discharging from reactor at least about 5%, preferably at least about 33%, more preferably from about 50% to about 90% and more more preferably from about 60% is transferred to the recirculation fraction to about 80% quilt.Expression in another way, the ratio of the volumetric flow rate of recirculation fraction 509 and primary reaction product fraction 508 generally is at least about 0.05: 1, preferably at least about 0.5: 1, more preferably from about 1: 1 to about 10: 1 and most preferably from about 1.5: 1 to about 5: 1.Before turning back to reactor, the recirculation fraction is in the exterior cooling of fixed bed, and cooling is carried out in heat exchanger 510.In an embodiment shown in Figure 8, the primary reaction mixture of discharging from reactor is divided into elementary product fraction and recirculation fraction, and removes the product fraction before the recirculation fraction feeds heat exchanger.This yes-no decision can be favourable in certain embodiments, for example, contains unreacted N-((phosphonomethyl)) the iminodiethanoic acid substrate or the by product C that will carry out oxidation in other reaction zone in elementary product fraction ₁The occasion of compound.In shown in Figure 8 one selective embodiment, preferably pass through whole primary reaction mixtures, or whole basically primary reaction mixtures feed in the external heat exchanger (as at 510 place's diagrammatic heat exchangers), after this refrigerative primary reaction mixture stream passes is divided into recirculation stream and the elementary fraction of refrigerative, produces refrigerative product fraction.

Refrigerative recirculation fraction 509 and water-containing material stream 505 are mixed, form the merging inlet stream of primary reaction zone.Because reaction; the N-of recirculation fraction ((phosphonomethyl)) iminodiethanoic acid substrate is poor relatively; can be used for making the maximized factor of productivity is to introduce the water-containing material mixture with high substrate content, comprises that concentration of substrate surpasses the solubility limit of this substrate at the raw mix aqueous phase.Because the substrate of recirculation fraction is poor relatively, the blended effect is to form the merging inlet stream that substrate content is starkly lower than the water-containing material mixture.This dilution effect makes that the concentration of raw mix can be more much higher than other possible mode.For example, raw mix can comprise the slurry in N-((phosphonomethyl)) the iminodiethanoic acid aqueous solution saturated or saturated substantially at it, and this slurry often can cause the obstruction of stationary catalyst bed when adopting alternate manner.Mix with the recirculation fraction and N-((phosphonomethyl)) iminodiacetic acid (salt) acid content to be reduced to be enough to dissolve slurry solids and the merging that does not contain solid substrate substantially inlet stream is provided.Usually, also make the temperature that merges logistics surpass the temperature of water-containing material mixture, further help the dissolving of substrate solid from the heat of recirculation fraction.And because before reaching high conversion, N-((phosphonomethyl)) iminodiethanoic acid to the oxidation of N-((phosphonomethyl)) glycine is zero level basically, so this dilution effect can influence speed of response sharply.Randomly, water-containing material mixture and recirculation fraction can be imported mixing tank, to guarantee that solid is dissolved before the inlet stream that will merge is incorporated into stationary catalyst bed.By this way; can introduce and comprise the water-containing material mixture of about 8wt% to N-((phosphonomethyl)) iminodiethanoic acid of about 15wt%, and by with this water-containing material mixture with comprise about 0.5wt% extremely the primary reactor recirculation fraction of N-((phosphonomethyl)) glycine of about 5wt% mix the inlet stream that produces merging.As mentioned below, be that the water-soluble salt and the product of N-((phosphonomethyl)) iminodiethanoic acid is the occasion of the water-soluble salt of N-((phosphonomethyl)) glycine at substrate, can handle obviously higher concentration.

Should be appreciated that, in the substrate content process that reduces the inlet stream that merges, water-containing material stream also plays the catalyst bed liquid phase inlet stream that reduces to merge and the effect of the substrate content difference between the logistics of catalyst bed liquid exit with the recycled matter diluted stream, and this difference can be remained on as mentioned above in the adiabatic reaction district in the admissible scope.Keeping this restriction to the ratio conversion of substrate in this reaction zone, is important in the system of Fig. 8, because catalyst bed adiabatic operation basically itself, though entire reaction system (comprising the recirculation loop) is not adiabatic operation.

In selective embodiment (not shown) of the present invention; the flow reactor system can comprise second oxidation reaction zone; can introduce part or all of primary reaction product fraction 508 continuously to this district, so that further transform N-((phosphonomethyl)) iminodiethanoic acid substrate and oxidation C ₁By product.In this embodiment, all primary reactor effluents 507 can be transferred in the heat exchanger recirculation loop, and tell elementary product fraction 508 in the recirculation fraction 509 in heat exchanger 510 downstreams.By this way, before elementary product fraction 508 is incorporated into second oxidation reaction zone, therefrom remove some exothermic heat of reaction.Second reaction zone contains oxide catalyst, and can carry out back mixing, as providing in the continuous stirred tank reactor, perhaps can comprise second stationary catalyst bed.In second reaction zone, residual N-((phosphonomethyl)) the iminodiethanoic acid substrate in the primary reaction product fraction is oxidized to N-((phosphonomethyl)) glycine continuously.In comprising the preferred embodiment of placed in-line two or more fixed-bed reactor; be reflected at that to proceed to N-((phosphonomethyl)) iminodiethanoic acid substrate in the primary oxidation reactor district higher (for example at least about 95% to the transformation efficiency of N-((phosphonomethyl)) glycine product; preferably at least about 98%); this is very feasible; because oxidation is carried out with apparent zeroth order reaction; up to initial N-((phosphonomethyl)) the iminodiethanoic acid substrate that small portion is only arranged, till for example being low to moderate 0.2ppm or being retained in the liquid phase below the 0.2ppm.By operation by this way, the thermal load of the reaction mainly heat exchanger in the recirculation loop of primary reactor 510 is scattered and disappeared, and second oxidation reaction zone can operate adiabaticly substantially, and temperature only suitably increases.Randomly, reaction heat can be removed to the cooling liqs of the heat exchanger (for example spiral coil cooling tube) that is arranged in second reaction zone.Do not have this configuration of round-robin make liquid reaction mixture in the mode of basic piston flow by second fixed bed (promptly not having the back mixing of liquid phase substantially).Plug flow operation is wished in second reaction zone, because substrate becomes the first order reaction of high conversion substantially to the oxidation of N-((phosphonomethyl)) glycine product.Plug flow operation makes the kinetics-driven power maximization of eliminating residual N-((phosphonomethyl)) iminodiethanoic acid substrate and the amount that has reduced the by product that is formed by peroxidation.

Preferably, elementary and second catalyst bed all contains precious metal/C catalyst, and this catalyzer is the efficient oxidation N-((phosphonomethyl)) iminodiethanoic acid substrate and C simultaneously ₁By product, i.e. formaldehyde and formic acid.

Because precious metal is mainly used in catalysis C ₁The oxidation of by product; and the oxidation of N-((phosphonomethyl)) iminodiethanoic acid substrate mainly comes catalysis by carbon; a selective embodiment of the present invention comprises that use mainly is made up of C catalyst, or bullion content obviously is less than the primary fixed bed of the catalyzer that disposes in second fixed bed.Second reactor comprises precious metal/C catalyst, to guarantee C ₁The oxidation of by product.Because C ₁Oxidation under any circumstance is first order reaction substantially, more effectively carries out under the basic plug flow conditions that it keeps in second reactor usually, owing to produce the heat release of much less in this stage.Thermal load in second reactor may be quite gentle, makes it to operate without external heat exchanger with without back mixing or recirculation.In fixed bed system, precious metal carrying capacity that can applying unit weight catalyzer is lower than the catalyzer of unit weight catalyzer precious metal carrying capacity best for continuous back mixing reactive system.

In another embodiment, the 3rd fixed bed reaction district can be provided, this district also preferably includes the fixed bed that contains precious metal/C catalyst, and can be substantially with plug flow operation and randomly, in fact preferably under adiabatic condition, operate.Only use the occasion of C catalyst at first reactor, this selection may be valuable especially.Therefore, N-((phosphonomethyl)) iminodiethanoic acid substrate to the oxidation of N-((phosphonomethyl)) glycine is fully being carried out in the primary oxidation reactor district in the presence of the C catalyst, but C ₁By product often is accumulated in the primary reactor effluent.Second reaction zone has promoted the elimination and the C of substrate ₁The oxidation of by product, the two is the promoted first order reaction of basic plug flow operation by second fixed bed substantially.Residual C ₁Compound is eliminated in the 3rd fixed bed oxidation reaction zone effectively.

In order in the primary oxidation reactor district, to obtain high conversion, each fixed bed reaction district, especially primary reaction zone is preferably operated under high relatively oxygen partial pressure, transfers in the liquid phase to promote oxygen.Integral mean oxygen partial pressure on the liquid phase flow process in the preferred primary oxidation reactor district is at least about 50psia, preferably at least about 100psia, more preferably at least about 200psia.In some embodiments, about 300psia can suit to the integral mean oxygen partial pressure of about 500psia.The oxygen level of the gas phase in gas reactor exit can be in 20% to 30% scope, or even lower.Can also be as mentioned below, the height ratio by the liquid reaction mixture volume in catalyst surface area and the fixed-bed reactor promotes the oxygen transmission.Coefficient of oxygen utilization in primary reaction zone preferably about 50% to about 95%.Usually, oxygen is with about 1.5 to about 10molO ₂The amount of/molN-((phosphonomethyl)) iminodiethanoic acid substrate is given to reactor.Total working pressure in fixed-bed reactor 500 generally can be higher than the total working pressure in the stirred-tank reactor, and preferably about 0 to about 1000psig, more preferably from about 300 to about 1000psig and more more preferably from about 100 arrive about 300psig.

Usually, low slightly oxygen partial pressure can be preferred in the second and/or the 3rd fixed bed oxidation reaction zone, so that avoid the peroxidation of catalyzer and undermine its oxidation C ₁The effectiveness of by product.Therefore, in the second or the 3rd reaction zone,, be more preferably about 30psia to about 100psia along the preferably about 30psia of the integral mean oxygen partial pressure of liquid flow path to about 300psia.Scheme as an alternative, the primary fixed bed bioreactor of Fig. 8 and/or the placed in-line second or the 3rd fixed-bed reactor can use oxygenant such as H ₂O ₂But not molecular oxygen operates, and in this case, total reaction pressure and oxygen partial pressure can be starkly lower than above-mentioned pressure.

In order to prevent the catalyzer peroxidation, generally preferably, the oxygen partial pressure of any fixed-bed reactor liquid outlet is not higher than about 100psia, and preferably about 10psia is to about 50psia.Further preferably, in any position of fixed bed, oxygen partial pressure is no more than about 50psia, and wherein the N-of liquid phase ((phosphonomethyl)) iminodiethanoic acid substrate content is lower than 0.2ppm; More preferably, in this any position, oxygen partial pressure is maintained at about below the 50psia, and wherein the substrate content of liquid phase is lower than about 0.1ppm.

In another embodiment, the flow reactor system can comprise the fixed-bed reactor of placed in-line a plurality of shorter (or narrower), makes from the intermediate reaction mixture outflow thing of one section discharge and enters next section.This embodiment is different from above-mentioned two or three reactor assemblies, and difference is, only obtains the transformation efficiency of appropriateness in any a section of narrow relatively fixed-bed reactor section series.Because the substrate conversion efficiency in any one is relatively limited, each can operate adiabaticly substantially, heat exchanger is placed between short fixed-bed reactor of each successive and the next reactor, with reaction mixture, make that the temperature of reaction mixture is no more than the desired procedure temperature in any one fixed-bed reactor.Comprise the occasion of two above reactors at described serial reaction device, may only need to cool off from first, two or three intermediate reaction mixtures that the fixed bed reaction district discharges, after this, remaining district can operate with adiabatic method.Temperature of reaction in fixed-bed reactor can also be controlled by for example introduce passage or conduit separately in fixed bed, heat-eliminating medium can flow through this passage or conduit.Be noted that in this embodiment all reactors that are not this series must be fixed-bed reactor.For example; first reactor of this series can be a continuous stirred tank reactor; in this reactor; N-((phosphonomethyl)) iminodiethanoic acid substrate to the oxidation of the zero level basically of N-((phosphonomethyl)) glycine product can proceed to basic conversion; produce the intermediate reaction mixture; this intermediate reaction mixture can be transferred to fixed-bed reactor, or serial fixed-bed reactor, transforms and oxidized residual C to finish ₁By product.

The fixed-bed reactor (for example comprising honeycomb substrate as shown in FIG. 1) that contain the catalyzer of integral form sometimes than the reactor of the fixed bed that contains the discrete catalyst particle more preferably.This is because if N-((phosphonomethyl)) the iminodiethanoic acid substrate that contains in water-containing material stream 505 precipitates with any significance degree in oxidation reaction zone, the fixed bed of catalyst particle may be blocked.Therefore, the concentration of general requirement N-((phosphonomethyl)) iminodiethanoic acid substrate in water-containing material stream 505 is no more than saturation concentration under reactor feed temperature, and this may significant limitation output.Yet; if fixed bed 501 comprises the catalyzer of honeycomb or similar integral form; passage wherein can be made straight substantially and have enough big cross section, makes them can not contained the reaction mixture obstruction of solid N-((phosphonomethyl)) iminodiethanoic acid substrate slurry.Even packed bed reactor is not blocked, integer catalyzer can be fallen operation at significantly lower pressure.Must weigh and consider that this potential advantage cost relevant with the production integral carriers that utilizes integer catalyzer in fixed-bed reactor increases (comparing with general preferred obviously more cheap usually pill or particulate vector in enforcement of the present invention).Be given to a plurality of fixed bed sections of each section with independent N-((phosphonomethyl)) iminodiethanoic acid substrate feedstream using, thereby in the feedstream that is given to the first fixed bed section, do not need high concentration of substrate to obtain the occasion of required output, especially like this.

Another advantage of fixed-bed reactor is that by merging different catalyzer, activity of such catalysts can optionally change in the total length of fixed-bed reactor section, or different with next section at the mobile direction the preceding paragraph of reaction mixture.For example, in the upstream portion of fixed-bed reactor section or former sections, low activity catalyst (for example only being C catalyst) can be used, and high activated catalyst (the metal/carbon catalyzer that for example drastic reduction is expensive) can be used in the downstream part of fixed-bed reactor section or back several sections of multistratum system at multi-stage fixed-bed reactor assembly.As selection, fixed bed can make up and comprise oxide catalyst body and being used to and promote other measure of gas/liquid mass transfer as annular, saddle type or structured packing.Annular, saddle type or other inert filler play the thinner of catalyzer, thereby regulate the activity of catalyst bed.By this way, the activity of catalyst bed can longshore current body flow direction changes with the variation of the surface-area of catalyst body surface-area/inert filler.The variation of this catalyst activity is used for compensating the density loss of N-((phosphonomethyl)) iminodiethanoic acid substrate at reaction mixture, reduces the catalyzer cost and the precious metal losses of this method simultaneously.

Fixed-bed reactor are owing to the piston flow characteristic produces the trend of undesirable by product of low concentration, can be significantly higher than the effective catalyst surface-area of the ratio that uses and the ratio of the liquid in the working volume promotes in typical back mixing (being thorough mixing) reactor by use.In fact, reaction mixture can be by using such ratio to reduce or eliminating fully with the demand that reduces impurity formation.The fact that this has increased speed of reaction and therefore reduced liquid residence time owing to big effective catalyst surface-area.Residence time that reduces and then often reduce impurity, the especially formation of N-methyl-N-((phosphonomethyl)) glycine that forms by homogeneous reaction.In this embodiment, the ratio of catalyst B ET surface-area and liquid (delay liquid) volume in the working volume of fixed-bed reactor is preferably at least about 3m ²/ cm ³, more preferably from about 100 arrive about 6000m ²/ cm ³And more more preferably from about 200 arrive about 2000m ²/ cm ³In some applications, the delay flowing fluid ratio in catalyst B ET surface-area and the reactor most preferably is about 400 to about 1500m ²/ cm ³Scope in.The volume ratio preferably about 0.1 to about 0.7 of being detained liquid and total bed volume in the fixed bed.In certain embodiments, low liquid residence time and high surface make to volume ratio can be advantageously at for example 150 ℃ relatively-high temperature degree range operation fixed-bed reactor, wherein the integral mean temperature of the liquid phase in the liquid-phase flow path of primary fixed bed is about 80 ℃ to about 130 ℃, preferred 105 ℃ to 120 ℃.

According to the present invention, as described at Fig. 8 for example or hereinafter, as long as enough thermal heat transfer capability are provided, fixed-bed reactor can be operated under high yield.Usually, surpassing under about 50% N-((phosphonomethyl)) the iminodiethanoic acid substrate conversion efficiency, fixed-bed reactor can be at about 0.5hr ^-1To about 20hr ^-1The down operation of liquid hourly space velocity degree, be that benchmark calculates with the total catalyst bed volume.About 0.5 to about 5hr ^-1The liquid hourly space velocity degree can obtain down to surpass 95% or 98% more high conversion.Be appreciated that the liquid hourly space velocity degree is based on total liquid phase feed flowmeter.Therefore, in the described reactive system of Fig. 8, liquid phase feed stream comprises by mixing water-containing material mixture stream passes and recirculation stream, and can be incorporated into any other recirculation of fixed-bed reactor or the merging inlet stream that the cross-stream logistics is obtained according to the special process schema.Based on combining of these space-time speed and above-mentioned transformation efficiency; have been found that; N-((phosphonomethyl)) iminodiethanoic acid substrate can be in single fixed-bed reactor; about 0.05 to about 4; more generally about 0.2 under the productivity of about 2 mol/1hr-N-((phosphonomethyl)) glycine/pound aqueous reaction mixture, is converted into N-((phosphonomethyl)) glycine product.

As mentioned above, the catalyzer that utilizes in fixed-bed reactor can adopt various forms and comprise dissimilar carriers, comprises pill carrier and integral carriers.As shown in Figure 8, the general preferred oxide catalyst that contains at fixed bed 501 form (for example, the catalyzer of above-mentioned drastic reduction comprises the carbon pill carrier that deposits precious metal on it) that is pill.These pill catalyzer generally have about 1mm to about 100mm, and more preferably from about 1.5mm is to the granularity of about 5mm.Determine further that with respect to the carrying capacity on the comparable catalyzer that uses, the precious metal carrying capacity in the precious metal/C catalyst that uses can be low in fixed bed in slurry-phase reactor.For example, above-mentioned 200 to 2000m ²/ cm ³The BET surface uses precious metal charge capacity on carbon only to be the catalyzer of 2wt% in the liquid hold-up volumetric ratio, has obtained the valid function of fixed bed.Usually, the carrying capacity that is lower than 35wt% can be gratifying.Comprise the occasion of Pt/C at catalyzer, can be lower than under identical temperature, to provide in the continuous stirred tank reactor that is utilizing the Pt/C slurry catalyst in the platinum carrying capacity on the catalyzer and be equal to 70% of the required carrying capacity of productivity (by pound N-((phosphonomethyl)) glycine product/(a hour pound catalyzer)).

In fixed-bed reactor, be difficult to keep for a long time constant catalyst activity and selectivity.At last, catalyst activity and selectivity are reduced to unacceptable level, make reactor assembly have to close, so that carry out the replacement and/or the reactivate of catalyzer.Compare with the above-mentioned flow reactor system (wherein catalyzer replacement and/or reactivate can carry out when reactor assembly keeps running) of one or more stirred-tank reactors that comprises, this is disadvantageous.Can be by providing, and operate them in the alternative mode with the parallel standby fixed-bed reactor that are connected in the rest part of reactive system of valve, solve that catalyzer is removed and the problem of reactivate.Can remove catalyzer and replace from the withdraw from service reactor with live catalyst; Or can in the reactor of off-line, carry out reactivation of catalyst on the spot.

According to another embodiment of the invention, utilizing the particle heterogeneous catalyst, carry out the oxidation of N-((phosphonomethyl)) iminodiethanoic acid substrate in the circulating fluid bed reactor of preferred above-mentioned drastic reduction beaded catalyst.Circulating fluid bed reactor generally provides higher coefficient of mass transfer than stirred-tank reactor, and can operate in the mode that beaded catalyst is remained in the oxidation reaction zone substantially, making does not need catalyst filter or other catalyst separating measure, or at least obviously reduces the requirement that size and pressure are fallen.Fig. 9 has shown the example of circulating fluid bed reactor 400, wherein defines an oxidation reaction zone.Import 403 by drainage tube 405; the water-containing material stream 401 that will comprise N-((phosphonomethyl)) iminodiethanoic acid substrate is pumped into the top of reactor 400, is discharged near the bottom of reactor 400 in the liquid reaction medium 406 that contacts with catalyst particle 407 again.Contain O ₂Gas can be ejected in the reaction mixture by the nozzle 409 of reactor 400 bottoms.Reaction soln 412 is discharged from reaction zone at overflow port 411, comprises CO ₂The top of steam by reactor discharge.This reactor has on the discharge outlet that obviously is positioned at drainage tube 405, but the reaction mixture circulation outlet 413 under overflow port 411.Have the reaction mixture that is suspended in beaded catalyst wherein and discharge, by heat exchanger 421 circulations,, merge with feedstream 401 then, so that be incorporated in the reactor again through drainage tube 405 so that remove reaction heat through external loop-around 420 at outlet 413 places.By in loop 420, keeping high speed circulation (with respect to the velocity of discharge of raw material 401 feed speeds and reaction soln 412), set up upward flow speed in slurry zone, the bottom of oxidation reaction zone (generally under outlet 413), it is more much higher than the upward flow speed in the decantation zone, top (generally on outlet 413) of oxidation reaction zone.Select the size and the control recirculation flow of this equipment, make in the upward velocity in slurry zone, bottom obviously on the settling velocity of catalyst particle 407 and therefore effectively keep catalyzer to suspend in (promptly carrying secretly) reaction medium in the slurry zone.Yet the upward velocity in the decantation zone on outlet 413 is obviously under the settling velocity of catalyst particle 407, so that separate from exporting the 411 transparent relatively reaction soln decantates 412 of discharging.Usually, the size of the catalyst particle 407 that utilizes in reactor reactor as shown in Figure 9 is that about 200 μ m are to about 1000 μ m.For example, can remove the less catalyst particle that is entrained in the decantate 412 with polishing filter (polish filter) (not shown) in the initial stage.Therefore, slurry catalyst remains in the reactor, do not need to filter, perhaps do not need to have when can be with the catalyst concn in catalyst concn in the reaction soln 412 of stream forward and slurry zone suitable needed speed at least and remove the strainer of the ability of catalyzer.

In order to remove catalyzer, circulating fluid bed reactor can also comprise catalyst separating loop 414, and it is also illustrated among Fig. 9.In this loop, discharge the effluent slurry and feed catalyst filter 417 from the outlet 415 in the slurry zone of reaction zone, so that remove catalyzer 418.Fresh catalyzer 419 can be joined in the filtering reaction soln, this solution is by mixing with flow of fresh feed 401 and recirculation stream 420 being incorporated into drainage tube 403, and is recycled in the reactor.(for example remove activity and/or selectivity reduce catalyzer) as required, catalyst separating loop 414 can be continuously or periodical operation, and saved regular off-response device so that the needs of replacement beaded catalyst.Yet the ability of catalyst filter 417 needn't be about the same big with the above-mentioned strainer that is used for the reaction slurry separating catalyst of discharging from continuous stirred tank reactor.Therefore, can realize a large amount of saving of capital, operation and maintenance expense.

Can make various changes to fluidized-bed reactor shown in Figure 9 400.For example, not to contain O ₂Gas injection but provides and similar ejector nozzle shown in Figure 7 at the top of reactor in the reaction mixture 406 of reactor 400 bottoms, by this nozzle, with water-containing material stream 401 with contain O ₂Gas merges, and is discharged in the reaction mixture 406 again.Perhaps, by impeller, so that reaction mixture is drawn,, provide the circulation of the reaction mixture that contains beaded catalyst downwards by drainage tube and enter into the mode of the lower region of oxidation reaction zone at drainage tube 405 internal rotation.In addition, catalyst separating loop 414 optional can be incorporated in the heat transfer cycle loop 420.The oxidation reaction condition of circulating fluid bed reactor and operating parameters be similar to above for the oxidation reaction zone that provides by stirred-tank reactor described those.

In Figure 10, illustrate also selective embodiment of the present invention; wherein N-((phosphonomethyl)) iminodiethanoic acid substrate to the oxidation of N-((phosphonomethyl)) glycine product is comprising a plurality of reactor 800A, 800B, 800C ... carry out in the distributed reaction device system of 800n, wherein reaction mixture in order a reactor from this series advance to next reactor.The primary raw materials mixture 814 that will comprise N-((phosphonomethyl)) iminodiethanoic acid substrate is incorporated among the reactor 800A, is divided into parallel component raw material stream 802B, 802C, the 802D that is assigned in the serial reaction device with replenishing raw mix ... 802n.Each reactor is through feed pipeline 804A, 804B, 804C ... 804n accepts oxygen or other oxidant constituents of distributed supply.Randomly, heat exchanger 806A, 806B, 806C etc. are inserted between each subsequent reactor and the last reactor, so that remove the intermediate reaction mixture 810A that discharges by front reactor 800A, 800B, 800C etc., the reaction heat of 810B, 810C etc., if desired and each reactor can be operated with adiabatic method.Perhaps, refrigerative recirculation stream 808A, 808B, 808C, 808D etc. can turn back to each reactor, so that remove exothermic heat of reaction and the cooling of reaction mixture in reactor is provided.In each of serial reaction device after the first reactor 800A, inlet stream 812B, the 812C, the 812D that merge ... 812n is component raw material stream 802B, 802C, 802D etc., deduct the binding substances of any recirculation stream 808A, 808B, 808C, 808D etc. and any recirculation stream 808B, 808C, 808D etc. from the intermediate reaction mixture of last reactor 810A, discharges such as 810B, 810C.Each reactor 800A, 800B etc. can suppose it is any mechanism described here, but preferably catalyzer is retained in the form (for example fixed bed or fluidized-bed reactor) of reactor wherein.Final reacting product 810n discharges from last reaction zone 800n of reaction zone series.

Each component raw material stream 802B, 802C etc. of distributed reaction device system can be highly spissated, thereby help the high productivity of this method.In fact, can use component raw material stream or the paste component feedstream that comprises dense thick N-((phosphonomethyl)) iminodiethanoic acid substrate slurry.In each subsequent reactor after the first reactor 800A (for example reactor 800B); can introduce slurry or paste component raw mix; although preferred (especially under the situation of fixed-bed reactor) component 802B raw material is formed; component 802B delivery rate; composition and the flow velocity of the intermediate reaction mixture 810A (deducting any recirculation 808A) that discharges from last reactor 800A come the combination of any recirculation 808B of the intermediate reaction mixture of autoreactor 800B should make the inlet stream 812B that merges not contain substrate solid or N-((phosphonomethyl)) glycine product solid substantially.Yet, it will be understood to those of skill in the art that in certain embodiments of the invention component raw material and intermediate reaction mixture can be slurry forms fully, for example be the occasion of homogeneous catalyst at oxide catalyst, or in the occasion of the fixed bed that utilizes integer catalyzer such as honeycomb style.

Though preferably other component raw material stream 802B, 802C etc. are incorporated into first reaction zone serial reaction district 800B afterwards with oxygenant, in each of 800C etc., but should be appreciated that, in application-specific, necessary or it is desirable to only the component reaction mixture be supplied to, rather than all in the subsequent reaction zone.In some instances, can not will oxygenant supply with all reaction zones, though in most of the cases, it is preferred that oxygenant is supplied with each district.

Fixed bed of the present invention and distribution raw material embodiment are particularly suitable for the water-soluble salt of N-((phosphonomethyl)) iminodiethanoic acid is converted into the water-soluble salt of N-((phosphonomethyl)) glycine.Because the basic metal and the amine salt of substrate acid and product acid, for example potassium, ammonium, isopropylamine and alkanol amine salt generally all have high-dissolvability, no matter be that fixed bed or stirred-tank reactor all can be operated under substrate more much higher than sour method and production concentration, the productivity of sour method is subjected to low relatively solubility limit.In fact, under the situation of salt, fixed-bed approach can be particularly advantageous because it can need not be used to remove crystallized product remove any filtration of catalyzer or the situation of centrifugally operated under operate.N-((phosphonomethyl)) glycinate solution can with the industrial application that is generally used for N-((phosphonomethyl)) glycine in and can come the various excipient of dissolved composite with minimum other processing.In order to produce desirable commercial concentrated solution, only need the enrichment step of appropriateness.Can not need a large amount of impurity to separate.

Because with the oxidation of high concentration substrate and the C of relative vast scale ₁The relevant bigger reaction heat of exothermic oxidation of following of by product such as formaldehyde and formic acid is loaded, the stirring tank reactive system, and especially the continuous stirred tank reactive system may be favourable for the synthetic of salt.Continuous stirred tank reactor provides significant advantage than batch reactor aspect the water-containing material of reactor utilizing the reaction heat preheating to be given to.The elementary continuous stirred tank that is used for initial conversion also can be favourable with combining of fixed bed end reaction device.

Yet the basic plug flow reactor of fixed bed provides special advantage, especially comprises the occasion of precious metal/carbon at catalyst bed, because plug flow operation can promote C ₁The oxidation of by product promptly is the C of one-level substantially ₁Substrate reactions.But because identical reason, piston flow has aggravated the reheat load relevant with the oxidation of the water-containing material mixture that contains high concentration substrate salt.Though it is heat passage fully that the recirculation reactive system of Fig. 8 can be used for setting up, the destruction kinetics of its PARA FORMALDEHYDE PRILLS(91,95) and formic acid has disadvantageous effect, although according to recirculation rate, to C ₁The destructive influence can keep being better than slightly complete back mixing reactor.

Therefore, in some instances, fixed bed may be favourable by hot indirect transfer is carried out in the refrigerative reactive system oxidizing reaction to the cooling fluid that comprises heat transfer fluid or process fluid therein, and wherein said cooling fluid is flowed through in the catalyst bed or the conduit of contact with it.For example, fixed bed can be arranged on the shell-side or the pipe side of shell-and-tube exchanger, and wherein cooling fluid is through the opposite side of interchanger.In such embodiment, fixed bed can comprise the polycomponent bed that separately is arranged in the heat exchanger tube, and wherein water-containing material mixture and oxygenant are assigned in each component bed, and the flow through shell-side of described heat exchanger of cooling fluid.In a selective embodiment, fixed bed can be included in the shell of heat exchanger, and the baffle plate on the shell-side is optional, and be used to guarantee to flow through this liquid phase is piston flow substantially.

Perhaps, the salt of N-((phosphonomethyl)) glycine can prepare in the serial reaction device that the aforesaid heat exchanger that is used to cool off intermediate reaction solution separates.The distributed charging reactive system of Figure 10 can be especially favourable handling aspect the thermal load that produces to the oxidation of N-((phosphonomethyl)) glycinate at N-((phosphonomethyl)) Iminodiacetate.Such as described, all are occasions of water-soluble salt at substrate and product, can obtain especially high productivity.For example, contain occasion at least about 15wt% substrate salt at the water-containing material mixture, final reacting mixture can contain the water-soluble products salt at least about 12wt%; Contain occasion at least about 25wt% water soluble substrate salt at the water-containing material mixture, final oxidation mixtures can contain the water-soluble products salt at least about 20wt%; With the occasion that contains at the water-containing material mixture at least about the water soluble substrate salt of 35wt%, final oxidation mixtures can contain the water-soluble products salt at least about 28wt%; All be by the acid equivalent benchmark.In fact, even can realize surpassing 35wt%, preferably surpass the high product salt concn of 40wt% and even 50wt%.As mentioned above, final reacting product can be the primary reaction mixture that obtains in single reaction vessel, as the elementary product fraction of the single recirculation fixed bed system described at Fig. 8 or as at last effluent of the above serial reaction device that further describes.

Final reacting product preferably further concentrates by removing to anhydrate.For example, final reacting mixture can be incorporated into flash zone, and in this district, pressure is lower than final oxidation mixture and discharges vapour pressure under last the temperature of reactor or serial reaction device at it.With low relatively energy expenditure, can from final oxidation reaction product, remove enough water, to obtain to contain concentrated solution at least about 40wt% (by acid equivalent) N-((phosphonomethyl)) glycine water-soluble salt.

Usually, in the oxidation mixtures effluent of being discharged by reactor assembly of the present invention, the concentration of N-((phosphonomethyl)) glycine product can be up to 40wt%, and is perhaps higher.Preferred N-((phosphonomethyl)) glycine production concentration is about 5 to about 40%, more preferably from about 8 to about 30% and also more preferably from about 9 to about 15%.The concentration of formaldehyde in product mixtures preferably is lower than about 5000ppm, more preferably less than about 4000ppm, also more preferably less than 2800ppm with also more more preferably less than 1500ppm, by weight.It is about 12 that the concentration of formic acid in product mixtures preferably is lower than, and 000ppm is more preferably less than about 4000ppm, also more preferably less than about 2000ppm with also more more preferably less than about 1500ppm, by weight.Aminomethylphosphonic acid (AMPA), N-methyl-aminomethylphosphonic acid (MAMPA), the concentration of N-methyl-N-((phosphonomethyl)) glycine (NMG) in product mixtures are controlled at easily and are lower than 9000ppm separately; usually can be controlled in and be lower than 4500ppm and remain on below the 1500ppm usually.It should be understood that; the concentration of these by products is based on the single-pass operation pattern, and the unique raw material that wherein is given to reactor assembly is to contain by N-((phosphonomethyl)) iminodiethanoic acid of the (phosphonomethyl) acquisition of iminodiethanoic acid or the aqueous mixture of its salt.Any recirculation stream is being incorporated into the occasion of reactor assembly as the decantate from the adiabatic crystallizer of the following stated, and the recirculation of following of by product has often increased the by-products content of mixture of reaction products.

Purifying and/or concentrated N-((phosphonomethyl)) glycine product

Another aspect of the present invention relates to purifying and/or is concentrated in N-((phosphonomethyl)) the glycine product that obtains in the oxidation mixtures effluent.The various improvement of being reclaimed by N-provided by the invention ((phosphonomethyl)) glycine product have widely uses, and for example can be used for oxidation mixtures recovery N-((phosphonomethyl)) the glycine product of producing from by described here various continuous oxidation reaction device system.Yet of the present invention this is not limited to this application or general and the system combined use of continuous oxidation reaction device on the other hand.Such as clear to the skilled person, the strategy of Chan Shuing can advantageously be applied to reclaim N-((phosphonomethyl)) glycine product from the oxidation mixtures effluent of producing by other reactor assembly (comprising the batch reactor system) here.

Except required N-((phosphonomethyl)) glycine product, reaction mixture normally also contains water and various impurity.These impurity can comprise for example various by products and unreacted starting raw material; as unreacted N-((phosphonomethyl)) iminodiethanoic acid substrate; N-formyl radical-N-((phosphonomethyl)) glycine, phosphoric acid, phosphorous acid; vulkacit H; aminomethylphosphonic acid, N-methyl-aminomethylphosphonic acid, iminodiethanoic acid; formaldehyde, formic acid etc.The value of N-((phosphonomethyl)) glycine product has normally been indicated the maximum product yield from reaction mixture, also usually provides at least a portion dilution reaction mixture is recycled to oxidation reaction zone so that further transform unreacted substrate and the motivation of the product that recovery is not recovered.

The consideration of commercial aspect also requires the concentration of N-in the mixture of commercial distribution ((phosphonomethyl)) glycine product to be significantly higher than concentration in the reaction mixture that uses above-mentioned oxidation system to form usually sometimes, especially is used for the occasion of agricultural purposes at N-((phosphonomethyl)) glycine product.For example; when using heterogeneous catalyst when preferred service temperature (promptly about 95 to about 105 ℃) prepares N-((phosphonomethyl)) glycine free acid down; the maximum concentration of N-((phosphonomethyl)) glycine product in reaction mixture preferably is not more than about 9wt%, so that it can keep dissolving.Yet, wish that sometimes the mixture of commercial distribution has significantly higher N-((phosphonomethyl)) glycine concentration.

Therefore, N-((phosphonomethyl)) glycine product formed and if necessary with catalyst separating after, general preferably product concentrated and product is separated with various impurity in the oxidation mixtures.

Smith (the U.S. patent No. 5,087,740) has described a kind of method that is used for purifying and concentrated N-((phosphonomethyl)) glycine product.Smith discloses the reaction mixture that will contain N-((phosphonomethyl)) glycine and has fed first ion exchange resin column; so that remove the impurity that acidity is better than N-((phosphonomethyl)) glycine; to feed second ion exchange resin column of absorption of N-((phosphonomethyl)) glycine from the effluent of first ion exchange resin column, reclaim N-((phosphonomethyl)) glycine by alkali or strong inorganic acid are fed second ion exchange resin column again.

Many other technology that are used for purifying and concentrated N-((phosphonomethyl)) glycine product comprise crystallisation step, and wherein N-((phosphonomethyl)) glycine product is by crystallization, so that separate it from least a portion residue reaction mixture.

Diagram and method for product recovery described below in Figure 11-14A; by the oxidation mixtures that contains easy crystalline N-((phosphonomethyl)) glycine product, those oxidation mixtures that especially contain N-((phosphonomethyl)) glycine free acid concentrate and reclaim in the product has special application.Dense N-((phosphonomethyl)) glycine free acid generally is used to prepare other N-((phosphonomethyl)) glycine product, as above-mentioned those.

In particularly preferred embodiments; (preferably there is not any catalyzer at least a portion final reacting mixture; especially do not have any heterogeneous catalyst or homogeneous catalyst with N-((phosphonomethyl)) glycine product cocrystallization) be incorporated in the nonadiabatic heat driving evaporative crystallizer; wherein heat is applied in oxidation mixtures; so that from this reaction mixture vaporize water, thereby and concentrate and crystallization N-((phosphonomethyl)) glycine product.The heat of using in nonadiabatic crystallizer is normally obtained by steam.Preferably in nonadiabatic crystallizer system, evaporate in the reaction mixture at least about 30%, more preferably at least about 50%, more more preferably from about 80% to about 100%, also more preferably from about 90% near 100% water.Evaporative crystallization is particularly advantageous, because it is also with product and small molecular weight impurity, formaldehyde separates with formic acid the most in particular, and these small molecular weight impurities often are evaporated from reaction mixture with water.

The pressure that heat drives in the evaporative crystallizer preferably is not higher than about 10psia, more preferably from about 1 arrives about 10psia, more more preferably from about 1 arrives about 5psia, also more preferably from about 2 arrives about 3psia and further preferably about 2.8psia.The service temperature that heat drives evaporative crystallizer preferably is not higher than about 80 ℃, and more preferably from about 40 ℃ to about 80 ℃, more more preferably from about 50 ℃ are arrived about 70 ℃ and also more preferably from about 60 ℃.

Figure 11 has shown the example that uses a system of evaporative crystallizer.The water-containing material 201 that will comprise N-((phosphonomethyl)) iminodiethanoic acid substrate is incorporated into the oxidation reactor system 203 that comprises one or more oxidation reaction zones; substrate is oxidized in this system, has formed the oxidation mixtures 205 that comprises N-((phosphonomethyl)) glycine product.Figure 11,12,13 and 14A in, the details of oxidation reactor system, (for example comprise the catalyst separating that may exist and recirculation unit, catalyst filter, catalyst stores jar, the preceding flash tank of strainer etc.) be omitted, this is interpreted as, the oxidation mixtures of discharging from reactor assembly according to employed specific reactor configuration, has been removed catalyzer as required substantially.Oxidation mixtures 205 is chosen wantonly can be by flash tank 206 before the crystallizer.Flash tank 206 is reduced to the pressure of reaction mixture 205 to a certain degree before the crystallizer, makes dissolved CO ₂Come out and from flash tank, discharge from the mixture flash distillation.Oxygen source (for example contains O ₂Gas) can be incorporated into the preceding flash tank 206 of crystallizer; with further oxidation N-((phosphonomethyl)) iminodiethanoic acid substrate in the unoxidized reaction mixture 205 in the oxidation reaction zone of reactor assembly 203, and further oxidation is present in formaldehyde and formic acid by product in the reaction mixture 205.By this way, flash tank 206 plays a part and reactor assembly 203 placed in-line oxidation reaction zones before the crystallizer.

Then evaporative crystallizer feedstream 239 is incorporated in the evaporative crystallizer 207 of heat driving, wherein heat is passed in the evaporative crystallizer feedstream 239, with with water (and small molecular weight impurity, as formaldehyde and formic acid) evaporation, form nonadiabatic crystallizer head space steam flow 209.Most of N-((phosphonomethyl)) glycine product (general about 50% to about 60%, by the per pass benchmark) precipitation produces evaporative crystallization slurry 211.Slurry 211 is discharged from nonadiabatic evaporative crystallizer 207, and can be incorporated into a hydrocyclone (or a draining power swirler) 213, forms to be rich in the concentrated slurry 215 of sedimentary N-((phosphonomethyl)) glycine product and the logistics 221 of solid poorness.To concentrate slurry 215 and be incorporated into solid separation equipment, preferred whizzer forms centrifugate 223 (its precipitation N-((phosphonomethyl)) glycine product is further poor) and N-((phosphonomethyl)) glycine product wet cake 219.

Usually, the concentration of N-((phosphonomethyl)) glycine product in wet cake 219 is at least about 95% (by the weight of all compounds and water).If wet cake 219 washes with water subsequently or with following more highly purified product blend, can allow lower production concentration.

Heat to small part drives the oxidation reaction zone that crystallizer top effluent 209 can be recycled to reactor assembly 203.In the embodiment depicted in fig. 11, with a part of 243 condensations, and recycled back, as the water source of dissolving N-((phosphonomethyl)) iminodiethanoic acid substrate with the feedstream 201 of formation reactor assembly 203.Comprise at reactor assembly 203 under the situation of placed in-line two or more oxidation reaction zones, preferably phlegma 243 is incorporated into upstream oxidation reaction zone.The same with nearly all recirculation stream of the present invention, logistics 243 alternatively (or in addition) is introduced directly into oxidation reaction zone, rather than merges with other composition (for example water-containing material stream 201) before being incorporated into oxidation reaction zone.Especially be the occasion of carbon-contained catalyst and more specifically in the occasion of the precious metal of catalyst pack carbon containing load at this catalyzer, the nonadiabatic crystallizer of part top effluent 209 can also be advantageously used in the reducing catalyst surface.This is generally to contain formaldehyde and/or formic acid because heat drives evaporative crystallizer top effluent 209, and the two all plays reductive agent, especially for carbon-contained catalyst with more specifically for the catalyzer of the precious metal that comprises the carbon load.Usually, the at first nonadiabatic crystallizer of part top effluent 209 condensations that will in this reduction is handled, use, this phlegma can be incorporated into the one or more catalyst stores jars in the reactor assembly 203, reduces processing there.Except reducing catalyst, this processing can be used for washing catalyst and utilize the residence time of catalyzer at the catalyst stores jar.In an especially preferred embodiment, with 209 further rectifying or the distillations of the nonadiabatic crystallizer of part top effluent, obtain to contain the steam flow of high-concentration formaldehyde and/or formic acid.This richness steam flow so can condensation with contact with carbon-contained catalyst.

Heat drives another part at least 241 of evaporative crystallizer top effluent 209, generally is eliminated (promptly discharging) as removing logistics 241 from system.In continuous system, this removing logistics 241 helps waste material semi-invariant in the minimizing system (especially small molecular weight impurity semi-invariant) and helps the water balance of management system.The waste material 241 of this removing and then can be further processed is so that remove impurity.This processing can comprise for example allowing removes logistics 241 and contains O ₂Gas contact with the catalyzer that comprises VIII family metal (especially platinum, palladium and/or rhodium) and optional carbon support, thereby with formaldehyde and formic acid oxidation, formation environmental friendliness CO ₂And water.Reaction is preferably arrived about 90 ℃ temperature (more preferably from about 50 ℃ to about 90 ℃) in about room temperature, about atmosphere is pressed onto the pressure of about 200psi, about 1 than under carries out with the reactor working volume to about 0.00040: 1 VIII family metal to the dissolved oxygen concentration of about 7ppm and about 0.00015: 1.This method is described in detail in the U.S. patent No. 5,606,107 by Smith.Drive that product that the oxidation of evaporative crystallizer top effluent 209 obtains can be recycled to the oxidation reaction zone of reactor assembly 203 and as the source of supplementary feed from heat.

The poor logistics 221 of hydrocyclone solid preferably is recycled to heat and drives in the evaporative crystallizer 207, is used for further reclaiming N-((phosphonomethyl)) glycine product.

Preferably will be recycled to heat from least a portion 231 of the centrifugate 223 of whizzer 217 and drive in the crystallizer 207, be used for further reclaiming N-((phosphonomethyl)) glycine product.As selecting (or in addition); the part 233 of centrifugate 223 can be recycled to the oxidation reaction zone of reactor assembly 203, so that be N-((phosphonomethyl)) glycine product with unreacted N-((phosphonomethyl)) iminodiethanoic acid substrate conversion in the centrifugate 223.As selecting (or in addition), the part 227 of centrifugate 223 can be removed away from system.

In continuous system, remove a part 227, help impurity accumulation (the especially macromole impurity accumulation) amount in the minimizing system, and therefore reduce impurity accumulation (the especially macromole impurity accumulation) amount in the wet cake 219 from the centrifugate 223 of whizzer 217.This processing for example can comprise:

1, remove as described in the logistics 241 about nonadiabatic crystallizer head space as above, remove logistics 227 can with O ₂Contact with VIII family metal catalyst, formaldehyde and the formic acid in the logistics 227 is removed in oxidation.

2, remove waste material 227 can with O ₂Contact with the catalyzer that contains precious metal; so that with any N-replacement-N-((phosphonomethyl)) glycine (being apparent that N-methyl-N-((phosphonomethyl)) glycine usually most) oxidation scission is other N-((phosphonomethyl)) glycine product; this product and then can collect in crystallizer is as by being recycled to it in the nonadiabatic crystallizer 207.Preferably; this is reflected at the pressure of normal atmosphere (more preferably from about 30 arriving about 200psig) at least; about 50 ℃ to about 200 ℃ (more preferably from about 70 ℃ to about 150 ℃; also more preferably from about 125 ℃ to about 150 ℃) temperature; the dissolved oxygen concentration that is not higher than about 2ppm; with carry out under the weight ratio of the precious metal of about 1: 500 to about 1: 5 (more preferably from about 1: 200 to about 1: 10 and also more preferably from about 1: 50 to about 1: 10) and N-replacement-N-((phosphonomethyl)) glycine by product.This treatment process is described in detail in the U.S. patent No. 6,005,140 by people such as Morgenstren.

3, removing waste material 227 can merge with the formaldehyde excessive with respect to N-((phosphonomethyl)) glycine compound and its derivatives chemical metering; then (for example at transition-metal catalyst; manganese, cobalt, iron, nickel, chromium, ruthenium, aluminium, molybdenum, vanadium, copper, zinc or cerium) down heating of existence, form more eco-friendly compound.This method is described in detail in the U.S. patent No. 4,851,131 by people such as Grabiak.

4, remove waste material 227 and can feed another crystallizer, be used for further reclaiming N-((phosphonomethyl)) glycine product.

In another particularly preferred embodiment; at least a portion oxidation mixtures effluent (is not preferably contained any catalyzer; especially do not contain any heterogeneous catalyst or homogeneous catalyst with the co-precipitation of N-((phosphonomethyl)) glycine product) be incorporated into thermal insulation substantially (promptly; any heat supply or heat extraction to crystallizer are not higher than the oxidation mixtures that about 200 kcal/kg are given to crystallizer) and more preferably fully in the crystallizer of adiabatic operation.Do not resemble the method for carrying out in above-mentioned nonadiabatic crystallizer, the sepn process of adiabatic crystallizer mainly produces by remove the concentrated effect that anhydrates because the solubleness that cooling brings descends.In preferred embodiments, the separate part of mother liquor and sedimentary crystalline solid is finished by decantation.Because the water yield of removing in adiabatic crystallization is few relatively, mother liquor has low relatively foreign matter content.According to the present invention, find that this mother liquor can directly be recycled to the source of oxidation reactor system as process water.Adiabatic crystallization process is favourable, because it need not evaporate required energy (general form with steam) in nonadiabatic crystallizer.

In especially preferred adiabatic crystallizer system, final reacting mixture descends at the unexpected pressure of flash zone experience, the portion water evaporation in the mixture that induces reaction.This evaporation and then cause residue reaction mixture cooling.Cooling has caused the precipitation of N-((phosphonomethyl)) glycine product.Then can the decantation mother liquor, so that concentrate the slurry of N-((phosphonomethyl)) glycine product.Adiabatic crystallization is favourable, because it need not evaporate required energy (general form with steam) in nonadiabatic crystallizer.

Figure 12 has shown an embodiment of the system that comprises adiabatic crystallizer 115.The water-containing material stream 101 that will comprise N-((phosphonomethyl)) iminodiethanoic acid substrate is incorporated into the oxidation reactor system 103 that comprises one or more oxidation reaction zones; substrate is oxidized therein, forms the oxidation mixtures 105 that comprises N-((phosphonomethyl)) glycine product.The oxidation mixtures of discharging from reactor assembly 103 105 is optional can to feed before the crystallizer the flash tank 107.Flash tank 107 is reduced to the pressure of reaction mixture 105 to a certain degree before the crystallizer, makes dissolved CO ₂Flash distillation is come out and is discharged from flash tank from mixture.The pressure that carries out oxidizing reaction in reactor assembly 103 is depended in preferred pressure drop.Usually, for example be the occasion of 115psia at oxidation reaction zone pressure, the pressure drop of flash tank 107 is not higher than about 100psig before the crystallizer, and more preferably from about 20 to about 80psig, more more preferably from about 60 arrive about 80psig and 75psig more preferably from about also; And be the occasion of 215psia at reaction zone pressure, preferred pressure drop is not higher than about 200psig, and more preferably from about 120 to about 180psig, more more preferably from about 160 arrive about 180psig and 175psig more preferably from about also.This final reacting mixture 105 that generally causes about at the most 1.5wt% (more generally about 0.2 arrives about 1wt%, even more generally about 0.2 arrives about 0.5wt% and also more generally about 0.25wt%) enters vapor phase.Usually, the pressure that leaves the gained crystallizer feedstream 114 of flash tank 107 before the crystallizer is at least about 15psia, more preferably from about 25 to about 100psia, more more preferably from about 30 arrive about 60psia and 40psia more preferably from about also.

Oxygen source (for example can be contained O ₂Gas) be incorporated in the preceding flash tank 107 of crystallizer; with further oxidation N-((phosphonomethyl)) iminodiethanoic acid substrate in the unoxidized reaction mixture 105 in oxidation reactor system 103, and further oxidation is present in formaldehyde and formic acid by product in the reaction mixture 105.By this way, flash tank 107 plays a part and reactor assembly 103 placed in-line oxidation reaction zones before the crystallizer.

Crystallizer feedstream 114 is incorporated in the adiabatic crystallizer 115.Below contact Figure 12 A provides the detailed description according to the operation of adiabatic crystallizer system of the present invention.The operation of adiabatic crystallizer 115 has produced the steam 117 (being adiabatic crystallizer top effluent) by the crystallizer top discharge, from knot ... decantate (being mother liquor) logistics 124 that brilliant device is discharged and the crystallized product slurry 125 that comprises sedimentary crystallization N-((phosphonomethyl)) glycine product of discharging by the crystallizer bottom.

At least a portion 132 of at least a portion 146 of adiabatic crystallizer top effluent 117 and/or the decantate 124 of discharging can be recycled to the oxidation reaction zone of reactor assembly 103.Usually, the adiabatic crystallizer top effluent 117 of recirculation and/or the decantate 124 of discharging are recycled to oxidation reaction zone, and as the water source of dissolving N-((phosphonomethyl)) iminodiethanoic acid substrate with the feedstream 101 of formation reactor assembly 103.Comprise at reactor assembly 103 under the situation of placed in-line two or more oxidation reaction zones, preferably the adiabatic crystallizer top effluent 117 of recirculation and/or the decantate 124 of discharging are incorporated into upstream oxidation reaction zone.It is favourable that at least a portion 132 of decantate 124 is recycled to reactor assembly, because it has reduced the refuse volume of water demand and system.It also usually allows, and unreacted N-((phosphonomethyl)) iminodiethanoic acid substrate reclaims additional N-((phosphonomethyl)) glycine product from decantate 124.This recirculation also has other benefit, and is because it usually can make other by product, oxidized as formaldehyde and formic acid.The recirculation of logistics 132 further is favourable, because it allows water directly be recycled to oxidation reaction zone by crystallizer 115, needn't consumes energy comes vaporize water (the above-mentioned top effluent that comes self-heating to drive evaporative crystallizer of recirculation is this situation).Because recirculation decantate 132 also remains on high relatively temperature (most preferably 60 ℃), so the decantate 132 of recirculation can be used in preheating water-containing material stream 101.When in reactor assembly 103, utilizing precious metal/C catalyst, can realize an also benefit of decantate recirculation stream 132, promptly the precious metal that is leached by catalyzer can turn back to reactor assembly.It is believed that the logistics such as the logistics 132 that will contain precious metal are recycled to reactor assembly 103, have reduced the net loss of precious metal from system.The precious metal that the part that contains in this recirculation stream leaches can be deposited on the surface of heterogeneous catalyst in the catalytic reactor system again.

Particularly be the occasion (with the occasion of the precious metal that is more in particular in the load of catalyst pack carbon containing) of carbon-contained catalyst, preferably by with adiabatic crystallizer top effluent 117 condensations of at least a portion with then with the indirect recirculation of phlegma and catalyst mix at catalyzer.This usually is favourable, because adiabatic crystallizer top effluent 117 contains formaldehyde and/or formic acid usually, as mentioned above, the two plays reductive agent.In an especially preferred embodiment, with effluent 117 rectifying of the adiabatic crystallizer of part top or condensation, further distillation again, the phlegma of formaldehyde and/or formic acid is rich in acquisition.This rich solution and then be that part of adiabatic crystallizer top effluent that contacts with carbon-contained catalyst.As mentioned above, this reduction is handled and can be carried out in the one or more catalyst stores jars in reactor assembly 103.

At least a portion 151 of the another part at least 149 of adiabatic crystallizer top effluent 117 and/or the decantate 124 of discharging is removed (promptly discharging) as waste material from system.In continuous system, this removing helps the impurity semi-invariant in the minimizing system.The waste material of this removing can further be handled as above described those technology of removing waste material logistics for nonadiabatic crystallizer downstream whizzer, so that remove impurity by technology known in the art again.For example, the waste material of this removing can with contain O ₂Gas contacts with VIII family metal catalyst, so that be CO with formaldehyde and formic acid oxidation ₂And water.The product of this oxide treatment can be recycled to the oxidation reaction zone of reactor assembly 103, and is used as the source of supplementary feed.

N-((phosphonomethyl)) the glycine product slurry 125 of discharging from the bottom of adiabatic crystallizer 115 contains a large amount of N-((phosphonomethyl)) glycine product.Usually slurry 125 is fed whizzer 155, so that further concentrate the wet cake 157 that slurry 125 and formation contain N-((phosphonomethyl)) glycine product.Usually the concentration of N-((phosphonomethyl)) glycine product in wet cake 157 is at least about 95% (by the weight of all compounds and water).For example can be recycled in the adiabatic crystallizer 115 or be recycled to the oxidation reaction zone of reactor assembly 103 from the poor logistics 161 of the solid of whizzer 155 (being centrifugate), as the water source in the water-containing material stream 101 through logistics 165 by logistics 169.In order impurity concentration to be remained on acceptable level and can advantageously to use recirculation decantate logistics 132, can remove at least a portion of the poor logistics 161 of solid through logistics 173.Logistics 173 can be handled by for example above described method for treatment of waste material of removing logistics about nonadiabatic heat driving crystallizer downstream whizzer subsequently.In another embodiment, logistics 173 is transported to heat drives evaporative crystallizer, so that reclaim other product with being similar to mode shown in Figure 13.

Figure 12 A is the synoptic diagram of the preferred adiabatic crystal system that uses in enforcement of the present invention.As shown, system 115 comprises vapour/liquid/gas separator 703, and it defines and generally is positioned at the vapour/liquid disengaging zone that keeps on the chamber 705 and keep the fluid flow contact with it.Vapour/liquid/gas separator 703 is separated with the contacting directly of upper area that keeps chamber 705, but gets in touch with keeping chamber lower region maintenance fluid flow by drainage tube 706, and the mouth 708 of drainage tube 706 is only separated by relative distance of lacking with the bottom that keeps the chamber.The mould assembly of this common configuration can be from HPD Products Division (Plainfield, Illinois, U.S.A) purchase of U.S.Filter.Crystallizer recirculation import 709 is positioned on vapour/liquid/gas separator 703, and keep the decanting liq outlet 711 that chamber 705 has the crystalline mother solution on the mouth 708 that is positioned at drainage tube 706, be positioned on the mouth of drainage tube and intermediate recycling slurry outlet 712 under the decanting liq outlet 711 and the bottom product slurry outlet 713 that is positioned at 705 bottoms, chamber.In operating process, keep chamber 705 basic filleds with fluid, and the liquid water horizontal line 715 in vapour/liquid/gas separator 703 keeps being lower than slightly crystallizer recirculation import 709.

Comprise the water-containing crystal device raw mix 716 (and various recirculation stream as described below) that the reaction mixture of being discharged by the oxidation reaction zone of oxidation reactor system flows out N-((phosphonomethyl)) the glycine product of thing 114 acquisitions, be incorporated into vapour/liquid/gas separator 703 by recirculation import 709.Vapour/liquid/gas separator has constituted by the vacuum system (not shown) and remains on sub-atmospheric pressure and be lower than the evaporating area of the vapour pressure of crystallization raw mix 716.Liquid water horizontal line 715 in vapour/liquid/gas separator 703 keeps by pressure equilibrium by the hole at drainage tube 708 epimeres that is communicated with reservation chamber 705.Crystallizer raw mix 716 comprises: (a) the oxidation mixtures effluent 114 (being starting soln) of discharging from the oxidation reaction zone of reactor assembly, and it can filter to remove catalyzer; (b) comprise the recycled slurry logistics 723 of at least a portion slurry of discharging by intermediate recycling slurry outlet 712 as described below; With the general centrifugate 165 that also has (c) to comprise the recirculation crystalline mother solution that comes by whizzer system 155 as described further below; what wherein introduce this whizzer system is from the crystallized product slurry 125 of outlet 713, is used to reclaim solid N-((phosphonomethyl)) glycine product.The pressure that keeps in vapour/liquid/gas separator 703 generally is not higher than about 8psia, and is preferred about 1.5 to about 4psia, more more preferably from about 2.5 arrives about 3.5psia and 3psia more preferably from about also.Usually, just at the pressure of the crystallizer raw mix 716 of vapour/liquid/gas separator upstream, should make this raw mix when entering into vapour/liquid/gas separator experience at least about 10psig, preferred about 10 to about 80psig, more preferably from about 30 to about 60psig and the also more preferably from about decompression of 38psig.The unexpected decline of pressure causes water and small molecular weight impurity (for example formaldehyde and formic acid) flash distillation from the raw mix 716 of vapour/liquid/gas separator 703 come out (i.e. evaporation).Separate the steam 117 (being the top effluent) that is produced, and discharge, import the condensing works (not shown) from the top of separator 703.Normally, be not higher than about 30wt%, more preferably from about 5 to about 30wt% and more more preferably from about 5 to about 10wt% oxidation mixtures 114 is discharged as steam 117.Result as evaporation; the residue of crystallizer raw mix 716 concentrates mutually partly significantly to be cooled off; thereby cause the precipitation of N-((phosphonomethyl)) glycine product and produce evaporate slurry 718, this evaporate slurry 718 comprises crystallization N-((phosphonomethyl)) the glycine product solid 719 that is suspended in the saturated substantially or oversaturated mother liquor of N-((phosphonomethyl)) glycine product.Preferably, preferably,, be enough to make the temperature of evaporate slurry 718 to hang down about 30 to about 40 ℃ than the temperature of the oxidation mixtures 114 that is incorporated into adiabatic crystal system by the cooling performance that the pressure drop that enters vapour/liquid/gas separator 703 causes.The temperature of evaporate slurry 718 is not higher than about 80 ℃, and more preferably from about 45 ℃ to about 80 ℃, more more preferably from about 55 ℃ to about 70 ℃ and especially about 60 ℃ to about 70 ℃.

Evaporate slurry 718 is discharged from separator 703 by descending drainage tube 706, and is introduced in the lower region that keeps reserved area in the chamber 705.The reserved area is divided into lower junction crystalline region (generally under the sea line 720) and top decantation district (generally on sea line 720).In the reserved area; evaporate slurry 718 is divided into upper strata liquid 722 that comprises mother liquor fraction (generally being its net products) and the second slurry logistics 723 that comprises sedimentary N-((phosphonomethyl)) glycine product crystallization and mother liquor, and this second slurry logistics 723 is discharged from keeping chamber 705 by middle slurry outlet 712.The decantate logistics 124 that comprises upper strata liquid 722 is discharged from keeping chamber 705 by near the decantation outlet 711 the reservation top, chamber in the decantation zone.

The crystallized product slurry 125 that comprises N-((phosphonomethyl)) glycine product slurry is discharged from the bottom that keeps chamber 705 by the outlet 713 of crystallizing field.The crystallized product slurry is delivered to whizzer system 155, separate as warm filter cake at this N-((phosphonomethyl)) glycine product crystal.Normally, the N-in the wet cake ((phosphonomethyl)) glycine product is at least about 95% (by the weight of all compounds and water).With 165 recirculation of gained centrifugate, and the decantation zone of reserved area and (being cloud bar) at the interface between crystal region, with the second section product slurry merging in the slurry logistics 723 of discharging by reservation chamber 705.The logistics that merges is incorporated into vapour/liquid/gas separator 703 with oxidation mixtures 114 as crystallizer raw mix 716.

Will be most of at least, preferred basic all second slurry logistics 723 of being discharged by outlet 712 are recycled to vapour/liquid/gas separator 703, mix with reaction mixture logistics 114 with from the centrifugate 165 of whizzer 155, form the raw mix 716 that is given to vapour/liquid/gas separator.In the decantation zone, from evaporate slurry 718, separate (being decantation) mother liquor 722.The speed of relative movement that decantation is introduced reaction mixtures 114 by maintenance by import 709 is finished; discharge decantate 124 from exporting 711; and through crystallizer feedstream 716 by middle slurry outlet 712 recirculation all or parts second slurry 723 (thereby control evaporate slurry 718 is incorporated into the speed of reserved area); upward flow speed under the feasible middle slurry outlet 712 in the bottom crystal region of reserved area is enough to keep sedimentary N-((phosphonomethyl)) glycine product crystal 719 to suspend (promptly carrying secretly) in liquid phase; simultaneously; upward flow speed in the decantation zone, top of the reserved area on middle slurry outlet 712 is lower than in the crystal region settling velocity at least about N-((phosphonomethyl)) the glycine product crystal 719 of 80wt%; preferably be lower than crystal 719 settling velocity, most preferably be lower than crystal 719 settling velocity at least about 98wt% at least about 95wt%.Therefore, decantation zone, the top of the reserved area of the mother liquor that contains substantial transparent and contain between the bottom crystal region of reserved area of crystallization slurry approximately in the middle of the level place of slurry outlet 712 set up the interface.

Preferred controlled oxidation reaction mixture 114 is incorporated into adiabatic crystal system 115; decantate 124 is discharged from exporting 711; product slurry 125 is discharged from exporting 713; with the speed of relative movement of centrifugate 165 from whizzer 155 recirculation; make N-((phosphonomethyl)) the glycine product solid in the crystal region of the bottom of reserved area and the ratio of mother liquor; the ratio that is higher than the increase of N-((phosphonomethyl)) the glycine product that obtains by evaporative effect and mother liquor; the ratio of this increase is the ratio of N-((phosphonomethyl)) glycine product solid that produces gradually and the mother liquor that produces gradually thus; that is the clean production of crystallization N-((phosphonomethyl)) glycine product.Expression in another way, the ratio of increase is if oxidation mixtures does not have (that is, there be not under the situation of recirculation second slurry) ratio that flash distillation obtained in the presence of the solid in the crystallizer raw mix.The effect that it should be understood that evaporation comprises concentrated effect and cooling effect; But when crystallizer is operated with basic adiabatic method (this is preferred); crystallization is mainly by obtaining liquid phase cools to certain temperature, significantly be lower than solubleness under its temperature at oxidation mixtures in the solubleness of N-((phosphonomethyl)) glycine product under this temperature.Preferably, the solid/mother liquor in the lower region of reserved area than be the quotient of difference that produces by evaporative effect at least about 2 times, and the concentration of product solid in crystal region also is at least 2 times of concentration that increase progressively generation.Expression in another way, N-((phosphonomethyl)) the glycine product solids concn in the crystal region of the bottom of reserved area is at least about 12wt%, preferably at least about 15wt%, is more preferably about 18wt% to about 25wt%.In the system of being given an example, solid product in the whizzer 155 and finally decide by system's material balance as the removal speed of the mother liquor of decantate 124, but the solid storage in the crystal region of the bottom of reserved area can or increase with respect to the product slurry via the decantation speed of outlet 711 by of short duration reduction and regulates from exporting 713 speed of discharging.As further discussing hereinafter, have been found that the control of the solid storage in the crystal region of reserved area provides the control of the mean particle size of N-((phosphonomethyl)) glycine product in the crystallisation process.

By according to the technology material balance and fixedly settling velocity decision keep the cross-sectional sizes of chamber 705, determine the stable state upward flow speed in decantation zone, the top of reserved area.The preferred high relatively upward velocity in the crystal region of the bottom of reserved area, set up (for example in 20: 1 to 100: 1 scope, the speed that is incorporated into the speed of crystal system or removes decantate 124 with respect to oxidation reaction medium 114) by second slurry 723 between slurry outlet 712 in the middle of remaining on and the recirculation import 709 to the high speed recirculation of vapour/liquid/gas separator 703.Centrifugate 165 fractions from whizzer 155 as a part of recirculation of crystallizer raw mix 716 have also increased recirculation rate and upward flow speed, but have often diluted the slurry in the crystal region in addition.By the second high slurry recirculation rate is combined with suitably determining the size that keeps chamber 705, upward flow speed in the crystal region of the bottom of reserved area can be controlled at least 4 times of the solid of the 80wt% at least settling velocity that wherein contains, and the upward flow speed in decantation zone, the top of reserved area can be based upon below four of containing in the second slurry logistics/of the solid of 80wt% at least settling velocity simultaneously.

In crystal region highly filled down operation with from second slurry 723 of middle slurry outlet 712 to the combining of the high speed recirculation of vapour/liquid/gas separator 703, further provide high solid concentration in whole evaporating area.Have been found that this operating method has remarkable favorable influence to the productivity of crystallization processes and the granularity and the draining characteristics of crystallization N-((phosphonomethyl)) the glycine product that is obtained simultaneously.Be contradictory between granularity and productivity, because productivity becomes positive correlation with oversaturated degree, but oversaturated degree generally becomes negative correlation with granularity.Yet; even under high relatively mean particle size; also increased effectively in highly filled down operation crystalline solid N-((phosphonomethyl)) glycine product crystalline surface can take place thereon; therefore crystallization processes can be carried out providing under the minimum relatively situation of the required liquid phase degree of supersaturation of crystallization motivating force with high productivity.Hang down the crystallization under the degree of supersaturation and then promoting big relatively crystalline to form.Therefore; for given evaporating area productivity; the mean particle size that crystallization processes of the present invention provides is obviously greater than the mean particle size that obtains in the contrast vaporizer; this contrast vaporizer is complete back mixing, and wherein the ratio of N-((phosphonomethyl)) glycine product solid and mother liquor equals the ratio of N-((phosphonomethyl)) glycine product solid that produces gradually by evaporative effect and the mother liquor that produces gradually thus.For example, crystallization processes of the present invention can be operated under high productivity, obtained to have the product of following feature: (1) is at least about 200 μ m, preferably at least about 225 μ m, more preferably at least about 250 μ m, more more preferably at least about 275 μ m, also more preferably at least about 300 μ m with especially at least about the intermediate value cube weighting granularity of 350 μ m; (2) at least about 85 μ m, preferably at least about 90 μ m, more preferably at least about 95 μ m, more more preferably at least about 100 μ m, also more preferably at least about 105 μ m with especially at least about the intermediate value length weighting granularity of 110 μ m; (3) be not higher than about 0.11m ²/ g is more preferably no higher than about 0.09m ²/ g is more more preferably no higher than about 0.07m ²/ g and also more preferably no higher than about 0.06m ²The BET of/g (Brunauer-Emmett-Teller) surface-area.An above-mentioned intermediate value cube weighted sum intermediate value length weighting granularity can use focused beam reflection measurement (FBRM) equipment as (LASENTECModel M100F U.S.A) measures for Redmond, Washington available from LaserSensor Technology Inc..

Account under the leading high flow rate in the recirculation path between the mouth 708 of middle slurry outlet 712 and drainage tube 706, crystal system is operated (that is not significant axially back mixing) with basic piston stream mode.The result, degree of super saturation descends along this path gradient, can be the integral mean motivating force maximization that crystallization utilizes thereby make, and the degree of supersaturation that the downstream end (being the mouth of drainage tube) in the piston flow path is obtained is lower than the degree of supersaturation that can obtain in the back mixing system.By the highly filled high crystal surface area that provides in recycled slurry, make and the effect of piston flow can be combined with generally low degree of supersaturation, net result under any given productivity will further reduce the degree of supersaturation in the liquid phase in the bottom crystal region of reserved area, and therefore reduce the degree of supersaturation in the decantation mother liquor of being removed by system 124.

For productivity, also can utilize plug flow operation and highly filled combining.Have been found that, can realize high productivity, even at high degree of supersaturation, be the crystalline motivating force (be expressed as in the aqueous liquid phase of any position in recirculation path N-((phosphonomethyl)) glycine production concentration and in the aqueous liquid phase of this position poor between the saturation concentration of N-((phosphonomethyl)) glycine product) be not higher than the occasion of about 0.7wt%, based on aqueous liquid phase; Or the integral mean degree of super saturation in whole recirculation path is not higher than 0.5% occasion.Be viewed in another way the relation between supersaturation and the productivity; described method can be carried out under than the condition that the identical per unit degree of supersaturation low 0.2% required with reference to evaporator operation volume crystallization throughput is provided effectively in the integral mean degree of supersaturation of recirculation path at least; wherein saidly be made up of complete back mixing evaporating area with reference to vaporizer, the ratio of N-in evaporating area ((phosphonomethyl)) glycine product solid and mother liquor equals the ratio of N-((phosphonomethyl)) glycine product solid that is produced gradually by evaporative effect and the mother liquor that produces gradually thus.

Because the crystal of producing according to Figure 12 A institute diagrammatic method has coarsness, so be used for the whizzer of product slurry 125 dehydrations or the ability of strainer are obviously improved subsidiary capital and the maintenance cost saved.For example,, obtained to have relative low water content, for example shown and be not higher than about 15wt%, more preferably no higher than crystallization N-((phosphonomethyl)) the glycine product of the drying loss of about 8wt% by using vertical centrifugal basket drier system or other dehydration equipment.Lower whizzer filter cake humidity directly causes the whizzer filter cake to be chlorinated pollution minimizings such as thing, NMG, unreacted N-((phosphonomethyl)) iminodiethanoic acid substrate.Therefore, the use of adiabatic crystal system provides the chance of producing N-((phosphonomethyl)) the glycine product of especially pure grade.For the abrasion of N-((phosphonomethyl)) glycine product crystalline are minimized, the use propeller pump comes the material in the adiabatic crystallizer system of recirculation.

Advantageously, the crystallization operation of Figure 12 A carries out with adiabatic method, promptly not through entering or leave vapour/liquid disengaging zone, the reserved area, be given to the raw mix of vapour/liquid disengaging zone, be recycled to second slurry of vapour/liquid disengaging zone or the centrifugate returned from the whizzer system heat passage realized enters or leave the heat passage in a large number of system.By the decompression of aforesaid raw mix, obtained sufficient evaporation, so that with the degree of liquid phase cools to realization N-((phosphonomethyl)) glycine product mass crystallization.By saving the demand of evaporator heat exchanger has been saved capital and energy, and eliminated the required process shutdown time of heat exchanger of regular overheated contamination.

And, carry out under the isolating situation at energy cost in a large number, decantation logistics 124 is provided, it can be easily as the source of the process water of the oxidation reaction zone that is recycled to oxidation reactor system.Because crystallization can be carried out with high productivity under relatively limited degree of supersaturation, the decantate that is recycled to oxidation reaction zone has almost minimum theoretical N-((phosphonomethyl)) glycine production concentration.Because the productivity of oxidation system generally is subjected to the restriction of the solubleness of N-((phosphonomethyl)) glycine product in reaction mixture outflow thing; especially in N-((phosphonomethyl)) glycine of preparation free acid form, utilize the occasion of beaded catalyst; N-in the recirculation decantate ((phosphonomethyl)) glycine product is being not the speed of N-((phosphonomethyl)) glycine product above N-((phosphonomethyl)) iminodiethanoic acid substrate conversion under the situation of N-((phosphonomethyl)) glycine product solubleness owing to having limited, and has reduced the clean productivity of oxidation reactor system at least in part.By in crystallizer, reclaiming near the N-((phosphonomethyl)) of the highest theoretical ratio thus glycine product and N-((phosphonomethyl)) the glycine product content of the current of recirculation is minimized, this appropriate cost relevant with decantate recirculation is reduced to minimum.

Though the system of describing in Figure 12 A is preferred; but one skilled in the art will realize that; exist other to select to set up in the crystal region of reserved area and to keep high N-((phosphonomethyl)) glycine product and mother liquor ratio, this can effectively provide thick relatively crystal.The method of Figure 12 A can effectively be retained in solid in the evaporating area; Perhaps can operate this method, make solid turn back to evaporating area.For example; if crystallization is being carried out in the back mixing evaporative crystallizer fully; might be by will be from the crystallized product recirculation of reclaiming N-((phosphonomethyl)) glycine product solid strainer or whizzer; filtrate/the centrifugate that do not circulate simultaneously or circulation be with respect to the filtrate/centrifugate of the small proportion of solid circle, and set up in crystallizer and keep high and out-of-proportion solid storage.Yet as those skilled in the art understood, the shortcoming of back one operation scheme need to be capital intensive filtration or centrifugal ability.A significant advantage of the preferred method of Figure 12 A is by decantation but not the mechanical system that is used for the costliness of solid/liquid separation has obtained the high solid storage.

Surprisingly, find, operate adiabatic crystallizer can not need concentrate decantation before slurry is incorporated into whizzer product slurry (as by using hydrocyclone) with above-mentioned optimal way.

Figure 13 has shown the example of a preferred embodiment, and wherein this method comprises the adiabatic crystallizer with nonadiabatic crystallizer serial operation.

Many the various logistics shown in Figure 13 be similar to above about independent nonadiabatic crystallizer and adiabatic crystallizer described those.The water-containing material stream 601 that will comprise N-((phosphonomethyl)) iminodiethanoic acid substrate is incorporated into the oxidation reactor system 603 that comprises one or more oxidation reaction zones; there, substrate is oxidized to the oxidation mixtures 605 that comprises N-((phosphonomethyl)) glycine product.Can choose wantonly flash tank 607 before the oxidation mixtures 605 feeding crystallizers.Flash tank 607 is reduced to the pressure of reaction mixture 605 to a certain degree before the crystallizer, makes dissolved CO ₂Flash distillation is come out and is discharged from flash tank from mixture.Oxygen source (for example can be contained O ₂Gas) be incorporated into the preceding flash tank 607 of crystallizer; with N-((phosphonomethyl)) the iminodiethanoic acid substrate of further oxidation in the unoxidized reaction mixture 605 of the oxidation reaction zone of reactor assembly 603, and the formaldehyde and the formic acid by product that exist in the further oxidation mixtures 605.By this way, flash tank 607 plays a part and reactor assembly 603 placed in-line oxidation reaction zones before the crystallizer.

The crystallizer feedstream 614 that will comprise most of N-((phosphonomethyl)) glycine product is incorporated into adiabatic crystallizer 615.The operation of adiabatic crystallizer 615 has produced the steam 617 (being adiabatic crystallizer top effluent) by the crystallizer top discharge, by decantate (the being elementary mother liquor) logistics 624 of crystallizer discharge and the primary crystallization product slurry 625 that comprises sedimentary crystallization N-((phosphonomethyl)) glycine product of being discharged by the crystallizer bottom.

At least a portion 632 of at least a portion 646 of adiabatic crystallizer top effluent 617 and/or the decantate 624 of discharging can be recycled to the oxidation reaction zone of reactor assembly 603.Usually, the adiabatic crystallizer top effluent 617 of recirculation and/or the decantate 624 of discharging are recycled to oxidation reaction zone, and as the water source of dissolving N-((phosphonomethyl)) iminodiethanoic acid substrate with the feedstream 601 of formation reactor assembly 603.Comprise at reactor assembly 603 under the situation of placed in-line two or more oxidation reaction zones, preferably the adiabatic crystallizer top effluent 617 of recirculation and/or the decantate 624 of discharging are incorporated into the oxidation reaction zone of upstream.It is favourable that at least a portion 632 of decantate 624 is recycled to oxidation reactor system, because it has reduced the refuse volume of water demand and system.It also makes usually and can reclaim other N-((phosphonomethyl)) glycine product by unreacted N-((phosphonomethyl)) iminodiethanoic acid substrate from decantate 624.This recirculation is favourable in addition, because it makes other by product such as formaldehyde and formic acid oxidized usually.The recirculation of logistics 632 further is favourable, because it makes water directly be recycled to oxidation reaction zone from crystallizer 615, at first consumed energy comes vaporize water (it is exactly like this that above-mentioned nonadiabatic heat drives crystallizer).Because recirculation decantate 632 also keeps high relatively temperature (most preferably 60 ℃), recirculation decantate 632 can be used in preheating water-containing material stream 601.

Especially be the carbon-contained catalyst occasion of (with this catalyzer that especially also comprises precious metal) at catalyzer, preferably make it recirculation indirectly by at least a portion and catalyst mix with adiabatic crystallizer top effluent 617.This is favourable because adiabatic crystallizer top effluent 617 usually contains formaldehyde and/or formic acid, as mentioned above, they the two play reductive agent.

In an especially preferred embodiment, the adiabatic crystallizer of part top effluent 617 is further distilled, to obtain to contain the solution of high-concentration formaldehyde and/or formic acid.This concentrated solution and then contact with carbon-contained catalyst.As mentioned above, this reduction is handled and can be carried out in one or more catalyst stores jars of reactor assembly 603.

At least a portion 651 of another part at least 649 of adiabatic crystallizer top effluent 617 and/or the decantate 624 of discharging can be used as waste material and remove (i.e. discharging) from system.In continuous system, this removing helps the impurity semi-invariant in the minimizing system.The waste material of this removing and then can be by technology known in the art is further handled as described those technology of waste streams of above removing about nonadiabatic crystallizer downstream whizzer, so that remove impurity.At least a portion 652 of the decantate 624 of discharging can be delivered in the nonadiabatic evaporative crystallizer 663 in addition.

Elementary N-((phosphonomethyl)) the glycine product slurry 625 of discharging from adiabatic crystallizer 615 bottoms contains most of N-((phosphonomethyl)) glycine product.Generally slurry 625 is fed whizzer 655, further to concentrate the wet cake 657 that slurry 625 and formation contain N-((phosphonomethyl)) glycine product.Normally, the concentration of N-((phosphonomethyl)) glycine product in wet cake 657 is at least about 95% (by the weight of all compounds and water).

On the other hand, will be from least a portion of the centrifugate 661 (being elementary mother liquor) of whizzer 655 (preferably at least about 1%, more preferably from about 1% to about 67%, more more preferably from about 20% to about 50%, also more preferably from about 30% to about 40% and also further more preferably from about 33%) being transported to heat drives evaporative crystallizer 663, and it is with heat supply centrifugate 661, so that vaporize water and small molecular weight impurity form evaporative crystallizer overhead vapor stream 665.Most of N-((phosphonomethyl)) glycine product precipitates in liquid medium 667.This liquid medium 667 is discharged from nonadiabatic evaporative crystallizer 663 and is incorporated in the hydrocyclone 669, forms the by-pass product logistics 673 and the poor logistics 671 of solid that are rich in sedimentary N-((phosphonomethyl)) glycine product.By-pass product logistics 673 is incorporated into whizzer 675, forms centrifugate 677 (its precipitation N-((phosphonomethyl)) glycine product is further poor) and N-((phosphonomethyl)) glycine product wet cake 679.Not exclusively be incorporated under the situation in the nonadiabatic crystallizer 663 from whole centrifugates 661 of whizzer 655 therein, the part 695 of centrifugate 661 can be recycled in the adiabatic crystallizer 615 and/or through removing logistics 693 and remove from system, and uses for example above-mentioned various liquid waste treatment processs to handle.

In the embodiment depicted in fig. 13, at least a portion heat can be driven evaporative crystallizer top effluent 665 and be recycled to reactor assembly 603.Usually, a part 685 is recycled to reactor assembly 603 also as the water source of dissolving N-((phosphonomethyl)) iminodiethanoic acid substrate with the feedstream 601 of formation oxidation reaction zone.Especially be the occasion of carbon-contained catalyst at catalyzer, can also advantageously use part heat to drive evaporative crystallizer top effluent 665 and come the reducing catalyst surface.This contains the fact of formaldehyde and/or formic acid usually owing to evaporative crystallizer top effluent 665, and the two plays reductive agent, especially to carbon-contained catalyst.Reduction is handled and can be carried out in one or more catalyst stores jars of reactor assembly 603.

Normally, effluent 665 do removing logistics 683 in the heat of another part driving evaporative crystallizer top are removed from system at least.In continuous system, this removing logistics 683 helps to reduce impurity accumulation (the especially small molecular weight impurity accumulation) amount of system.The waste material of removing 683 and then can further processing as described in the overhead stream of above removing for adiabatic crystallizer and nonadiabatic crystallizer is so that remove impurity.

Preferably will be recycled to heat from least a portion 689 of the centrifugate 677 of whizzer 675 and drive evaporative crystallizer 663 and/or adiabatic crystallizer 615) in, so that further reclaim N-((phosphonomethyl)) glycine product.Scheme (or in addition) as an alternative; the part 691 of centrifugate 677 is recycled to the oxidation reaction zone of reactor assembly 603, so that be N-((phosphonomethyl)) glycine product with unreacted N-((phosphonomethyl)) iminodiethanoic acid substrate conversion in the centrifugate 677.Usually also from system, remove the part 687 of centrifugate 677.In continuous system, this removing logistics 687 helps to reduce impurity accumulation (the especially macromole impurity accumulation) amount of system.The waste material 687 of this removing can constructedly further be handled by for example above alveolar fluid clearance waste material about adiabatic and nonadiabatic crystallizer is described, so that remove impurity.

In yes-no decision, not that the centrifugate 661 from whizzer 655 is given to nonadiabatic crystallizer 663, or in addition, alienate oneself at least a portion 652 of discharge decantate 624 of thermal crystalline device 615 in the future (preferably at least about 1%, more preferably from about 1 to about 67%, more more preferably from about 20 to about 50%, and also more preferably from about 30 to about 40% and also further preferably about 33%) be incorporated in the nonadiabatic crystallizer 663.In this case, centrifugate 661 can for example be recycled to adiabatic crystallizer 615 (through logistics 695), is recycled to reactor assembly 603, removes from system (through logistics 693), and/or is incorporated into nonadiabatic crystallizer 663.

Figure 14 has shown the example of a particularly preferred embodiment, and wherein this method comprises adiabatic crystallizer 319 and nonadiabatic crystallizer 343.Here, adiabatic crystallizer 319 and nonadiabatic crystallizer 343 are operated in the mid-shunt mode.

Many the various logistics shown in Figure 14 be similar to above about independent nonadiabatic crystallizer and adiabatic crystallizer described those.The water-containing material stream 301 that will comprise N-((phosphonomethyl)) iminodiethanoic acid substrate is incorporated into the oxidation reactor system 303 that comprises one or more oxidation reaction zones with oxygen; at this N-((phosphonomethyl)) iminodiethanoic acid substrate oxidation scission in the presence of catalyzer, form oxidation reaction product solution 305.To be incorporated into from the oxidation reaction product solution 305 that last oxidation reaction zone of reactor assembly 303 is discharged then before the crystallizer the flash tank 306, to reduce pressure and to flash off most of dissolved CO ₂In the embodiment depicted in fig. 14, gained liquid stream 308 usefulness catalyst filters 307 are filtered, to remove the heterogeneous beaded catalyst that is suspended in the liquid stream 308 and to form catalyst recycle logistics 309 and filtrate 311.Filtrate 311 is divided into a plurality of fractions; and with a part 317 (they being first fraction of reaction product solution) be incorporated in the adiabatic crystallizer 319; acquisition comprises the elementary product slurry of sedimentary N-((phosphonomethyl)) glycine product crystal and elementary mother liquor; simultaneously another part 315 (being second fraction of reaction product solution) is incorporated into nonadiabatic heat and drives evaporative crystallizer 343, obtain to comprise the evaporative crystallization slurry 344 (being the secondary products slurry) of sedimentary N-((phosphonomethyl)) glycine product crystal and secondary mother liquor.In this embodiment, can at first the described part 315 that is incorporated into the filtrate 311 of evaporative crystallizer 343 be incorporated into crystallizer feeding trough (not shown), there, it mixes with poor solid hydrocyclone logistics 351 and/or recirculation centrifugate 365.Except the blended place was provided, this feeding trough for example also provided the temporary transient buffering of preserving material in the beginning of this method and stopped process.

The operation of adiabatic crystallizer 319 has produced the steam 369 (being adiabatic crystallizer top effluent) by the crystallizer top discharge, by decantate (the being elementary mother liquor) logistics 323 of crystallizer discharge and the primary crystallization product slurry 321 that comprises sedimentary crystallization N-((phosphonomethyl)) glycine product and elementary mother liquor of being discharged by the crystallizer bottom.Preferably at least a portion (with all preferred) of the decantate 323 of discharging with adiabatic crystallizer top effluent 369 and/or by adiabatic crystallizer 319 is recycled to the oxidation reaction zone of reactor assembly 303.Usually, the part 324 of at least a portion 377 of adiabatic crystallizer top effluent 369 and/or the decantate 323 of discharging is recycled to reactor assembly 303, and as the water source of oxidation reaction zone.At least a portion 325 of the decantate 323 of discharging can be transported to nonadiabatic evaporative crystallizer 343 in addition.Adiabatic crystallizer top effluent 369 recirculation indirectly of at least a portion (through logistics 379) are used for the reducing catalyst surface to reactor assembly 303.As mentioned above, this reduction is handled and is usually carried out in catalyst stores jar 373.

Because have lower impurity (especially large molecular impurity) concentration from the poor liquid stream of the solid of adiabatic crystallizer 319 (being decantate stream 323) with from the poor logistics of solid (being centrifugate) 357 that the general specific heat of the poor liquid stream of solid (being centrifugate logistics 335) of subsequently centrifuge 331 drives the centrifuge 355 (for example solid bowl centrifuge) in crystallizing evaporator 343 downstreams; Usually whole discharging decantates 323 of thermal crystalline device 319 and the optional poor logistics 335 of all solids from adiabatic crystallizer 319 downstream centrifuges 331 of more preferably alienating oneself in the future is recycled to reactor assembly 303, and the poor logistics of solid (being centrifugate) 357 of using simultaneously heat to drive crystallizing evaporator 343 downstream centrifuges 355 to remove large molecular impurity (through removing logistics 361) from system. Therefore removing is favourable for continuous system, because it has reduced the cumulative percentage of pollutent in the system, makes from the recirculation of the poor logistics of solid (being logistics 323 and 335) of adiabatic crystallizer 319 more feasible.As the waste streams of above-mentioned removing, the waste material 361 of this removing can be handled by for example further crystallization.It can also be by Smith in the U.S. patent No. 5,606, and the technology described in 107 is handled.It can be handled by the technology that people such as for example Morgenstern are described in detail in the U.S. patent No. 6,005,140 in addition.It can be handled by the technology that people such as Grabiak are described in detail in the U.S. patent No. 4,851,131 in addition.

On the other hand, from poor logistics 335 general whole for example adiabatic crystallizer 319 (through logistics 337) or the reactor assemblies 303 (through logistics 341) of being recycled to of the solid of adiabatic crystallizer 319 downstream whizzers 331.The poor logistics 351 of solid that comes self-heating to drive evaporative crystallizer 343 downstream hydrocyclones 349 can be recycled to evaporative crystallizer.Any non-removing part 365 from the poor logistics 357 of the solid of evaporative crystallizer 343 downstream whizzers 355 generally is recycled to evaporative crystallizer.Heat drives at least a portion of evaporative crystallizer top effluent 345 and generally removes from system through logistics 347, though a part 350 optional can be directly through logistics 383 or be recycled to oxidation reactor system 303 through logistics 381 indirectly, with reductive agent as catalyzer.

Preferably will not contain catalyzer oxidation mixtures (being logistics 311) about 30% to about 85%, more preferably from about 50% to about 80%, more more preferably from about 65% to about 75% be incorporated in the adiabatic crystallizer 319 as first step lease making logistics 317, remainder is incorporated into nonadiabatic heat as second stage lease making logistics 315 and drives in the crystallizer 343 simultaneously.Second fraction 315 that is given to system and the weight ratio preferably about 0.1 of N-((phosphonomethyl)) iminodiethanoic acid substrate be to about 9, and more preferably from about 2 to about 7, and more more preferably from about 2.5 to 4.

Operate embodiment (as shown in Figure 14 a kind of) that adiabatic crystallizer and heat drives evaporative crystallizer generally more preferably in the mid-shunt mode than the embodiment of the adiabatic crystallizer of operating series and evaporative crystallizer.This for set evaporative crystallizer size, generally can obtain the fact of higher crystallizing power owing to for example in the occasion of crystallizer parallel connection.This provides higher handiness in the existing factory of renovation.

System among Figure 14 provides the logistics of two kinds of N-((phosphonomethyl)) glycine product wet cake: from the wet cake logistics 333 of adiabatic crystallizer 319 downstream whizzers 331 and the wet cake logistics 359 that comes the whizzer 355 in self-heating driving evaporative crystallizer 343 downstreams.Normally; wet cake logistics 333 from adiabatic crystallizer 319 preferably has at least 90% (by the weight of all compounds and water); more preferably at least 95% (by the weight of all compounds and water); more more preferably at least about N-((phosphonomethyl)) the glycine production concentration of 99% (by the weight of all compounds and water); and have at least about 85% (by the weight of all compounds and water) from the wet cake logistics 359 of evaporative crystallizer 343; more preferably at least about 90% (by the weight of all compounds and water) with more more preferably at least about N-((phosphonomethyl)) the glycine production concentration of 95% (by the weight of all compounds and water).Usually, the purity from the wet cake 333 of adiabatic crystallizer 319 parts is higher than to come self-heating to drive the purity of the wet cake 359 of evaporative crystallizer 343.

Usually advantageously, these wet cakes 333 and 359 are merged.Because the purity level that obtains in the wet cake 333 of being discharged by adiabatic crystallizer 319 is higher usually, this merging makes can allow lower from the purity level in the wet cake 359 of evaporative crystallizer 343.Therefore, for example, if merge wet cake 45% from evaporative crystallizer 343 and merge wet cake 55% from adiabatic crystallizer 319, purity level from the wet cake 359 of evaporative crystallizer 343 can be low to moderate 90.2wt%, so that in the occasion that has 99wt% purity from the wet cake 333 of adiabatic crystallizer 319, obtain the merging purity level of 95wt% at least.Normally, the wet cake that wish to merge has at least about 95% (by the weight of all compounds and water) with more preferably at least about N-((phosphonomethyl)) the glycine production concentration of 96% (by the weight of all compounds and water).

Figure 14 A has shown the example of another especially preferred embodiment, and wherein this method comprises that the adiabatic crystallizer and the nonadiabatic heat of operating in the mid-shunt mode described in above Figure 14 drive evaporative crystallizer.Yet this reactive system further comprises the second reactor system with one or more secondary oxidation reaction zones, is used to handle the fraction that heat drives the mixture of reaction products of evaporative crystallizer that is transported to from the primary oxidation reactor system.

Various logistics shown in many Figure 14 A and above about shown in Figure 14, wherein adiabatic reactor 319 and heat drive reactive system that evaporative crystallizer 343 operates in the mid-shunt mode described those are similar.The water-containing material stream 301 that comprises N-((phosphonomethyl)) iminodiethanoic acid substrate is incorporated into the primary oxidation reactor system 303 that comprises one or more oxidation reaction zones with oxygen; at this N-((phosphonomethyl)) iminodiethanoic acid substrate oxidation scission in the presence of catalyzer, form the reaction product solution 305 that comprises N-((phosphonomethyl)) glycine product and unreacted N-((phosphonomethyl)) iminodiethanoic acid substrate.If necessary at separating catalyst (for example by filtering) afterwards, the reaction product solution 305 from primary reactor system 303 is divided into a plurality of fractions that comprise elementary fraction 317 and secondary oxidation reactor feedstocks fraction 315.Elementary fraction 317 is incorporated in the adiabatic crystallizer 319, and cools off, to reclaim N-((phosphonomethyl)) glycine product as mentioned above by flash distillation water under reduced pressure.Secondary oxidation reactor feedstocks fraction 315 is incorporated into the secondary oxidation reactor assembly 316 that comprises one or more oxidation reaction zones; oxidized at this unreacted N-((phosphonomethyl)) iminodiethanoic acid substrate, produce the secondary oxidation reactor effluent 318 that comprises N-((phosphonomethyl)) glycine product.Second reactor raw material fraction 315 can be cooled off before being incorporated into secondary oxidation reactor assembly 316, to remove the heat release that produces and reduce production of by-products in primary oxidation reactor system 303.Reactor effluent 318 is incorporated into nonadiabatic heat drives in the evaporative crystallizer, be evaporated, thereby precipitate as mentioned above and reclaim N-((phosphonomethyl)) glycine product at this water.

In the reactive system of Figure 14 A, it should be understood that the one or more oxidation reaction zones that provided by various reactor configuration can be provided respectively for elementary and second reactor system 303 and 316, comprise flow reactor system for example mentioned above.Illustrate, primary reactor system 303 can comprise the single stirred-tank reactor shown in Fig. 2,2A and 2B, placed in-line two stirred-tank reactors shown in Fig. 3-6, one or more fixed-bed reactor as shown in Figure 8.In one embodiment, primary reactor system 303 comprises placed in-line one or more oxidation reaction zone, and reaction product solution 305 last oxidation reaction zone from this serial reaction district is discharged, and filters as required.Yet, it should be understood that, before last oxidation reaction zone of primary reactor system 303, can cut apart reaction product solution 305, make elementary fraction 317 before being introduced in adiabatic crystallizer 319, enter the residue oxidation reaction zone of primary reactor system.

The one or more oxidation reaction zones that provided by the one or more fixed-bed reactor that use the beaded catalyst slurry or stirred-tank reactor or their combination are provided in preferred second reactor system 316.Yet fixed-bed reactor generally are preferred, because can avoid using the catalyst recycle system that comprises catalyst filter in second reactor system 316.And; dissipation and temperature controlled problem about the thermopositive reaction heat that occurs during as first oxidation reaction zone of primary reactor system 303 when fixed-bed reactor; in second reactor system 316, avoided greatly, because the preferably oxidation in primary reactor system 303 of most of N-((phosphonomethyl)) iminodiethanoic acid substrate.Therefore, can adiabatic operation at the intrasystem oxidation reaction zone of second reactor.According to particularly preferred embodiment, the single oxidation reaction zone that is provided by fixed-bed reactor is provided in second reactor system 316.Preferred this fixed-bed reactor adopt in the same way the mode of gas and liquid communication peroxidation district to operate.

The existence of second reactor system 316 in the reactive system shown in Figure 14 A can design and operate primary reactor system 303 in the mode of unreacted N-((phosphonomethyl)) the iminodiethanoic acid substrate that allows higher concentration in reaction mixture 305.For example, second of primary reactor system 303 or the subsequent oxidation reaction zone can be quite little or omit (being that primary reactor system 303 can comprise single oxidation reaction zone) fully.Yet; unreacted N-((phosphonomethyl)) iminodiethanoic acid substrate is in reaction product solution 305; still preferably keep enough low with the therefore concentration in being transported to the elementary fraction 317 of adiabatic crystallizer 319, under leading stream temperature, precipitate to avoid unreacted N-((phosphonomethyl)) iminodiethanoic acid substrate.For the typical operation temperature (for example 60 ℃) of adiabatic crystallizer, the concentration of N-((phosphonomethyl)) iminodiethanoic acid substrate in reaction product solution 305 is not higher than about 2wt%.Yet; allow primary reactor system 303 with the more economical mode designed size and the second reactor system 316 of operation in order to utilize, the concentration of N-((phosphonomethyl)) iminodiethanoic acid substrate in reaction product solution 305 is preferably at least about 0.2wt% with more preferably at least about 0.5wt%.

Preferably be recovered in unreacted N-((phosphonomethyl)) the iminodiethanoic acid substrate in the elementary fraction 317 that is incorporated into adiabatic crystallizer 319; decantate 323 through discharging from adiabatic crystallizer 319 turns back to primary reactor system 303 again, and at least a portion of the poor logistics 335 of solid of the thermal crystalline device 319 downstream whizzers 331 of randomly alienating oneself in the future is recycled to the primary reactor system through logistics 341.By using high dewatering centrifuge (for example vertical centrifugal basket drier) as whizzer 331; improved the recovery of unreacted N-((phosphonomethyl)) iminodiethanoic acid substrate in the poor logistics 335 of solid, simultaneously the fraction of unreacted N-((phosphonomethyl)) the iminodiethanoic acid substrate in wet cake logistics 333 has been minimized.

In another embodiment of the present invention; can improve by increasing the second reactor system in the system shown in Figure 13, with further oxidation from unreacted N-((phosphonomethyl)) the iminodiethanoic acid substrate in the centrifugate 661 of nonadiabatic evaporative crystallizer 663 upstream whizzers 655.

Especially be the occasion of N-((phosphonomethyl)) glycine itself at N-((phosphonomethyl)) glycine product, know that very early this product can be converted into various salt or ester,, make its more convenient commercial applications to increase its solvability in water.This for example by Franz in the U.S. patent No. 3,977,860 and 4,405, discussed prevailingly in 531.The preferably salt of N-((phosphonomethyl)) glycine comprises for example an alkali metal salt (especially sylvite), alkanol amine salt (especially monoethanolamine salt), alkylamine salt (especially sec.-propyl amine salt) and alkyl sulfonium salt (especially trimethylammonium sulfonium salt).The sec.-propyl amine salt of N-((phosphonomethyl)) glycine is especially preferred.Consult for example people such as Bugg, the U.S. patent No. 5,994,269.The general specific ionization acid of this salt has obviously higher activity, and is about 40 times of free acid 25 ℃ of following solvabilities for example.

In some embodiments of the present invention, the N-that forms in oxidation reaction zone ((phosphonomethyl)) glycine product comprises ester or salt, the mixture that its content enough has required commercial concentration with formation greatly.Under those situations, can significantly reduce or eliminate fully the needs of the processing step of enriched product (for example crystallization, hydrocyclone, centrifugal etc.).Therefore if described catalyzer is above-mentioned drastic reduction catalyzer, especially like this, the drastic reduction catalyzer has generally formed to have low impurity concentration and needs purifying seldom or do not need the reaction mixture of purifying.

For example in some embodiments, the N-that forms in oxidation reaction zone ((phosphonomethyl)) glycine product is the sec.-propyl amine salt of N-((phosphonomethyl)) glycine.Under preferred oxidation operation temperature (promptly about 95 to about 105 ℃), this product still keeps dissolving under up to about 50wt% or higher concentration.The salt product can form in oxidation reaction zone by the following method: (a) use the sec.-propyl amine salt of N-((phosphonomethyl)) iminodiethanoic acid as substrate; (b) isopropylamine is incorporated into oxidation reaction zone with at oxidation reaction zone amination oxidation products, and/or (c) isopropylamine is incorporated into the container before oxidation reaction zone downstream and catalyzer filter.In the occasion with placed in-line above oxidation reaction zone, usually preferred (though not being indispensable) sec.-propyl amine salt of using N-((phosphonomethyl)) iminodiethanoic acid is incorporated in first of oxidation reaction zone as substrate and/or with isopropylamine.Howsoever, preferably there is at least 1 equivalent isopropylamine positively charged ion of (with more preferably a little higher than 1 equivalent) in formed every mole N-((phosphonomethyl)) glycine product.Should be realized that, generally also be applicable to form other salt an alkali metal salt (especially sylvite) for example, alkanol amine salt (especially monoethanolamine salt) about these principles that form the sec.-propyl amine salt, alkylamine salt except the sec.-propyl amine salt and alkyl sulfonium salt (especially trimethylammonium sulfonium salt).

Particularly, the invention provides following technical scheme:

1, prepare the method for N-((phosphonomethyl)) glycine product, this method comprises:

The water-containing material stream that will comprise N-((phosphonomethyl)) iminodiethanoic acid substrate is incorporated into oxidation reactor system,

In oxidation reactor system, in the presence of oxide catalyst,, generate the reaction product solution that comprises N-((phosphonomethyl)) glycine product with the oxidation of N-((phosphonomethyl)) iminodiethanoic acid substrate;

Reaction product solution is divided into a plurality of fractions that comprise elementary fraction and secondary fraction;

N-((phosphonomethyl)) glycine product crystal is precipitated out from elementary fraction, forms the elementary product slurry that comprises sedimentary N-((phosphonomethyl)) glycine product crystal and elementary mother liquor; With

Be precipitated out in the moisture secondary crystallization raw mix of N-((phosphonomethyl)) the glycine product that N-((phosphonomethyl)) glycine product crystal is contained from be included in described secondary fraction, form the secondary products slurry that comprises sedimentary N-((phosphonomethyl)) glycine product crystal and secondary mother liquor.

2, as scheme 1 described method; wherein with elementary fraction cooling; so that from elementary fraction, be settled out N-((phosphonomethyl)) glycine product; with water is evaporated from moisture secondary crystallization raw mix so that from moisture secondary crystallization raw mix, be settled out N-((phosphonomethyl)) glycine product crystal.

3,, wherein when pressure evaporates water outlet from elementary fraction elementary fraction is being cooled off by reducing as scheme 2 described methods.

4,, wherein under basic adiabatic condition, water is evaporated from elementary fraction as scheme 3 described methods.

5, as scheme 4 described methods, wherein said evaporation is cooled to about 45 ℃ with elementary fraction and arrives about 80 ℃ temperature.

6, as scheme 4 described methods, wherein about 5% weight is evaporated to the elementary fraction of about 30% weight.

7,, comprise that also decantation separates sedimentary N-((phosphonomethyl)) the glycine product crystal in elementary mother liquor and the elementary product slurry as scheme 4 described methods.

8, as scheme 7 described methods, also comprise with elementary product slurry in the isolating elementary mother liquor of precipitation N-((phosphonomethyl)) glycine product crystal decantation be recycled to oxidation reactor system, as the source of process water.

9,, wherein will be recycled to oxidation reactor system with isolating basic all the elementary mother liquors of precipitation N-((phosphonomethyl)) the glycine product crystal decantation in the elementary product slurry as scheme 8 described methods.

10, as scheme 9 described methods, wherein oxide catalyst comprises heterogeneous catalyst, and this heterogeneous catalyst contains the precious metal that is deposited on the carbon support.

11, as scheme 10 described methods, wherein N-((phosphonomethyl)) iminodiethanoic acid substrate with liquid reaction medium that oxide catalyst contacts in oxidation, and the chlorine ion concentration in liquid reaction medium remains on and is not higher than about 500 ppm by weight.

12, as scheme 11 described methods, wherein the chlorine ion concentration in the liquid reaction medium remains on and is not higher than 300 ppm by weight.

13, as scheme 12 described methods, wherein the chlorine ion concentration in the liquid reaction medium remains on and is not higher than 100 ppm by weight.

14, as scheme 11 described methods; wherein use the preparation of N-((phosphonomethyl)) iminodiethanoic acid substrate source to be incorporated into the water-containing material stream of reactor assembly; and the concentration of chlorion in N-((phosphonomethyl)) iminodiethanoic acid substrate source is lower than about 5000 ppm by weight, by drying schedule.

15, as scheme 14 described methods, wherein the concentration of chlorion in N-((phosphonomethyl)) iminodiethanoic acid substrate source is lower than about 3000 ppm by weight, by drying schedule.

16, as scheme 15 described methods, wherein the concentration of chlorion in N-((phosphonomethyl)) iminodiethanoic acid substrate source is lower than about 2000 ppm by weight, by drying schedule.

17, as scheme 16 described methods, wherein the concentration of chlorion in N-((phosphonomethyl)) iminodiethanoic acid substrate source is lower than about 1000 ppm by weight, by drying schedule.

18, as scheme 4 described methods, wherein said method also comprises removes the secondary mother liquor so that remove by product and impurity from this method.

19,, wherein from this method, remove basic all secondary mother liquors as scheme 18 described methods.

20, as scheme 4 described methods, wherein elementary fraction is about 30% to about 85% of a reaction product solution.

21, as scheme 20 described methods, wherein elementary fraction is about 50% to about 80% of a reaction product solution.

22, as scheme 21 described methods, wherein elementary fraction is about 65% to about 75% of a reaction product solution.

23, as scheme 20 described methods, wherein reactor assembly comprises placed in-line first and second oxidation reaction zones;

Water-containing material stream is incorporated into first oxidation reaction zone;

N-((phosphonomethyl)) iminodiethanoic acid substrate by oxidation continuously, produces the intermediate reaction mixture that comprises N-((phosphonomethyl)) glycine product and unreacted N-((phosphonomethyl)) iminodiethanoic acid substrate in first oxidation reaction zone;

Middle water-containing material stream is incorporated into second oxidation reaction zone, and this centre water-containing material stream is included in N-((phosphonomethyl)) glycine product and unreacted N-((phosphonomethyl)) the iminodiethanoic acid substrate that obtains in the intermediate reaction mixture;

N-((phosphonomethyl)) iminodiethanoic acid substrate by oxidation continuously, generates the reaction product solution that comprises N-((phosphonomethyl)) glycine product in second oxidation reaction zone; With

Reaction product solution is divided into comprises the elementary and a plurality of fractions secondary fraction.

24, as scheme 23 described methods, wherein oxide catalyst contacts with liquid reaction medium in each oxidation reaction zone.

25, as scheme 24 described methods, wherein oxide catalyst comprises heterogeneous beaded catalyst.

26, as scheme 25 described methods, wherein heterogeneous beaded catalyst comprises the precious metal that is deposited on the granulated carbon carrier.

27, the method for scheme 4, the transpiration cooling of wherein said elementary fraction comprises:

Moisture evaporation raw mix is incorporated into evaporating area, and described water-containing material mixture comprises described elementary fraction;

In described evaporating area, in the presence of solid particulate N-((phosphonomethyl)) glycine product, water is evaporated from described moisture evaporation raw mix, thereby produce the vapor phase that comprises water vapour, from aqueous liquid phase, be settled out N-((phosphonomethyl)) glycine product, and generation comprises N-((phosphonomethyl)) glycine product solid and N-((phosphonomethyl)) glycine product is saturated substantially or the evaporate of oversaturated elementary mother liquor; With

In described evaporating area, the ratio that keeps particle N-((phosphonomethyl)) glycine product solid and elementary mother liquor is greater than the ratio of the N-that is produced gradually by evaporative effect ((phosphonomethyl)) glycine product solid with the mother liquor that produces gradually thus.

28, as scheme 27 described methods, wherein described evaporate is cut apart, to provide poor relatively N-((phosphonomethyl)) the glycine product solid fraction of mother liquor relative poor elementary mother liquor fraction with N-((phosphonomethyl)) glycine product solid.

29,, wherein in described evaporating area, keep the ratio of described particle N-((phosphonomethyl)) glycine product solid and mother liquor to comprise that the solid that will obtain turns back to described evaporating area or the solid that will obtain is retained in the described district in described solid fraction in described solid fraction as scheme 28 described methods.

30, as scheme 29 described methods, comprising:

The evaporation raw mix that will comprise described elementary fraction is incorporated into the vapour of described evaporating area/liquid disengaging zone, wherein pressure is lower than the vapour pressure of described mixture, thereby water flash distillation from the evaporation raw mix is come out, produced the vapor phase that comprises water vapour, and N-((phosphonomethyl)) glycine product is precipitated out from liquid phase, produced first slurry flow of particle N-((phosphonomethyl)) the glycine product that is included in saturated or the supersaturation mother liquor;

Described vapor phase is separated with described first slurry flow;

Described first slurry flow is incorporated into the reserved area, separate with second slurry flow that comprises sedimentary N-((phosphonomethyl)) glycine product and mother liquor at this upper strata liquid that comprises described mother liquor fraction, described reserved area has the import of described first slurry, be positioned at the decanting liq outlet that is used for described upper strata liquid on the described import, and be positioned on the described import but the outlet of described second slurry under the decanting liq outlet; With

Keep described first slurry is incorporated into described reserved area; the speed of relative movement that described second slurry is discharged by described second slurry outlet and described upper strata liquid is discharged by described decanting liq outlet; make the upward flow speed in the lower region of the described reserved area under described second slurry outlet be enough to keep sedimentary N-((phosphonomethyl)) glycine product to be suspended in the liquid phase, and the upward flow speed in the upper area of the described reserved area on described second slurry outlet is under the settling velocity of N-((phosphonomethyl)) glycine product particle of at least 80% weight in lower region.

31, as scheme 30 described methods, at least a portion of wherein said second slurry flow is recycled to described vapour/liquid disengaging zone.

32, as scheme 31 described methods, at least a portion of wherein said second slurry flow and described elementary fraction constitute the evaporation raw mix that is incorporated into described vapour/liquid disengaging zone together.

33, as scheme 32 described methods, wherein remove the 3rd slurry flow from the lower region in described district.

34; as scheme 33 described methods; wherein said elementary level is diverted to described vapour/liquid disengaging zone; all or part of described second slurry flow is recycled to described vapour/liquid disengaging zone; described upper strata liquid is discharged from described decanting liq outlet; described the 3rd slurry flow is discharged from the lower region of described reserved area; and any liquid or solid logistics of carrying the logistics of any solid/liquid separation that is stood from described the 3rd slurry turns back to the speed of relative movement of described evaporating area; be enough to set up at the lower region in described district the ratio of certain N-((phosphonomethyl)) glycine product solid and mother liquor, this ratio is higher than the ratio by evaporative effect precipitated solid N-((phosphonomethyl)) the glycine product that produces gradually and the mother liquor that produces gradually thus of described elementary fraction.

35, as scheme 34 described methods; wherein control the relative velocity of described each logistics; make N-((phosphonomethyl)) glycine product solids concn at the lower region in described district; be such solid and mother liquor mixture, promptly under the situation that does not have the described recirculation second slurry logistics in described gas/liquid district N-((phosphonomethyl)) the glycine product solids concn by the solid that maybe will produce by the described elementary fraction of flash distillation and mother liquor mixture at least about 2 times.

36, as scheme 35 described methods, wherein from described the 3rd slurry, remove solid, obtain to be recycled to the recycled liquid fraction of described vapour/liquid disengaging zone, thereby described evaporation raw mix also comprises described recycled liquid fraction.

37, as scheme 36 described methods, wherein said elementary fraction and described recycled liquid fraction were mixed with described second slurry flow before being incorporated into described vapour/liquid disengaging zone.

38, as scheme 37 described methods; wherein described secondary fraction is incorporated into the second reactor system that comprises the tertiary oxidation reaction zone; unreacted N-((phosphonomethyl)) the iminodiethanoic acid substrate that contains in described secondary fraction is converted into N-((phosphonomethyl)) glycine product in described tertiary oxidation reaction zone; produce the tertiary oxidation reaction mixture, described secondary crystallization raw mix is included in N-((phosphonomethyl)) the glycine product that contains in the described tertiary oxidation reaction mixture.

39, as scheme 37 described methods, wherein control described whole logistics, comprise the relative velocity of described recycled liquid fraction, make that the solids content of the slurry in the lower region in described district is at least about 12% weight.

40,, comprise that also decantation separates sedimentary N-((phosphonomethyl)) the glycine product crystal in elementary mother liquor and the elementary product slurry as scheme 39 described methods.

41, as scheme 39 described methods, also comprise elementary mother liquor is recycled to described oxidation reactor system, use as the water source.

42,, also comprise and remove the secondary mother liquor so that from this method, remove by product and impurity as scheme 39 described methods.

43, as scheme 39 described methods, wherein said oxidation reactor system comprises the series at least two continuous oxidation reaction districts, and this method further comprises:

Oxide catalyst is separated with reaction product solution; With

Isolating oxide catalyst is recycled at least one oxidation reaction zone continuously.

44, prepare the method for N-((phosphonomethyl)) glycine product, this method comprises:

The water-containing material stream that will comprise N-((phosphonomethyl)) iminodiethanoic acid substrate is incorporated into oxidation reactor system;

In oxidation reactor system, in the presence of oxide catalyst,, produce the reaction product solution that contains N-((phosphonomethyl)) glycine product with the oxidation of N-((phosphonomethyl)) iminodiethanoic acid substrate;

N-((phosphonomethyl)) glycine product crystal is precipitated out from reaction product solution, produces the elementary product slurry that comprises sedimentary N-((phosphonomethyl)) glycine product crystal and elementary mother liquor; With

Water is evaporated from elementary mother liquor, thereby is settled out other N-((phosphonomethyl)) glycine product crystal and obtains the secondary mother liquor.

45, as scheme 44 described methods, wherein with the reaction product solution cooling, from reaction product solution, to be settled out N-((phosphonomethyl)) glycine product crystal.

46,, wherein when pressure evaporates water outlet from reaction product solution reaction product solution is being cooled off by reducing as scheme 45 described methods.

47, as scheme 46 described methods, wherein under basic adiabatic condition from reaction product solution vaporize water.

48, as scheme 47 described methods, wherein evaporate with reaction product solution be cooled to about 45 ℃ to about 80 ℃ temperature.

49, as scheme 47 described methods, wherein about 5% weight is evaporated to the reaction product solution of about 30% weight.

50, as scheme 47 described methods, wherein this method also comprises removing secondary mother liquor so that remove by product and impurity from this method.

51,, wherein from this method, remove basic all secondary mother liquors as scheme 50 described methods.

52, prepare the method for N-((phosphonomethyl)) glycine product, this method comprises:

The water-containing material stream that will comprise N-((phosphonomethyl)) iminodiethanoic acid substrate is incorporated into the primary oxidation reactor system that comprises one or more oxidation reaction zones;

In the primary oxidation reactor system,, produce the reaction product solution that comprises N-((phosphonomethyl)) glycine product and unreacted N-((phosphonomethyl)) iminodiethanoic acid substrate with the oxidation of N-((phosphonomethyl)) iminodiethanoic acid substrate;

Reaction product solution is divided into a plurality of fractions that comprise elementary fraction and secondary oxidation reactor feedstocks fraction;

From elementary fraction, be settled out N-((phosphonomethyl)) glycine product crystal, produce the elementary product slurry that comprises sedimentary N-((phosphonomethyl)) glycine product crystal and elementary mother liquor;

Secondary oxidation reactor feedstocks fraction is incorporated into the secondary oxidation reactor assembly that comprises one or more oxidation reaction zones;

In the secondary oxidation reactor assembly,, produce the secondary oxidation reactor effluent that comprises N-((phosphonomethyl)) glycine product with the oxidation of N-((phosphonomethyl)) iminodiethanoic acid substrate; With

N-((phosphonomethyl)) glycine product crystal is precipitated out from the secondary oxidation reactor effluent, produces the secondary products slurry that comprises sedimentary N-((phosphonomethyl)) glycine product crystal and secondary mother liquor.

53, as scheme 52 described methods; wherein with elementary fraction cooling; from elementary fraction, to be settled out N-((phosphonomethyl)) glycine product crystal; and by evaporating water outlet in the secondary oxidation reactor effluent, from the secondary oxidation reactor effluent, to be settled out N-((phosphonomethyl)) glycine product crystal.

54,, wherein when pressure evaporates water outlet from elementary fraction elementary fraction is being cooled off by reducing as scheme 53 described methods.

55,, wherein under basic adiabatic condition, from elementary fraction, evaporate water outlet as scheme 54 described methods.

56, as scheme 52 described methods, wherein the primary reactor system comprises placed in-line a plurality of oxidation reaction zone.

57, as scheme 56 described methods, wherein after placed in-line last oxidation reaction zone, cut apart reaction product solution.

58, as scheme 56 described methods; wherein before placed in-line last oxidation reaction zone, cut apart reaction product solution, and from elementary fraction, be settled out the before elementary fraction of N-((phosphonomethyl)) glycine product crystal through at least one the additional oxidation step district in the primary reactor system.59, as scheme 52 described methods, wherein the primary reactor system comprises single oxidation reaction zone.

60, as scheme 52 described methods, wherein the secondary oxidation reactor assembly comprises stirred-tank reactor.

61, as scheme 52 described methods, wherein the secondary oxidation reactor assembly comprises fixed-bed reactor.

62, as scheme 61 described methods, wherein fixed-bed reactor take gas and liquid flow to operate by the mode of oxidation reaction zone in the same way.

63, as scheme 61 described methods, wherein fixed-bed reactor are operated with adiabatic method.

64, as scheme 52 described methods, wherein secondary oxidation raw material fraction was cooled before being incorporated into the secondary oxidation reactor assembly.

65, prepare the method for N-((phosphonomethyl)) glycine product by oxidation N-((phosphonomethyl)) iminodiethanoic acid substrate, this method comprises:

N-((phosphonomethyl)) iminodiethanoic acid substrate is incorporated in the interior liquid reaction medium of oxidation reaction zone, oxidation reaction zone basic back mixing and contain the catalyst for oxidation reaction that contacts with liquid reaction medium in liquid phase, liquid reaction medium comprises N-((phosphonomethyl)) glycine product;

Oxygenant is incorporated into oxidation reaction zone;

Continuous oxidation N-((phosphonomethyl)) iminodiethanoic acid substrate in oxidation reaction zone forms N-((phosphonomethyl)) glycine product; With

Discharge the reaction mixture that comprises N-((phosphonomethyl)) glycine product continuously from oxidation reaction zone and flow out thing.

66, as scheme 65 described methods, wherein catalyzer comprises the heterogeneous beaded catalyst that is suspended in the interior liquid reaction medium of oxidation reaction zone, and this catalyzer comprises the precious metal that is deposited on the granulated carbon carrier.

67, as scheme 66 described methods, wherein oxidation reaction zone is provided by the ejector nozzle loop reactor.

68, as scheme 67 described methods, wherein oxygenant is to contain O ₂Gas, and the ejector nozzle by the ejector nozzle loop reactor and water-containing material stream are incorporated into oxidation reaction zone simultaneously.

69, as scheme 66 described methods, wherein oxidation reaction zone is provided by fluidized-bed reactor.

70, as scheme 66 described methods, wherein oxidation reaction zone is provided by continuous stirred tank reactor.

71, as scheme 70 described methods, wherein the size-grade distribution of granulated carbon carrier is that to make the overall dimension of about 95% granules of catalyst be about 3 to about 100 μ m.

72, as scheme 71 described methods, wherein the mean particle size of beaded catalyst is about 15 to about 40 μ m.

73, as scheme 71 described methods, wherein the concentration of the beaded catalyst in oxidation reaction zone is about 0.1 to about 10% weight, based on the gross weight of catalyzer in the oxidation reaction zone and liquid reaction medium.

74, as scheme 70 described methods, also comprise the cooling liqs reaction medium.

75, as scheme 74 described methods, wherein liquid reaction medium cools off in comprising the external heat transfer cycle loop of heat exchanger.

76, as scheme 70 described methods, wherein oxygenant is to contain O ₂Gas, and in the liquid reaction medium of spray cloth in the oxidation reaction zone.

77, as scheme 70 described methods, wherein the reaction mixture outflow thing from the oxidation reaction zone discharging does not contain beaded catalyst substantially, stirred-tank reactor comprises the internal activator strainer, to prevent that beaded catalyst from flowing out thing with reaction mixture and discharging from oxidation reaction zone.

78, as scheme 70 described methods, wherein the reaction mixture outflow thing of discharging from oxidation reaction zone also comprises beaded catalyst, and this method also comprises:

Flow out separating particles catalyzer the thing from reaction mixture, form the catalyst recycle logistics that comprises isolating beaded catalyst; With

At least a portion beaded catalyst that will contain in the catalyst recycle logistics is incorporated into oxidation reaction zone.

79, as scheme 78 described methods, wherein from the catalyst recycle logistics, remove catalyzer.

80, as scheme 79 described methods, wherein live catalyst is joined in the catalyst recycle logistics.

81, as scheme 78 described methods, wherein in catalyst filter, flow out separating particles catalyzer the thing from reaction mixture, form the catalyst recycle logistics and do not have beaded catalyst substantially and comprise the filtrate of N-((phosphonomethyl)) glycine product.

82,, wherein adopt catalyst filter to come to flow out continuous separating particles catalyzer the thing from reaction mixture as scheme 81 described methods.

83, as scheme 82 described methods, wherein catalyst filter is continuous cross-flow filter.

84, as scheme 82 described methods, wherein catalyst filter is continuous back-flushing filter.

85, as scheme 84 described methods, wherein back-flushing filter comprises filter element, and part filtrate is used for the back-flushing filter element and removes isolating catalyzer from filter element.

86, as scheme 84 described methods, wherein reaction mixture outflow thing also comprises dissolved CO ₂, reaction mixture flows out thing and fed flash tank before being incorporated into catalyst filter, flows out the pressure of thing and remove dissolved CO from reaction mixture outflow thing so that reduce reaction mixture ₂

87, as scheme 84 described methods, wherein before being introduced in oxidation reaction zone, at least a portion beaded catalyst that contains in the catalyst recycle logistics is passed into the catalyst stores jar.

88, as scheme 87 described methods, wherein the catalyst stores jar does not contain O substantially ₂

89,, comprise well non-oxidizing gas is incorporated into the catalyst stores jar as scheme 88 described methods.

90, as scheme 88 described methods, wherein the residence time of catalyst recycle in the catalyst stores jar is at least about 2 minutes.

91, as scheme 81 described methods, wherein filtrate comprises unreacted N-((phosphonomethyl)) iminodiethanoic acid substrate, and this method further comprises:

Filtrate is incorporated into second oxidation reaction zone continuously;

Oxygenant is incorporated into second oxidation reaction zone; With

In second oxidation reaction zone,, form additional N-((phosphonomethyl)) glycine product with the continuous oxidation of N-((phosphonomethyl)) iminodiethanoic acid substrate.

92, as scheme 91 described methods, wherein second oxidation reaction zone basic back mixing in liquid phase.

93, as scheme 92 described methods, wherein second oxidation reaction zone is provided by second stirred-tank reactor.

94, as scheme 92 described methods, wherein second oxidation reaction zone is provided by the ejector nozzle loop reactor.

95, as scheme 91 described methods, wherein second oxidation reaction zone is provided by fixed-bed reactor.

96, prepare the method for N-((phosphonomethyl)) glycine product by oxidation N-((phosphonomethyl)) iminodiethanoic acid substrate, this method comprises:

N-((phosphonomethyl)) iminodiethanoic acid substrate is incorporated in the interior liquid reaction medium of oxidation reaction zone, and liquid reaction medium comprises N-((phosphonomethyl)) glycine product and the particle heterogeneous catalyst that is used for oxidizing reaction that is suspended in wherein;

Oxygenant is incorporated into oxidation reaction zone;

Continuous oxidation N-((phosphonomethyl)) iminodiethanoic acid substrate in the liquid reaction medium in oxidation reaction zone forms N-((phosphonomethyl)) glycine product;

The continuous blow-down reaction mixture flows out thing from described oxidation reaction zone, and reaction mixture flows out thing and comprises N-((phosphonomethyl)) glycine product;

Flow out continuous separating particles catalyzer the thing from reaction mixture, form the catalyst recycle logistics that comprises isolating catalyzer; With

At least a portion beaded catalyst that will contain in the catalyst recycle logistics is recycled to described oxidation reaction zone.

97, as scheme 96 described methods, wherein before being incorporated into described oxidation reaction zone, the beaded catalyst that contains in the catalyst recycle logistics is other oxidation reaction zone by at least one.

98, as scheme 96 described methods, wherein the beaded catalyst that will contain in the catalyst recycle logistics is introduced directly into described oxidation reaction zone.

99, as scheme 96 described methods, wherein in catalyst filter, flow out separating particles catalyzer the thing from reaction mixture, form the catalyst recycle logistics and do not have beaded catalyst substantially and comprise the filtrate of N-((phosphonomethyl)) glycine product.

100,, wherein adopt catalyst filter to flow out continuous separating particles catalyzer the thing from reaction mixture as scheme 99 described methods.

101, prepare the method for N-((phosphonomethyl)) glycine product by oxidation N-((phosphonomethyl)) iminodiethanoic acid substrate in reactor assembly, this method comprises:

The water-containing material stream that will comprise N-((phosphonomethyl)) iminodiethanoic acid substrate is incorporated into first oxidation reaction zone;

Oxygenant is incorporated into first oxidation reaction zone;

In first oxidation reaction zone,, form N-((phosphonomethyl)) glycine product with the continuous oxidation of N-((phosphonomethyl)) iminodiethanoic acid substrate;

Discharge the intermediate reaction mixture that comprises N-((phosphonomethyl)) glycine product and unreacted N-((phosphonomethyl)) iminodiethanoic acid substrate continuously from the-oxidation reaction zone and flow out thing;

Middle water-containing material stream is incorporated into second oxidation reaction zone continuously, and described middle water-containing material stream is included in the intermediate reaction mixture and flows out N-((phosphonomethyl)) glycine product and unreacted N-((phosphonomethyl)) the iminodiethanoic acid substrate that obtains in the thing;

Oxygenant is incorporated into second oxidation reaction zone;

In second oxidation reaction zone,, form other N-((phosphonomethyl)) glycine product with the continuous oxidation of N-((phosphonomethyl)) iminodiethanoic acid substrate; With

From second oxidation reaction zone, discharge the reaction mixture that comprises N-((phosphonomethyl)) glycine product continuously and flow out thing.

102, as scheme 101 described methods, wherein first and second oxidation reaction zones contain catalyst for oxidation reaction.

103, as scheme 102 described methods, wherein the catalyzer in first oxidation reaction zone is heterogeneous beaded catalyst, and is suspended in the liquid reaction medium that comprises N-((phosphonomethyl)) iminodiethanoic acid substrate.

104, as scheme 103 described methods, wherein first oxidation reaction zone basic back mixing in liquid phase.

105, as scheme 104 described methods, wherein first oxidation reaction zone is provided by stirred-tank reactor.

106, as scheme 104 described methods, wherein first oxidation reaction zone is provided by the ejector nozzle loop reactor.

107, as scheme 104 described methods, wherein first oxidation reaction zone is provided by fluidized-bed reactor.

108, as scheme 104 described methods, wherein second oxidation reaction zone is provided by the fixed bed that wherein has catalyzer.

109, as scheme 102 described methods, wherein the catalyzer in first and second oxidation reaction zones is heterogeneous beaded catalyst, and is suspended in the liquid reaction medium that comprises N-((phosphonomethyl)) iminodiethanoic acid substrate.

110, as scheme 109 described methods, wherein first and second oxidation reaction zones basic back mixing in liquid phase.

111, as scheme 110 described methods, the oxygenant that wherein is incorporated into first and second oxidation reaction zones is to contain O ₂Gas, and the basic back mixing in gas phase of second oxidation reaction zone.

112, as scheme 111 described methods, wherein first and second oxidation reaction zones are provided by first and second continuous stirred tank reactors respectively, stirred-tank reactor contains the head space on liquid reaction medium, second stirred-tank reactor has and is suitable for gas is drawn into impeller system the liquid reaction medium from head space, thereby reduces poor between the oxygen partial pressure of the oxygen partial pressure of the gas that is drawn into liquid reaction medium and head space gas.

113, as scheme 112 described methods, wherein will contain O ₂Gas is incorporated into the head space on the liquid reaction medium in second stirred-tank reactor.

114, as scheme 111 described methods, wherein first oxidation reaction zone is provided by continuous stirred tank reactor, and second oxidation reaction zone is provided by the ejector nozzle loop reactor.

115, as scheme 110 described methods, wherein first and second oxidation reaction zones are provided by first and second continuous stirred tank reactors respectively.

116, as scheme 115 described methods, wherein heterogeneous beaded catalyst comprises the precious metal that is deposited on the granulated carbon carrier.

117, as scheme 116 described methods, wherein the size-grade distribution of granulated carbon carrier is that to make the overall dimension of about 95% catalyst particle be about 3 to about 100 μ m.

118, as scheme 117 described methods, wherein the mean particle size of beaded catalyst is about 15 to about 40 μ m.

119,, be about 0.1 to about 10% weight, based on the gross weight of catalyzer in oxidation reaction zone and liquid reaction medium wherein in the first and second oxidation reaction zone endoparticle catalyst concentration as scheme 117 described methods.

120, as scheme 119 described methods, wherein the reaction mixture outflow thing of being discharged by second oxidation reaction zone also comprises beaded catalyst, this method also comprises separating particles catalyzer from the reaction mixture outflow thing of being discharged by second oxidation reaction zone, forms the catalyst recycle logistics that comprises isolating catalyzer.

121,, comprise that also at least a portion beaded catalyst that will contain is incorporated at least one of first and second oxidation reaction zones in the catalyst recycle logistics as scheme 120 described methods.

122, as scheme 121 described methods, wherein in catalyst filter, flow out thing separating particles catalyzer from reaction mixture, form the filtrate that the catalyst recycle logistics reaches not to be had beaded catalyst substantially and comprise N-((phosphonomethyl)) glycine product.

123,, wherein adopt catalyst filter to flow out the continuous separating particles catalyzer of thing from reaction mixture as scheme 122 described methods.

124, as scheme 123 described methods, wherein catalyst filter is continuous back-flushing filter.

125, as scheme 124 described methods, wherein back-flushing filter comprises filter element, and part filtrate is used for the back-flushing filter element and removes isolating catalyzer by filter element.

126,, before at least a portion beaded catalyst that wherein contains in the catalyst recycle logistics one of is being incorporated in first and second oxidation reaction zones at least, be passed in the catalyst stores jar as scheme 124 described methods.

127, as scheme 126 described methods, wherein the catalyst stores jar does not contain O substantially ₂

128, as scheme 127 described methods, also comprise non-oxidizing gas is incorporated into the catalyst stores jar.

129, as scheme 127 described methods, wherein the residence time of catalyst recycle in the catalyst stores jar is at least about 2 minutes.

130, as scheme 121 described methods, at least a portion beaded catalyst that wherein contains in the catalyst recycle logistics and N-((phosphonomethyl)) iminodiethanoic acid substrate are incorporated into first oxidation reaction zone simultaneously.

131, as scheme 121 described methods, at least a portion beaded catalyst that wherein contains in the catalyst recycle logistics is incorporated into second oxidation reaction zone simultaneously with unreacted N-((phosphonomethyl)) the iminodiethanoic acid substrate that obtains in middle aqueous reaction mixture effluent.

132, as scheme 121 described methods; a part of beaded catalyst that wherein contains in the catalyst recycle logistics and N-((phosphonomethyl)) iminodiethanoic acid substrate are incorporated into first oxidation reaction zone simultaneously, and another part beaded catalyst that contains in the catalyst recycle logistics is incorporated into second oxidation reaction zone simultaneously with unreacted N-((phosphonomethyl)) the iminodiethanoic acid substrate that obtains in middle aqueous reaction mixture effluent.

133, as scheme 121 described methods, wherein from the catalyst recycle logistics, remove catalyzer.

134, as scheme 133 described methods, wherein live catalyst is added in the catalyst recycle logistics.

135, as scheme 119 described methods, wherein the intermediate reaction mixture outflow thing of being discharged by first oxidation reaction zone also comprises beaded catalyst.

136, as scheme 135 described methods, the middle water-containing material stream that wherein is incorporated into second oxidation reaction zone also is included in the intermediate reaction mixture and flows out the beaded catalyst that obtains in the thing.

137, as scheme 135 described methods, also comprise:

Flow out separating particles catalyzer the thing from the intermediate reaction mixture of discharging, form the catalyst recycle logistics that comprises isolating catalyzer by first oxidation reaction zone; With

At least a portion beaded catalyst that will contain in the catalyst recycle logistics and N-((phosphonomethyl)) iminodiethanoic acid substrate are incorporated into first oxidation reaction zone simultaneously.

138, as scheme 137 described methods; wherein in catalyst filter, go out separating particles catalyzer the thing from middle flow of reaction mixture; form the catalyst recycle logistics and do not have beaded catalyst substantially and comprise the filtrate of N-((phosphonomethyl)) glycine product, and the middle water-containing material stream that is incorporated into second oxidation reaction zone comprises described filtrate.

139, as scheme 138 described methods, wherein the reaction mixture outflow thing of being discharged by second oxidation reaction zone also comprises beaded catalyst, this method further comprises separating particles catalyzer from the reaction mixture outflow thing of being discharged by second oxidation reaction zone, forms the second catalyst recycle logistics that comprises isolating catalyzer.

140, as scheme 139 described methods; wherein in second catalyst filter, flow out separating particles catalyzer the thing, form the second catalyst recycle logistics and do not contain beaded catalyst and second filtrate that comprises N-((phosphonomethyl)) glycine product substantially from reaction mixture.

141,, comprise that also at least a portion beaded catalyst that the second catalyst recycle logistics is contained is incorporated at least one of first and second oxidation reaction zones as scheme 140 described methods.

142, as scheme 141 described methods, wherein at least a portion beaded catalyst that will contain in the second catalyst recycle logistics is incorporated in second oxidation reaction zone simultaneously with unreacted N-((phosphonomethyl)) the iminodiethanoic acid substrate that obtains in intermediate reaction mixture outflow thing.

143,, wherein be different from average catalyst age age at second oxidation reaction zone at the average catalyst of first oxidation reaction zone as scheme 142 described methods.

144, as scheme 143 described methods, wherein the average catalyst age in first oxidation reaction zone is greater than the average catalyst age in second oxidation reaction zone.

145, as scheme 143 described methods, wherein the average catalyst age in first oxidation reaction zone is less than the average catalyst age in second oxidation reaction zone.

146,, wherein adopt catalyst filter to go out continuous separating particles catalyzer thing and the reaction mixture outflow thing from middle flow of reaction mixture as scheme 140 described methods.

147, as scheme 119 described methods, also comprise the liquid reaction medium that cools off first oxidation reaction zone.

148, as scheme 147 described methods, wherein the liquid reaction medium of first oxidation reaction zone cools off in the external heat exchange cycles loop that comprises heat exchanger that links to each other with first stirred-tank reactor.

149, as scheme 147 described methods, wherein second oxidation reaction zone is operated with adiabatic method.

150, as scheme 147 described methods, further comprise the liquid reaction medium that cools off second oxidation reaction zone.

151, as scheme 150 described methods, wherein the liquid reaction medium of second oxidation reaction zone cools off in the external heat exchange cycles loop that comprises heat exchanger that links to each other with second stirred-tank reactor.

152, as scheme 150 described methods, wherein the temperature at the liquid reaction medium of first oxidation reaction zone is maintained at about 95 ℃ to about 105 ℃, and the temperature of the liquid reaction medium of second oxidation reaction zone is maintained at about 100 ℃ to about 105 ℃.

153, as scheme 119 described methods, wherein N-((phosphonomethyl)) the iminodiethanoic acid concentration of substrate in water-containing material stream is that about 7% weight is to about 15% weight.

154, as scheme 153 described methods, wherein oxygenant is to contain O ₂Gas, and will contain O ₂In the liquid reaction medium of gas spray cloth in first and second oxidation reaction zones.

155, as scheme 154 described methods; wherein for every mole of N-((phosphonomethyl)) iminodiethanoic acid substrate in being incorporated into the water-containing material stream of first stirred-tank reactor, the total oxygen demand that is incorporated into first and second oxidation reaction zones is about 0.5 to about 5 moles of O ₂

156, as scheme 155 described methods; wherein for every mole of N-((phosphonomethyl)) iminodiethanoic acid substrate in being incorporated into the water-containing material stream of first stirred-tank reactor, the total oxygen demand that is incorporated into first and second oxidation reaction zones is about 1 to about 3 moles of O ₂

157, as scheme 156 described methods; wherein for every mole of N-((phosphonomethyl)) iminodiethanoic acid substrate in being incorporated into the water-containing material stream of first stirred-tank reactor, the total oxygen demand that is incorporated into first and second oxidation reaction zones is about 1.5 to about 2.5 moles of O ₂

158, as scheme 156 described methods, wherein flowing out N-((phosphonomethyl)) iminodiethanoic acid concentration of substrate in the thing at the reaction mixture of being discharged by second stirred-tank reactor is about 200 to about 2000 ppm by weight.

159, as scheme 158 described methods, wherein flowing out N-((phosphonomethyl)) iminodiethanoic acid concentration of substrate in the thing at the reaction mixture of being discharged by second stirred-tank reactor is about 500 to about 1500 ppm by weight.

160, as scheme 159 described methods, wherein flowing out N-((phosphonomethyl)) iminodiethanoic acid concentration of substrate in the thing at the reaction mixture of being discharged by second stirred-tank reactor is about 500 to about 700 ppm by weight.

161, as scheme 156 described methods, wherein N-((phosphonomethyl)) iminodiethanoic acid substrate to the transformation efficiency of N-((phosphonomethyl)) glycine product is at least about 70% in first oxidation reaction zone.

162, as scheme 161 described methods, wherein N-((phosphonomethyl)) iminodiethanoic acid substrate to the transformation efficiency of N-((phosphonomethyl)) glycine product is about 80% to about 95% in first oxidation reaction zone.

163, as scheme 162 described methods, wherein will be incorporated into first and second oxidation reaction zones total oxygen about 70% be incorporated into first stirred-tank reactor to about 90%.

164, as scheme 154 described methods, wherein contain O ₂Gas is so that at least about 60% O ₂The speed that is utilized in first oxidation reaction zone is incorporated into first oxidation reaction zone.

165, as scheme 164 described methods, wherein contain O ₂Gas is so that at least about 80% O ₂The speed that is utilized in first oxidation reaction zone is incorporated into first oxidation reaction zone.

166, as scheme 165 described methods, wherein contain O ₂Gas is so that at least about 90% O ₂The speed that is utilized in first oxidation reaction zone is incorporated into first oxidation reaction zone.

167, as scheme 154 described methods, wherein contain O ₂Gas is so that at least about 60% O ₂The speed that is utilized in second oxidation reaction zone is incorporated into second oxidation reaction zone.

168, as scheme 167 described methods, wherein contain O ₂Gas is so that at least about 80% O ₂The speed that is utilized in second oxidation reaction zone is incorporated into second oxidation reaction zone.

169, as scheme 168 described methods, wherein contain O ₂Gas is so that at least about 90% O ₂The speed that is utilized in second oxidation reaction zone is incorporated into second oxidation reaction zone.

170, as scheme 119 described methods, wherein the ratio of the working volume of the working volume of the liquid reaction medium in first stirred-tank reactor and the liquid reaction medium in second stirred-tank reactor is greater than 1.

171, as scheme 170 described methods, wherein the ratio of the working volume of the working volume of the liquid reaction medium in first stirred-tank reactor and the liquid reaction medium in second stirred-tank reactor is about 1.1 to about 5.

172, as scheme 119 described methods, wherein the residence time in first stirred-tank reactor is about 10 to about 30 minutes.

173, as scheme 172 described methods, wherein the residence time in second stirred-tank reactor is about 6 to about 20 minutes.

174, as scheme 119 described methods, wherein beaded catalyst also comprises catalyst surface promotor, its ratio be catalyzer at least about 0.05% weight.

175, as scheme 174 described methods, wherein catalyst surface promotor comprises bismuth, tin, cadmium, magnesium, manganese, nickel, aluminium, cobalt, lead, titanium, antimony, selenium, iron, rhenium, zinc, cerium, zirconium, tellurium or germanium.

176,, also comprise supplemental promoter being incorporated into reactor assembly and it being mixed with beaded catalyst as scheme 174 described methods.

177,, wherein supplemental promoter is incorporated in the liquid reaction medium at least one oxidation reaction zone as scheme 176 described methods.

178,, wherein supplemental promoter is incorporated into first oxidation reaction zone as scheme 177 described methods.

179,, wherein supplemental promoter is incorporated into reactor assembly continuously or intermittently as scheme 176 described methods.

180, as scheme 176 described methods, the supplemental promoter that wherein is incorporated into reactor assembly has increased the formaldehyde that the beaded catalyst oxidation produces or the activity and/or the selectivity of formic acid in N-((phosphonomethyl)) iminodiethanoic acid substrate oxidising process.

181, as scheme 176 described methods, the supplemental promoter that wherein is incorporated into reactor assembly has increased activity and/or the selectivity that catalyzer is oxidized to N-((phosphonomethyl)) iminodiethanoic acid substrate N-((phosphonomethyl)) glycine product.

182, as scheme 176 described methods, wherein supplemental promoter has reduced the leaching of precious metal from the carbon support.

183, as scheme 176 described methods, wherein supplemental promoter comprises bismuth, lead, germanium, tellurium, titanium, copper and/or nickel.

184, as scheme 183 described methods, wherein supplemental promoter comprises bismuth.

185, as scheme 184 described methods, the supplemental promoter that wherein is incorporated into reactor assembly is the bismuth oxide compound, bismuth oxyhydroxide, the bismuth muriate, the bismuth bromide, the bismuth iodide, bismuth sulphide, the bismuth selenide, the bismuth telluride, bismuth sulphite, bismuth vitriol, oxygen bismuth vitriol, oxygen bismuth nitrite, bismuth nitrate, oxygen bismuth nitrate, two nitrate of bismuth and magnesium, the bismuth phosphite, bismuth phosphoric acid salt, the bismuth pyrophosphate salt, oxygen bismuth carbonate, the bismuth perchlorate, the bismuth stibnate, the bismuth arsenate, the bismuth selenite, the bismuth titanate, the bismuth vanadate, the bismuth niobate, the bismuth tantalate, the bismuth chromic salt, oxygen bismuth dichromate, oxygen bismuth chromic salt, two chromic salt of oxygen bismuth and potassium, the bismuth molybdate, two molybdates of bismuth and sodium, the bismuth tungstate, the bismuth permanganate, the bismuth zirconate, the bismuth acetate, oxygen bismuth propionic salt, the bismuth benzoate, oxygen bismuth salicylate, the bismuth oxalate, the bismuth tartrate, the bismuth magma hydrochlorate, the bismuth Citrate trianion, the bismuth gallate, the bismuth pyrogallate, the bismuth phosphide, bismuth arsenide, sodium bismuthate, bismuth-thiocyanic acid, the sodium salt of bismuth-thiocyanic acid, the sylvite of bismuth-thiocyanic acid, trimethylammonium, triphenyl, the form of bismuth oxychloride or bismuth oxyiodide.

186, as scheme 185 described methods, the supplemental promoter that wherein is incorporated into reactor assembly is the bismuth oxide form.

187, as scheme 186 described methods, the supplemental promoter that wherein is incorporated into reactor assembly is Bi ₂O ₃

188, remove from the initial aqueous solution that comprises N-((phosphonomethyl)) glycine product and anhydrate and make therefrom crystalline method of N-((phosphonomethyl)) glycine product, this method comprises:

Moisture evaporation raw mix is incorporated into evaporating area, and described raw mix comprises the described initial aqueous solution;

In the presence of solid particulate N-((phosphonomethyl)) glycine product, in described evaporating area, from described raw mix, water is evaporated, thereby produce the vapor phase that comprises water vapour, from aqueous liquid phase, be settled out N-((phosphonomethyl)) glycine product, and generation comprises N-((phosphonomethyl)) glycine product solid and N-((phosphonomethyl)) glycine product is saturated substantially or the evaporate of oversaturated mother liquor; With

The ratio that keeps particle N-((phosphonomethyl)) glycine product solid and mother liquor in described evaporating area is greater than the ratio of the N-that is produced gradually by evaporative effect ((phosphonomethyl)) glycine product solid with the mother liquor that produces gradually thus.

189,, wherein described evaporate is divided into the relative poor mother liquor fraction of poor relatively N-((phosphonomethyl)) the glycine product solid fraction of mother liquor with N-((phosphonomethyl)) glycine product solid as scheme 188 described methods.

190,, wherein in described evaporating area, keep the ratio of described particle N-((phosphonomethyl)) glycine product solid and mother liquor to comprise that the solid that will obtain turns back to described evaporating area and the solid that will obtain is retained in the described district in described solid fraction in described solid fraction as scheme 189 described methods.

191, as scheme 190 described methods, comprising:

The evaporation raw mix that will comprise the described initial aqueous solution is incorporated into the vapour of described evaporating area/liquid disengaging zone, wherein pressure is lower than the vapour pressure of described mixture, thereby water flash distillation from the evaporation raw mix is come out, produced the vapor phase that comprises water vapour, and N-((phosphonomethyl)) glycine product is precipitated out from liquid phase, produced first slurry flow of particle N-((phosphonomethyl)) the glycine product that is included in saturated or the supersaturation mother liquor;

Described vapor phase is separated with described first slurry flow;

Described first slurry flow is incorporated into the reserved area, separate with second slurry flow that comprises sedimentary N-((phosphonomethyl)) glycine product and mother liquor at this upper strata liquid that comprises described mother liquor fraction, described reserved area has the import of described first slurry, be positioned at the decanting liq outlet that is used for described upper strata liquid on the described import, and be positioned on the described import but the outlet of described second slurry under the decanting liq outlet; With

Keep described first slurry is incorporated into described reserved area; the speed of relative movement that described second slurry is discharged by described second slurry outlet and described upper strata liquid is discharged by described decanting liq outlet; make the upward flow speed in the lower region of the described reserved area under described second slurry outlet be enough to keep sedimentary N-((phosphonomethyl)) glycine product to be suspended in the liquid phase, and the upward flow speed in the upper area of the described reserved area on described second slurry outlet is under the settling velocity of N-((phosphonomethyl)) glycine product particle of at least 80% weight in lower region.

192, as scheme 191 described methods, wherein at least a portion with the described second slurry logistics is incorporated into described vapour/liquid disengaging zone.

193, as scheme 192 described methods, at least a portion of the wherein said second slurry logistics and the described initial aqueous solution have constituted the evaporation raw mix that is incorporated into described vapour/liquid disengaging zone together.

194,, wherein the described initial aqueous solution and the described second slurry logistics are mixed before the disengaging zone being incorporated into described vapour/liquid as scheme 193 described methods.

195, as scheme 193 described methods, wherein remove the 3rd slurry logistics from the lower region in described district.

196, as scheme 195 described methods, wherein said the 3rd slurry logistics is removed from described lower region by the slurry outlet that separates with described second slurry outlet.

197, as scheme 195 described methods, wherein by the described second slurry logistics being divided into recirculation stream and described the 3rd slurry logistics obtains described the 3rd slurry logistics.

198; as scheme 195 described methods; wherein said initial water solution flow is to described vapour/liquid disengaging zone; all or part of described second slurry flow is recycled to described vapour/liquid disengaging zone; described upper strata liquid is discharged from described decanting liq outlet; described the 3rd slurry flow is discharged from the lower region of described reserved area; and any liquid or solid logistics of carrying the logistics of any solid/liquid separation that may stand from described the 3rd slurry turns back to the speed of relative movement of described evaporating area; be enough to set up at the lower region in described district the ratio of certain N-((phosphonomethyl)) glycine product solid and mother liquor, this ratio is higher than the ratio of precipitated solid N-((phosphonomethyl)) glycine product that produces gradually by evaporative effect and the mother liquor that produces gradually thus.

199, as scheme 198 described methods; wherein control the relative velocity of described each logistics; make N-((phosphonomethyl)) glycine product solids concn at the lower region in described district; be such solid and mother liquor mixture, promptly under the situation that does not have the described recirculation second slurry logistics in described vapour/liquid zone N-((phosphonomethyl)) the glycine product solids concn by the solid that maybe will produce by the described initial aqueous solution of flash distillation and mother liquor mixture at least about 2 times.

200, as scheme 199 described methods, wherein from described the 3rd slurry, remove solid, produce the recycled liquid fraction that is recycled to described vapour/liquid disengaging zone, thereby described evaporation raw mix further comprises described recycled liquid fraction.

201, as scheme 200 described methods, the wherein said initial aqueous solution and described recycled liquid fraction were mixed with the described second slurry logistics before being incorporated into described vapour/liquid disengaging zone.

202, as scheme 201 described methods, wherein control whole described logistics, comprise the relative velocity of described recycled liquid fraction, make that the slurry solids content in the lower region in described district is at least about 12% weight.

203, as scheme 201 described methods, wherein control the relative velocity of described each logistics, the feasible solid of removing from described the 3rd slurry has the intermediate value cube weighting granularity at least about 200 μ m.

204, as scheme 201 described methods, wherein control the relative velocity of described each logistics, make the solid of from described the 3rd slurry, removing have and be not higher than about 0.09m ²The BET surface-area of/g.

205, as scheme 203 described methods, wherein the upward flow speed in described lower region is at least 4 times of at least 80% weight solid settling velocity that wherein contains, and the upward flow speed in the upper area in this district is less than 1/4th of at least 80% weight solid settling velocity in described second slurry.

206, as scheme 199 described methods; wherein said raw mix comprises the slurry of N-((phosphonomethyl)) glycine product in the oversaturated aqueous liquid phase of N-((phosphonomethyl)) glycine product; described raw mix is along flowing not significant axially back mixing at described second slurry outlet and the recirculation path that enters between the import of described vapour/liquid disengaging zone.

207, as scheme 206 described methods, the solid surface-area that wherein contains in described raw mix is enough to produce crystallization N-((phosphonomethyl)) the glycine product that intermediate value cube weighting granularity is at least about 200 μ m.

208, as scheme 207 described methods; wherein the degree of supersaturation of the difference expression between the saturation concentration of N-((phosphonomethyl)) glycine product is the highest with N-((phosphonomethyl)) glycine production concentration in the aqueous liquid phase of any position in described recirculation path with in the aqueous liquid phase of this position is not more than about 0.7% weight, based on aqueous liquid phase.

209, as scheme 207 described methods; wherein the integral mean degree of supersaturation with the difference expression between N-((phosphonomethyl)) the glycine product saturation concentration of N-((phosphonomethyl)) the glycine production concentration of aqueous liquid phase in whole described recirculation path and aqueous liquid phase is not more than about 0.5% weight, based on aqueous liquid phase.

210; as scheme 207 described methods; wherein with the integral mean degree of supersaturation of the difference expression between N-((phosphonomethyl)) the glycine product saturation concentration of N-((phosphonomethyl)) the glycine production concentration of aqueous liquid phase in whole described recirculation path and aqueous liquid phase; than providing identical with reference to the required degree of supersaturation low at least 0.2% of vaporizer per unit working volume crystallization throughput; wherein saidly be made up of complete back mixing evaporating area with reference to vaporizer, the ratio of N-in evaporating area ((phosphonomethyl)) glycine product solid and mother liquor equals the ratio of N-((phosphonomethyl)) glycine product solid that is produced gradually by evaporative effect and the mother liquor that produces gradually thus.

211, as scheme 199 described methods, the speed that wherein said second slurry is recycled to described vapour/liquid disengaging zone be described upper strata liquid from the described decanting liq outlet velocity of discharge at least about 20 times.

212, as scheme 191 described methods, wherein said vapour/liquid disengaging zone is on the lower region and the interface between the upper area of described reserved area, and isolate with described upper area, described vapour/liquid disengaging zone keeps flow communication through the lower region of drainage tube and described reserved area, so that described first slurry flows to described lower region from described disengaging zone.

213, as scheme 191 described methods, wherein this method is to operate under the heat passage situation that does not arrive or leave described vapour/liquid disengaging zone, described reserved area, described raw mix or described second slurry substantially.

214, as scheme 191 described methods, wherein when evaporation N-((phosphonomethyl)) glycine product precipitation mainly by evaporating area in the cooling of aqueous liquid phase cause.

215, as scheme 191 described methods, comprising:

Remove the evaporate slurry from the lower region of described reserved area;

Described evaporate slurry is carried out solid/liquid separation, obtain the relative poor mother liquor fraction of poor relatively N-((phosphonomethyl)) the glycine product solid fraction of mother liquor with N-((phosphonomethyl)) glycine product solid; With

The solid that will obtain in described solid fraction turns back to described evaporating area or the solid that will obtain in described solid fraction is retained in the described district, thereby keeps particle N-((phosphonomethyl)) the glycine product solid and the ratio of mother liquor to surpass by N-((phosphonomethyl)) the glycine product solid of evaporation generation and the ratio of consequent mother liquor in described evaporating area.

216, be used for removing from the initial aqueous solution that comprises N-((phosphonomethyl)) glycine product and anhydrate and make therefrom crystalline method of N-((phosphonomethyl)) glycine product, this method comprises:

The evaporation raw mix that will comprise the described initial aqueous solution is incorporated into vapour/liquid disengaging zone, wherein pressure is lower than the vapour pressure of described mixture, thereby water flash distillation from the evaporation raw mix is come out, produced the vapor phase that comprises water vapour, and make N-((phosphonomethyl)) glycine product be increased to concentration above N-((phosphonomethyl)) glycine product solubleness in the concentration of residue in the liquid phase, thereby N-((phosphonomethyl)) glycine product is precipitated out from liquid phase, has produced the first slurry logistics of particle N-((phosphonomethyl)) the glycine product that is included in saturated or the supersaturation mother liquor;

Described vapor phase is separated with the described first slurry logistics;

The described first slurry logistics is incorporated into the decantation district, in this district, the upper strata liquid that comprises described mother liquor fraction separates with the second slurry logistics that comprises sedimentary N-((phosphonomethyl)) glycine product and mother liquor, described decantation district has the import of described first slurry, be positioned at the decanting liq outlet that is used for described upper strata liquid on the described import, and vertically be positioned on the described import but the outlet of described second slurry under the outlet of described upper strata liquid; With

Keep described first slurry is incorporated into described decantation district; the speed of relative movement that described second slurry is discharged by described second slurry outlet and described upper strata liquid is discharged by described decanting liq outlet; make the upward flow speed in the lower region in the described decantation district under described second slurry outlet be enough to keep sedimentary N-((phosphonomethyl)) glycine product to be suspended in the liquid phase, and the upward flow speed in the upper area in the described decantation district on described second slurry outlet is under the settling velocity of N-((phosphonomethyl)) glycine product particle of at least 80% weight in lower region.

217, remove from the initial aqueous solution that comprises N-((phosphonomethyl)) glycine product and anhydrate and make therefrom crystalline method of N-((phosphonomethyl)) glycine product, this method comprises:

Moisture evaporation raw mix is incorporated into evaporating area, and described raw mix comprises the described initial aqueous solution;

In the presence of solid particulate N-((phosphonomethyl)) glycine product, in described evaporating area, water is evaporated from described raw mix, thereby produce the vapor phase that comprises water vapour, from aqueous liquid phase, be settled out N-((phosphonomethyl)) glycine product, and generation comprises N-((phosphonomethyl)) glycine product solid and N-((phosphonomethyl)) glycine product is saturated substantially or the evaporate of oversaturated mother liquor;

Described evaporate is divided into the relative poor mother liquor fraction with N-((phosphonomethyl)) glycine product solid of poor relatively N-((phosphonomethyl)) the glycine product solid fraction of mother liquor; With

The ratio that keeps particle N-((phosphonomethyl)) glycine product solid and mother liquor in described evaporating area is greater than the ratio of the N-that is produced gradually by evaporative effect ((phosphonomethyl)) glycine product solid with the mother liquor that produces gradually thus.

218, prepare the method for N-((phosphonomethyl)) glycine product, comprising:

The water-containing material mixture that will comprise N-((phosphonomethyl)) iminodiethanoic acid substrate is incorporated in the liquid reaction medium;

Catalyzed oxidation N-((phosphonomethyl)) iminodiethanoic acid substrate in described liquid, aqueous reaction medium, thus acquisition comprises the reaction mixture of N-((phosphonomethyl)) glycine product;

To be included in the primary crystallization raw mix cooling of N-((phosphonomethyl)) the glycine product that produces in the described reaction mixture, thereby make N-((phosphonomethyl)) glycine product precipitation and generation comprise the elementary mother liquor of N-((phosphonomethyl)) glycine product;

N-((phosphonomethyl)) the glycine product of precipitation separation from described elementary mother liquor; With

Be incorporated in the described liquid reaction medium with elementary mother liquor recirculation and with it, N-((phosphonomethyl)) iminodiethanoic acid substrate is oxidized to N-((phosphonomethyl)) glycine product there.

219, as scheme 128 described methods, wherein described reaction mixture is divided into elementary fraction and secondary fraction, described primary crystallization raw mix is included in N-((phosphonomethyl)) the glycine product that obtains in the described elementary fraction.

220, as scheme 219 described methods; crystallization goes out N-((phosphonomethyl)) glycine product in the secondary crystallization device raw mix of N-((phosphonomethyl)) the glycine product that wherein obtains from be included in described secondary fraction, thereby produces the secondary mother liquor of the by product that comprises N-((phosphonomethyl)) glycine product and described oxidizing reaction.

221, as scheme 220 described methods; the moisture second reactor raw mix of unreacted N-((phosphonomethyl)) the iminodiethanoic acid substrate that wherein will be included in N-((phosphonomethyl)) the glycine product that obtains in the described secondary fraction and wherein contain is incorporated into the secondary oxidation reaction zone; there; unreacted N-((phosphonomethyl)) iminodiethanoic acid substrate is oxidized; generation contains the secondary oxidation reaction mixture of additional N-((phosphonomethyl)) glycine product, and described secondary crystallization device raw mix comprises described secondary oxidation reaction mixture.

222, as scheme 221 described methods, wherein said secondary oxidation reaction zone comprises the fixed bed that contains oxide catalyst.

223, as scheme 220 described methods, wherein N-((phosphonomethyl)) glycine product crystalline process from described primary crystallization raw mix comprises the transpiration cooling of described primary raw materials mixture.

224,, wherein in the transpiration cooling process, remove about 5% the water that accounts for described primary crystallization raw mix to about 30% weight as scheme 223 described methods.

225, as scheme 223 described methods, wherein said transpiration cooling is carried out with basic adiabatic method.

226, as scheme 224 described methods, wherein said N-((phosphonomethyl)) glycine product crystalline process from described secondary crystallization raw mix comprises heat and drives evaporative crystallization.

227, as scheme 218 described methods, wherein N-((phosphonomethyl)) iminodiethanoic acid substrate is oxidized in the described liquid, aqueous reaction medium in primary oxidation reactor district, thereby generates the primary oxidation product, and this method further comprises:

Described primary oxidation product is divided into finishes reacting material mixture and primary crystallization fraction, described water-containing crystal raw mix comprises described primary crystallization fraction;

The described reacting material mixture of finishing is incorporated into and finishes reaction zone; With

Will to finish residual N-((phosphonomethyl)) the iminodiethanoic acid substrate catalyzed oxidation that contains in the reacting material mixture be N-((phosphonomethyl)) glycine product described, obtain final reacting mixture.

228, as scheme 227 described methods, wherein said primary oxidation product contains 0.5 unreacted N-((phosphonomethyl)) iminodiethanoic acid to about 2% weight of having an appointment.

229, as scheme 228 described methods; wherein the secondary crystallization device raw mix that is included in N-((phosphonomethyl)) the glycine product that obtains in the described final reacting mixture is carried out heat and drive evaporative crystallization, thereby be settled out the secondary mother liquor that N-((phosphonomethyl)) glycine product and generation comprise N-((phosphonomethyl)) glycine product and N-((phosphonomethyl)) iminodiethanoic acid substrate oxidized byproduct.

230, as scheme 218 described methods, wherein N-((phosphonomethyl)) iminodiethanoic acid substrate oxidation continuously in the presence of precious metal/C catalyst.

231, prepare the method for N-((phosphonomethyl)) glycine product, comprising:

The water-containing material mixture that will comprise N-((phosphonomethyl)) iminodiethanoic acid substrate is incorporated into the catalytic reactor system that comprises one or more catalytic reaction zones,

In described catalytic reactor system, N-((phosphonomethyl)) iminodiethanoic acid substrate Catalytic Oxygen is changed into N-((phosphonomethyl)) glycine product, generate product mixtures;

Described product mixtures is divided into elementary fraction and secondary fraction;

N-((phosphonomethyl)) glycine product is crystallized out from described elementary fraction, obtain solid N-((phosphonomethyl)) glycine product fraction and elementary mother liquor;

With elementary mother liquor recirculation, as the water source of the described raw mix of preparation.

232, as scheme 231 described methods, wherein basic all described elementary mother liquor recirculation is as the water source of the described raw mix of preparation.

233, as scheme 231 described methods, wherein N-((phosphonomethyl)) glycine crystallizes out from described elementary fraction by evaporative crystallization.

234, as scheme 233 described methods, wherein other N-((phosphonomethyl)) glycine crystallizes out from described secondary fraction, thereby produces the secondary mother liquor.

235, as scheme 234 described methods, wherein N-((phosphonomethyl)) glycine crystallizes out from described secondary fraction by evaporative crystallization.

236, as scheme 235 described methods, wherein N-((phosphonomethyl)) glycine crystallizes out from described elementary fraction by the evaporative crystallization that carries out with basic adiabatic method.

237, as scheme 235 described methods, wherein described raw mix is incorporated into described reactor assembly continuously, the basic back mixing with regard to liquid phase wherein of described intrasystem reaction zone, exothermic heat of reaction are used for content with raw mix and are heated at described back mixing reaction zone and account for leading temperature of reaction.

238, as scheme 237 described methods, wherein said catalyst for reaction comprises precious metal, and can effectively will be selected from the C of formaldehyde and formic acid ₁The by product oxidation, described C ₁The oxidation of by product further helps to heat the content of described water-containing material mixture.

239, as scheme 231 described methods; wherein N-((phosphonomethyl)) iminodiethanoic acid oxidation in the presence of the heterogeneous catalyst that comprises precious metal; the small portion precious metal is leached from described catalyzer in described catalyst oxidation reactor system, and the leaching precious metal that contains in described elementary fraction turns back to described catalytic reactor system in described elementary mother liquor.

240, as scheme 239 described methods, wherein the leaching precious metal that contains in the elementary mother liquor of described recirculation has suppressed precious metal further leaching from catalyzer in described catalytic reactor system.

241, as scheme 239 described methods, the precious metal that the part that wherein contains in described recirculation mother liquor leaches is deposited on the surface of described heterogeneous catalyst in described catalytic reactor system again.

242, be used for catalyzed oxidation N-((phosphonomethyl)) iminodiethanoic acid substrate to generate the continuation method of N-((phosphonomethyl)) glycine product, this method comprises:

The liquid phase feed stream that will comprise the water-containing material stream that contains N-((phosphonomethyl)) iminodiethanoic acid substrate is incorporated into the primary oxidation reactor district, and the primary oxidation reactor district comprises the primary fixed bed that contains oxide catalyst;

Oxygenant is incorporated into the primary oxidation reactor district;

In the primary oxidation reactor district, N-((phosphonomethyl)) iminodiethanoic acid substrate is oxidized to N-((phosphonomethyl)) glycine product continuously, thereby forms the primary reaction mixture that comprises N-((phosphonomethyl)) glycine product and unreacted N-((phosphonomethyl)) iminodiethanoic acid substrate;

Discharge the primary reaction mixture from the primary oxidation reactor district; With

The water-containing material that unit weight sensible heat content difference between described reaction mixture and described water-containing material stream is remained below per unit weight flows the thermopositive reaction heat that produces in reaction zone.

243, as scheme 242 described methods, the measure that wherein the unit weight sensible heat content difference between described reaction mixture and described water-containing material stream is remained below the thermopositive reaction heat that the water-containing material stream of per unit weight produces in reaction zone comprises, by hot indirect transfer is cooled off described fixed bed to the heat-transfer fluid or the process fluid of the conduit of flowing through in described or touching with described bench grafting.

244, as scheme 242 described methods; the measure that wherein the unit weight sensible heat content difference between described reaction mixture and described water-containing material stream is remained below the thermopositive reaction heat that the water-containing material stream of per unit weight produces in reaction zone comprises; the recirculation fraction that is included in N-((phosphonomethyl)) glycine that produces in the reaction is incorporated in the described bed, and wherein said recirculation fraction is cooled in the outside of described fixed bed.

245, as scheme 244 described methods, comprising:

The primary reaction mixture is divided into elementary product fraction and primary reactor circulation fraction;

Allow primary reaction mixture or primary reactor recirculation fraction by heat exchanger, so that remove the heat of oxidation of N-((phosphonomethyl)) iminodiethanoic acid substrate; With

Primary reactor recirculation fraction is turned back to the primary oxidation reactor district.

246,, wherein before described primary reaction mixture is cut apart, make described primary reaction mixture by described heat exchanger as scheme 245 described methods.

247, as scheme 245 described methods, wherein the ratio of the volumetric flow rate of the volumetric flow rate of primary reactor recirculation fraction and elementary product fraction is at least about 0.5: 1.

248, as scheme 247 described methods, wherein the ratio of the volumetric flow rate of the volumetric flow rate of primary reactor recirculation fraction and elementary product fraction be about 1: 1 to about 10: 1.

249, as scheme 244 described methods, wherein water-containing material stream and primary reactor recirculation fraction are mixed, obtain the inlet stream of merging, the liquid phase feed stream that is incorporated into oxidation reaction zone comprises the imported raw material stream of described merging.

250; as scheme 249 described methods; wherein water-containing material stream comprises the slurry of N-((phosphonomethyl)) iminodiethanoic acid substrate in the saturated substantially aqueous solution of N-((phosphonomethyl)) iminodiethanoic acid substrate; and primary reactor recirculation fraction has N-((phosphonomethyl)) the iminodiethanoic acid substrate content lower than water-containing material stream, does not contain N-((phosphonomethyl)) iminodiethanoic acid substrate solid under the leading condition substantially thereby account in the liquid-inlet zone of primary fixed bed by the inlet stream of water-containing material stream being mixed the merging of acquisition with primary reactor recirculation fraction.

251, as scheme 250 described methods; wherein water-containing material stream comprises the slurry that contains 8 N-to about 15% weight ((phosphonomethyl)) the iminodiethanoic acid substrate of having an appointment, and primary reactor recirculation fraction comprises the solution that contains 0.5 N-to about 5% weight ((phosphonomethyl)) the iminodiethanoic acid substrate of having an appointment.

252, as scheme 242 described methods, further comprise:

The second reactor feedstocks mixture that will comprise the elementary product fraction of at least a portion is incorporated into second oxidation reaction zone, and second oxidation reaction zone comprises second fixed bed that contains oxide catalyst;

Oxygenant is incorporated in second oxidation reaction zone; With

In second oxidation reaction zone,, generate second mixture of reaction products that contains N-((phosphonomethyl)) glycine product with N-((phosphonomethyl)) iminodiethanoic acid substrate and the continuous oxidation of by product C1 compound.

253, as scheme 252 described methods, at least 95% N-((phosphonomethyl)) the iminodiethanoic acid substrate that wherein contains in water-containing material stream is oxidized in elementary and second oxidation reaction zone.

254, as scheme 253 described methods, at least 98% N-((phosphonomethyl)) the iminodiethanoic acid substrate oxidation in elementary and second oxidation reaction zone that wherein in water-containing material stream, contains.

255, as scheme 242 described methods, wherein the primary fixed bed in the primary oxidation reactor district contains precious metal/C catalyst.

256, as scheme 255 described methods, wherein the primary fixed bed in the primary oxidation reactor district contains the C catalyst of non precious metal.

257, as scheme 256 described methods, further comprise:

At least a portion of second reaction mixture is incorporated into the 3rd oxidation reaction zone that comprises the fixed bed that contains oxide catalyst;

Oxygenant is incorporated into the 3rd oxidation reaction zone; With

In the 3rd oxidation reaction zone with by product C ₁The continuous oxidation of compound generates the 3rd mixture of reaction products that contains N-((phosphonomethyl)) glycine product.

258,, further be included in the 3rd oxidation reaction zone the oxidation of N-((phosphonomethyl)) iminodiethanoic acid substrate as scheme 257 described methods.

259, as scheme 257 described methods, wherein the fixed bed in the 3rd oxidation reaction zone contains precious metal/C catalyst, and the reaction in the 3rd oxidation reaction zone comprises the C that catalyzed oxidation keeps in second reaction mixture ₁Compound.

260, as scheme 257 described methods, wherein liquid reaction mixture is with basic piston flow with do not having described the 3rd mixture of reaction products recirculation substantially or therefrom telling under the situation of other effluent by the 3rd fixed bed.

261, as scheme 260 described methods, wherein the 3rd oxidation reaction zone is operated under the situation that does not have the liquid reaction mixture back mixing substantially.

262, as scheme 255 described methods, wherein the fixed bed in the primary oxidation reactor district contains precious metal/C catalyst, C ₁Compound is oxidized in the primary oxidation reactor district.

263, as scheme 252 described methods, wherein liquid reaction mixture is with basic piston flow with do not having the described second mixture of reaction products recirculation substantially or therefrom telling under the situation of other effluent by second fixed bed.

264, as scheme 252 described methods, wherein second oxidation reaction zone is operated under the situation that does not have the liquid reaction mixture back mixing substantially.

265,, comprise that further the reaction heat that will produce is delivered in the cooling fluid in second oxidation reaction zone as scheme 252 described methods.

266, as scheme 252 described methods, wherein second oxidation reaction zone is operated with basic adiabatic method.

267, as scheme 242 described methods, wherein oxygenant is to contain O ₂Gas, and the integral mean oxygen partial pressure on the liquid-phase flow path in the primary oxidation reactor district is at least about 50psia.

268, as scheme 267 described methods, wherein the integral mean oxygen partial pressure on the liquid-phase flow path in the primary oxidation reactor district is at least about 100psia.

269,, be about 20% to about 30% volume wherein at the oxygen concn of the gas phase in gas reactor exit as scheme 267 described methods.

270, as scheme 267 described methods, wherein the coefficient of oxygen utilization in the primary oxidation reactor district is about 50% to about 95%.

271,, it is being about 80 ℃ to about 130 ℃ wherein through the integral mean liquidus temperature on the liquid-phase flow path in primary oxidation reactor district as scheme 242 described methods.

272,, it is being about 105 ℃ to about 120 ℃ wherein through the integral mean liquidus temperature on the liquid-phase flow path in primary oxidation reactor district as scheme 242 described methods.

273, as scheme 242 described methods, wherein the ratio of the volume of catalyst surface area and the liquid reaction mixture in the primary fixed bed is about 100 to about 6000m ²/ cm ³

274, as scheme 273 described methods, wherein the ratio of the volume of catalyst surface area and the liquid reaction mixture in the primary fixed bed is about 200 to about 2000m ²/ cm ³

275, as scheme 242 described methods, wherein oxygenant is to contain O ₂Gas, and the liquid and gas concurrent is through the primary fixed bed.

276, as scheme 242 described methods, wherein oxygenant is to contain O ₂Gas, and the liquid and gas reverse direction flow is through the primary fixed bed.

277, as scheme 242 described methods, wherein the catalyst activity in the primary fixed bed is along changing through the liquid-phase flow path of reactor, at the catalyst activity that is lower than with respect to the catalyst activity in the upstream portion of the primary fixed bed of the direction of liquid phase stream in the downstream part.

278, be used for catalyzed oxidation N-((phosphonomethyl)) iminodiethanoic acid substrate to generate the method for N-((phosphonomethyl)) glycine product, this method comprises:

The water-containing material stream that will comprise N-((phosphonomethyl)) iminodiethanoic acid substrate is incorporated into first of serial oxidation reaction zone, and each of serial oxidation reaction zone comprises oxide catalyst;

In first oxidation reaction zone,, produce the intermediate oxidation reaction product with the oxidation of N-((phosphonomethyl)) iminodiethanoic acid substrate;

The intermediate oxidation reaction product is incorporated into second oxidation reaction zone that comprises the fixed bed that contains precious metal/C catalyst; With

Oxidized byproduct formaldehyde and/or formic acid in second oxidation reaction zone.

279, as scheme 278 described methods, wherein first and second oxidation reaction zones comprise the continuous oxidation reaction district, water-containing material stream is incorporated into first oxidation reaction zone continuously or intermittently, and second oxidation reaction zone is discharged and be incorporated into continuously or intermittently to intermediate oxidation product continuously or intermittently from first oxidation reaction zone.

280, as scheme 279 described methods, wherein the intermediate oxidation reaction product was cooled before being incorporated into second oxidation reaction zone.

281, as scheme 280 described methods; wherein each oxidation reaction zone comprises to contain and is useful on the fixed bed that N-((phosphonomethyl)) iminodiethanoic acid substrate is oxidized to the catalyzer of N-((phosphonomethyl)) glycine product; except this series each oxidation reaction zone last has all produced intermediate reaction product; described product is introduced in the next oxidation reaction zone in this series, and the final reacting product that comprises N-((phosphonomethyl)) glycine product is discharged from last oxidation reaction zone.

282, as scheme 281 described methods, wherein this series comprises two above oxidation reaction zones, and the intermediate reaction mixture of each discharge of two oxidation reaction zones was cooled before being incorporated into next oxidation reaction zone in the past.

283, as scheme 282 described methods, wherein the intermediate reaction mixture was cooled before being incorporated into next oxidation reaction zone.

284, as scheme 282 described methods; wherein said water-containing material mixture contains the water-soluble salt at least about N-((phosphonomethyl)) iminodiethanoic acid of 15% weight; by the acid equivalent benchmark; and described final reacting mixture contains the water-soluble salt at least about the N-of 12% weight ((phosphonomethyl)) glycine, by the acid equivalent benchmark.

285, as scheme 284 described methods; wherein said water-containing material mixture contains the water-soluble salt at least about N-((phosphonomethyl)) iminodiethanoic acid of 25% weight; by the acid equivalent benchmark; and described final oxidation mixtures contains the water-soluble salt at least about N-((phosphonomethyl)) glycine of 20% weight, by the acid equivalent benchmark.

286, as scheme 285 described methods; wherein said water-containing material mixture contains the water-soluble salt at least about N-((phosphonomethyl)) iminodiethanoic acid of 35% weight; by the acid equivalent benchmark; and described final oxidation mixtures contains the water-soluble salt at least about N-((phosphonomethyl)) glycine of 28% weight, by the acid equivalent benchmark.

287, as scheme 284 described methods, wherein final oxidizing reaction concentrates by the water of removing wherein.

288, as scheme 287 described methods, wherein described final reacting mixture is incorporated into flash zone, pressure is lower than the vapour pressure of described final oxidation mixtures under its temperature when last of described serial reaction device discharged in the flash zone.

289, as scheme 278 described methods, wherein first oxidation reaction zone is included in the basic back mixing oxidation reaction zone in the continuous stirred tank reactor.

290, be used for catalyzed oxidation N-((phosphonomethyl)) iminodiethanoic acid substrate to generate the continuation method of N-((phosphonomethyl)) glycine product, this method comprises:

The water-containing material stream that will contain N-((phosphonomethyl)) iminodiethanoic acid substrate is incorporated in the oxidation reaction zone that comprises the fixed bed that contains oxide catalyst;

To contain O ₂Gas is incorporated into oxidation reaction zone; With

In oxidation reaction zone, N-((phosphonomethyl)) iminodiethanoic acid substrate is oxidized to N-((phosphonomethyl)) glycine product continuously; thereby produce the oxidation mixtures that comprises N-((phosphonomethyl)) glycine product, the mass flow rate of the liquid phase in the fixed bed is about 20 to about 800 with the mass flow rate of gas phase ratio.

291, be used for catalyzed oxidation N-((phosphonomethyl)) iminodiethanoic acid substrate to generate the continuation method of N-((phosphonomethyl)) glycine product, this method comprises:

The water-containing material stream that will contain N-((phosphonomethyl)) iminodiethanoic acid substrate is incorporated in the oxidation reaction zone that comprises the fixed bed that contains oxide catalyst;

To contain O ₂Gas is incorporated into oxidation reaction zone; With

In oxidation reaction zone, N-((phosphonomethyl)) iminodiethanoic acid substrate is oxidized to N-((phosphonomethyl)) glycine product continuously; thereby obtain to comprise the oxidation mixtures of N-((phosphonomethyl)) glycine product, the liquid phase residual amount in fixed bed is about 0.1 to about 0.5 with the volume ratio of total bed volume.

292, be used for catalyzed oxidation N-((phosphonomethyl)) iminodiethanoic acid substrate to generate the continuation method of N-((phosphonomethyl)) glycine product, this method comprises:

The water-containing material stream that will contain N-((phosphonomethyl)) iminodiethanoic acid substrate is incorporated into the oxidation reaction zone that comprises the fixed bed that contains oxide catalyst;

To contain O ₂Gas is incorporated into oxidation reaction zone; With

In oxidation reaction zone, N-((phosphonomethyl)) iminodiethanoic acid substrate is oxidized to N-((phosphonomethyl)) glycine product continuously; thereby obtain to comprise the oxidation mixtures of N-((phosphonomethyl)) glycine product, be not higher than about 100psia in the oxygen partial pressure of the liquid outlet of fixed bed.

293,, be about 10 to about 50psia wherein in the oxygen partial pressure of fixed bed liquid outlet as scheme 292 described methods.

294, be used for catalyzed oxidation N-((phosphonomethyl)) iminodiethanoic acid substrate to generate the continuation method of N-((phosphonomethyl)) glycine product, this method comprises:

The water-containing material stream that will contain N-((phosphonomethyl)) iminodiethanoic acid substrate is incorporated into the oxidation reaction zone that comprises the fixed bed that contains oxide catalyst;

To contain O ₂Gas is incorporated into oxidation reaction zone; With

In oxidation reaction zone, N-((phosphonomethyl)) iminodiethanoic acid substrate is oxidized to N-((phosphonomethyl)) glycine product continuously; thereby obtain to comprise the oxidation mixtures of N-((phosphonomethyl)) glycine product; N-in liquid phase ((phosphonomethyl)) iminodiethanoic acid concentration of substrate is lower than the optional position of the fixed bed of about 0.1ppm, and oxygen partial pressure is not higher than about 50psia.

295, as scheme 294 described methods, wherein N-((phosphonomethyl)) iminodiethanoic acid concentration of substrate is lower than any position of the fixed bed of about 0.2ppm in liquid phase, and oxygen partial pressure is not higher than about 50psia.

296, be used for catalyzed oxidation N-((phosphonomethyl)) iminodiethanoic acid substrate to generate the continuation method of N-((phosphonomethyl)) glycine product, this method comprises:

The water-containing material stream that will contain N-((phosphonomethyl)) iminodiethanoic acid substrate is incorporated into the oxidation reaction zone that comprises the fixed bed that contains oxide catalyst, and catalyst surface area is about 100 to about 6000m with the ratio of liquid holdup in the fixed bed ²/ cm ³

Oxygenant is incorporated into oxidation reaction zone; With

In oxidation reaction zone, N-((phosphonomethyl)) iminodiethanoic acid substrate is oxidized to N-((phosphonomethyl)) glycine product continuously, thereby obtains to comprise the oxidation mixtures of N-((phosphonomethyl)) glycine product.

297, as scheme 296 described methods, wherein the ratio of catalyst surface area and liquid holdup is about 200 to about 2000m in the fixed bed ²/ cm ³

298, as scheme 297 described methods, wherein the ratio of catalyst surface area and liquid holdup is about 400 to about 1500m in the fixed bed ²/ cm ³

299, as scheme 297 described methods; wherein catalyzer comprises the platinum that loads on the carbon; and be lower than to provide under identical temperature in the continuous stirred tank reactor that is utilizing the Pt/C slurry catalyst in the platinum carrying capacity on the catalyzer and be equal to 70% of the required carrying capacity of productivity, described productivity is represented with pound N-((phosphonomethyl)) glycine product/(hour pound catalyzer).

300, as scheme 297 described methods, wherein catalyzer comprises and contains the platinum/C catalyst that is less than 3% weight platinum.

301, as scheme 296 described methods, wherein the integral mean oxygen partial pressure along the liquid flow path in the fixed bed is at least about 50psia.

302, as scheme 296 described methods, wherein the integral mean temperature of liquid phase is about 80 ℃ to about 130 ℃ in fixed bed.

303, as scheme 296 described methods, N-in liquid phase ((phosphonomethyl)) iminodiethanoic acid concentration of substrate is lower than the optional position of the fixed bed of about 0.1ppm, and oxygen partial pressure is not higher than about 50psia.

304, as scheme 297 described methods, wherein N-((phosphonomethyl)) iminodiethanoic acid concentration of substrate is lower than the optional position of the fixed bed of about 0.2ppm in liquid phase, and oxygen partial pressure is not higher than about 50psia.

305, as scheme 296 described methods, wherein the coefficient of oxygen utilization in oxidation reaction zone is between about 50% and about 95%.

306, be used for catalyzed oxidation N-((phosphonomethyl)) iminodiethanoic acid substrate to generate the continuation method of N-((phosphonomethyl)) glycine product, this method comprises:

The water-containing material stream that will contain N-((phosphonomethyl)) iminodiethanoic acid substrate is incorporated into the oxidation reaction zone that comprises the fixed bed that contains oxide catalyst;

To contain O ₂Gas is incorporated into oxidation reaction zone; With

In oxidation reaction zone, N-((phosphonomethyl)) iminodiethanoic acid substrate is oxidized to N-((phosphonomethyl)) glycine product continuously; thereby obtain to comprise the oxidation mixtures of N-((phosphonomethyl)) glycine product; integral mean oxygen partial pressure along liquid flow path in fixed bed is at least about 50psia, and the integral mean temperature of the liquid phase in fixed bed is about 80 ℃ to about 130 ℃.

307, as scheme 306 described methods, wherein the integral mean oxygen partial pressure along liquid flow path is at least about 100psia in fixed bed, and the integral mean temperature of the liquid phase in fixed bed is about 105 ℃ to about 120 ℃.

308, as scheme 306 described methods, wherein the oxygen partial pressure at the fixed bed liquid outlet is not higher than about 100psia.

309, as scheme 306 described methods, wherein in liquid phase N-((phosphonomethyl)) iminodiethanoic acid concentration of substrate be lower than about 0.1ppm the bed the optional position, oxygen partial pressure is not higher than about 50psia.

310, be used for catalyzed oxidation N-((phosphonomethyl)) iminodiethanoic acid substrate to generate the continuation method of N-((phosphonomethyl)) glycine product, this method comprises:

The water-containing material stream that will contain N-((phosphonomethyl)) iminodiethanoic acid substrate is incorporated into oxidation reaction zone, and this oxidation reaction zone comprises the fixed bed that contains the oxide catalyst body and be used to promote other measure of gas/liquid mass transfer;

To contain O ₂Gas is incorporated into oxidation reaction zone; With

In oxidation reaction zone, N-((phosphonomethyl)) iminodiethanoic acid substrate is oxidized to N-((phosphonomethyl)) glycine product continuously, thereby obtains to comprise the oxidation mixtures of N-((phosphonomethyl)) glycine product.

311, as scheme 310 described methods, other measure of wherein said promotion gas/liquid mass transfer comprises inert filler.

312, as the method for scheme 311, wherein said filler plays the thinner of catalyzer, thus the activity of regulation and control catalyst bed.

313, as scheme 312 described methods, wherein at fluid flow direction, the activity of catalyst bed changes with the variation of the ratio of the surface-area of the surface-area of catalyst body in described direction and inert filler.

314, as scheme 311 described methods, wherein said inert filler is selected from ring-type, saddle and structured packing.

315, be used for catalyzed oxidation N-((phosphonomethyl)) iminodiethanoic acid substrate to generate the continuation method of N-((phosphonomethyl)) glycine product, this method comprises:

The liquid phase feed stream that will comprise the water-containing material mixture that contains N-((phosphonomethyl)) iminodiethanoic acid substrate is incorporated into the primary oxidation reactor district, and this primary oxidation reactor district comprises the fixed bed that contains oxide catalyst;

Oxygenant is incorporated into the primary oxidation reactor district;

In the primary oxidation reactor district, N-((phosphonomethyl)) iminodiethanoic acid substrate is oxidized to N-((phosphonomethyl)) glycine product continuously, thereby produce the liquid phase outlet logistics that comprises the primary reaction mixture, described primary reaction mixture contains N-((phosphonomethyl)) glycine product and unreacted N-((phosphonomethyl)) iminodiethanoic acid substrate; With

Discharge liquid phase outlet logistics from the primary oxidation reactor district; The described liquid phase feed stream introducing speed and the described liquid phase outlet logistics velocity of discharge should make that the liquid phase space-time speed based on total bed volume is about 0.5hr in the described fixed bed ^-1To about 20hr ^-1

316, as scheme 315 described methods, wherein the liquid phase space-time speed in described fixed bed is about 3hr ^-1To about 20hr ^-1

317, as scheme 315 described methods, wherein N-((phosphonomethyl)) iminodiethanoic acid substrate to the transformation efficiency of N-((phosphonomethyl)) glycine product is at least about 50% in described fixed bed.

318, as scheme 315 described methods, wherein said liquid phase space-time speed is about 0.5h ^-1To about 5hr ^-1, and N-((phosphonomethyl)) iminodiethanoic acid substrate to the transformation efficiency of N-((phosphonomethyl)) glycine product is at least about 95% in described fixed bed.

319, as scheme 315 described methods, wherein residual N-((phosphonomethyl)) the iminodiethanoic acid substrate in described primary oxidation reactor mixture is not higher than about 0.2ppm.

320; as scheme 319 described methods; wherein said water-containing material mixture contains the water-soluble salt at least about N-((phosphonomethyl)) iminodiethanoic acid of 15% weight; by the acid equivalent benchmark; and wherein the final reacting mixture of Chan Shenging contains the water-soluble salt at least about N-((phosphonomethyl)) glycine of 12% weight; by the acid equivalent benchmark; described final oxidation mixtures comprises described primary oxidation reactor mixture; elementary product comprises the part of described primary oxidation reactor mixture; or by described primary reaction mixture or described elementary product fraction being incorporated into the second order reaction system that comprises one or more other reaction zones, other reaction mixture that obtains so that further N-((phosphonomethyl)) iminodiethanoic acid substrate is oxidized to N-((phosphonomethyl)) glycine product and/or oxidation of formaldehyde or formic acid.

321, as scheme 320 described methods; wherein said water-containing material mixture contains the water-soluble salt at least about N-((phosphonomethyl)) iminodiethanoic acid of 25% weight; by the acid equivalent benchmark; contain water-soluble salt with described final oxidation mixtures, by the acid equivalent benchmark at least about N-((phosphonomethyl)) glycine of 20% weight.

322, as scheme 321 described methods; wherein said water-containing material mixture contains the water-soluble salt at least about N-((phosphonomethyl)) iminodiethanoic acid of 35% weight; by the acid equivalent benchmark; contain water-soluble salt with described final oxidation mixtures, by the acid equivalent benchmark at least about N-((phosphonomethyl)) glycine of 28% weight.

323, as scheme 320 described methods, wherein final oxidation mixtures anhydrates to concentrate by therefrom removing.

324, as scheme 323 described methods, wherein described final reacting mixture is incorporated into flash zone, wherein pressure is lower than described final oxidation mixture and discharges vapour pressure under the temperature of described primary reactor or described second order reaction system at it.

325, as scheme 323 described methods, wherein from described final oxidation reaction product, remove and anhydrate, produce and contain by the concentrated solution of acid equivalent benchmark at least about N-((phosphonomethyl)) the glycine product water-soluble salt of 40% weight.

326, as scheme 325 described methods, wherein from described final oxidation reaction product, remove and anhydrate, produce and contain by the concentrated solution of acid equivalent benchmark at least about N-((phosphonomethyl)) the glycine product water-soluble salt of 40% weight.

327, as scheme 315 described methods, wherein keep below the spontaneous adiabatic reaction temperature of reference from the temperature of the described liquid phase outlet logistics of described primary reaction zone, this temperature is to be absorbed in the reaction heat that produces in the described primary reaction zone and the temperature that produces by described primary reaction mixture under the situation without any the measure that keeps low temperature out.

328, as scheme 327 described methods, wherein the measure that the temperature of described liquid phase outlet logistics is remained on below the described reference temperature(TR) comprises, by with the cooling fluid of hot indirect transfer, comprise heat-transfer fluid or process fluid and cool off described fixed bed to the conduit of flowing through in described bed or touching with described bench grafting.

329, as scheme 328 described methods, wherein described fixed bed is arranged on the shell-side or the pipe side of shell and-tube heat exchanger, described cooling fluid is through the opposite side of interchanger.

330, as scheme 329 described methods; wherein said fixed bed comprises the polycomponent bed in the pipe that separately is arranged on shell and-tube heat exchanger; described water-containing material mixture and oxygenant are distributed in the described component bed; so that be described N-((phosphonomethyl)) glycine product with described N-((phosphonomethyl)) iminodiethanoic acid substrate conversion therein, the flow through shell-side of described heat exchanger of described cooling fluid.

331, as scheme 329 described methods, wherein said fixed bed is included in the shell of shell and-tube heat exchanger.

332, as scheme 327 described methods, wherein said fixed bed comprises precious metal/C catalyst, and liquid reaction mixture with basic piston stream mode by the fixed bed in the described heat exchanger, thereby promote by product formaldehyde and/or formic acid oxidation therein.

333, as scheme 327 described methods; wherein the measure that will remain on below the described reference temperature(TR) from the temperature of described described liquid phase of discharging comprises; the recirculation fraction that is included in N-((phosphonomethyl)) the glycine product that produces in the reaction is incorporated into described bed; wherein said recirculation fraction is cooled in the outside of described fixed bed, and described liquid phase feed stream comprises described water-containing material mixture and described recirculation fraction.

334, as scheme 333 described methods, comprising:

Liquid phase is exported logistics be divided into elementary product fraction and primary reactor circulation fraction;

Allow liquid phase outlet logistics or primary reactor circulation fraction by heat exchanger, so that remove N-((phosphonomethyl)) the iminodiethanoic acid substrate heat of oxidation; With

Make primary reactor circulation fraction turn back to the primary oxidation reactor district.

335,, wherein before cutting apart described primary reaction mixture, allow described primary reaction mixture by described heat exchanger as scheme 334 described methods.

336, as scheme 315 described methods, wherein said catalyst pack platiniferous/C catalyst, this catalyzer contain and are not higher than 3% platinum, by the total catalyst benchmark.

337, be used for catalyzed oxidation N-((phosphonomethyl)) iminodiethanoic acid substrate to generate the continuation method of N-((phosphonomethyl)) glycine product, this method comprises:

The first component raw material stream that will comprise N-((phosphonomethyl)) iminodiethanoic acid substrate is incorporated into first of serial continuous reaction zone, and each of described serial reaction district contains oxide catalyst;

Oxygenant is incorporated into first of this serial reaction district;

The described substrate of catalyzed oxidation in described first reaction zone generates the intermediate reaction mixture stream passes that comprises N-((phosphonomethyl)) glycine product;

To transfer to second of this serial reaction district from the intermediate reaction mixture that described first reaction zone is discharged;

Described substrate of catalyzed oxidation in each of described serial reaction district;

Discharge the intermediate reaction mixture from each described reaction zone;

To be incorporated in each follow-up reaction zone at the intermediate reaction mixture that last reaction zone produces;

Other component raw material stream is incorporated in each of one or more described reaction zones after in described series first reaction zone, each described other feedstream comprises N-((phosphonomethyl)) iminodiethanoic acid substrate;

Oxygenant is incorporated in one or more reaction zones after in described series first reaction zone; With

From last of described serial reaction district, discharge final reacting product.

337, as scheme 336 described methods, other component raw material stream that wherein will comprise N-((phosphonomethyl)) iminodiethanoic acid substrate is incorporated in each of described serial reaction district.

338, as scheme 337 described methods, other component raw material stream that wherein will comprise N-((phosphonomethyl)) iminodiethanoic acid substrate is incorporated in each of described serial reaction district.

339, as scheme 338 described methods, wherein oxygenant is incorporated in each of described serial reaction district.

340, as scheme 339 described methods, in described series, comprise at least three continuous reaction zones.

341, as scheme 337 described methods, wherein one or more described other component raw material streams contain solid N-((phosphonomethyl)) iminodiethanoic acid substrate.

342, as scheme 337 described methods; wherein said N-((phosphonomethyl)) iminodiethanoic acid substrate comprises the water-soluble salt of N-((phosphonomethyl)) iminodiethanoic acid; and the mean concns of described salt in described component raw material solution should make described final oxidation mixtures contain N-((phosphonomethyl)) the glycine water-soluble salt at least about 10% weight, by the acid equivalent benchmark.

343, as scheme 342 described methods, the mean concns of wherein said salt in described component raw material solution should make described final oxidation mixtures contain N-((phosphonomethyl)) the glycine water-soluble salt at least about 20% weight, by the acid equivalent benchmark.

344, as scheme 343 described methods, the mean concns of wherein said salt in described component raw material solution should make described final oxidation mixtures contain N-((phosphonomethyl)) the glycine water-soluble salt at least about 28% weight, by the acid equivalent benchmark.

345, as scheme 341 described methods, wherein final oxidation mixtures anhydrates to concentrate by therefrom removing.

346, as scheme 345 described methods, wherein described final reacting mixture is incorporated into flash zone, wherein pressure is lower than the vapour pressure under the temperature of described final oxidation mixtures when it discharges described primary reactor or described second order reaction system.

347, as scheme 345 described methods, wherein from described final oxidation reaction product, remove and anhydrate, produce and contain by the concentrated solution of acid equivalent benchmark at least about N-((phosphonomethyl)) the glycine water-soluble salt of 40% weight.

Embodiment

Following examples only are used for further specifying and explaining the present invention.Therefore the present invention is not subjected to the restriction of any details among the embodiment.

Embodiment 1 measures the pore volume of carbon support

Use Micromeritics ASAP 2000 surface-area and pore volume distribution instrument to obtain data.Total surface area is measured and is included in steady temperature, for example under the temperature of liquid nitrogen is-196 ℃, the solid of known weight is exposed to the non-special adsorbed gas of certain pressure.In equilibrium process, gas molecule leaves bulk gas, is adsorbed onto on the surface, causes that the mean molecule number descends in the bulk gas, and then has reduced pressure.Record is with the saturation vapour pressure p of gas ₀Relative pressure p during the balance that changes and change.By volume, use perfect gas law and can calculate the amount (being molecule number) of adsorbed gas in conjunction with this pressure decline and container and sample.These data are at about 0.1 to 0.3 relative pressure (p/p _o) measure down, generally be suitable for Brunauer, Emmett and Teller (BET) equation of multilayer absorption in this situation.With the number of known adsorption gas molecule, can use " known " sectional area reckoner area of adsorptive.For the occasion (being the bright wrong that thermoisopleth of I type) that only takes place owing to the physical adsorption of Van der Waals force,, use the BET equation to determine surface-area by measured pressure change.Aperture and pore size distribution are by obtaining near p/p _oThe relative pressure data of=1 (state of multilayer absorption and capillary condensation promptly wherein takes place) are calculated.Method by using the Kelvin formula and being developed by Barrett, Joyner and Halenda (BJH) can obtain pore volume and area.

The high temperature deoxidation of embodiment 2 carbon supports

Can use in the high temperature deoxidation program described in following examples, obtain the deoxidation carbon support with any carbon support.

UseNH ₃ /H ₂O The single step high temperature deoxidation #1 of gas

Absorbent charcoal carrier (2.5g) is packed in 1.9cm (internal diameter) * long silica tube of 40.6cm.This is managed and passes through 70-100ml/min N ₂Air-flow sprays the 10%NH through 70 ℃ ₄The airflow connection that the OH aqueous solution obtains.Then silica tube is put into the 30.5cm tube furnace of preheating,, do not contacted the dry N of any air then 930 ℃ of following pyrolysis 60 minutes ₂Cool to room temperature under the atmosphere.

UseNH ₃ /H ₂O The single step high temperature deoxidation #2 of gas

Absorbent charcoal carrier (3.55g) is put in 1.9cm (internal diameter) * long silica tube of 35.6cm.The NH of this pipe and 50ml/min ₃With the airflow connection of the steam of 89ml/min, put into then in the 30.5cm tube furnace of preheating, and 930 ℃ of following pyrolysis 30 minutes.Subsequently this pipe is not being contacted the dry N of any air ₂Cool to room temperature under the atmosphere.

In order to be presented at precious metal is distributed to before the carrier surface advantage with the carbon support deoxidation, the performance of following two kinds of catalyzer: a kind of have carbon support, a processing deoxidation more than using before platinum is distributed to this carrier surface; A kind of have the SA-30 carbon support (VA), the sample that it presses Westvaco use for Westvaco Corp.Carbon, Department Coyington.Use is distributed to platinum in the technology described in following examples 3 surface of carbon support.Then with catalyst reduction.In an experiment, catalyzer uses NaBH ₄Reduction (rules are consulted embodiment 12).In second experiment, by with catalyzer at 20%H ₂Came reducing catalyst in 8 hours with under 640 ℃, heating in 80% argon gas.

Employing uses described reductive catalyzer to come the oxidation of catalyzing N-((phosphonomethyl)) iminodiethanoic acid to N-((phosphonomethyl)) glycine (being glyphosate) at the reaction conditions described in the embodiment 5.Table 1 has provided the result.The use of deoxidation carbon support has obtained littler CO desorb value, and precious metal still less leaches, the active and shorter reaction times of higher formaldehyde.

Table 1

Before the surface that precious metal is distributed to carbon support with the effect of carbon support deoxidation

Deoxidation is handled	CO desorb (mmol/g) from the carbon support	Reduction	Pt in the solution (μ g/g glyphosate product)	CH 2O (mg/g glyphosate product)	Reaction times 1(min)
						Single step high temperature deoxidation #2	?0.23	?NaBH 4Reduction (embodiment 12)	8.6	?28.5	?35.1
SA-30 presses sample and uses	?1.99	Identical	54.3	?43.1	?62.7
						Single step pyroprocessing #2	?0.23	At 20%H 2, following 8 hours at 640 ℃ among 80 %Ar	4.8	?15.6	?29.8
SA-30 presses sample and uses	?1.99	Identical	31	?19.7	?50.7

1, when 〉=98% N-((phosphonomethyl)) iminodiethanoic acid has been consumed.

Embodiment 3, platinum deposited to the surface of carbon support

(Westvaco Corp.CarbonDepartment, Covington VA) mixed slurry 2 hours in 2L water with the NUCHAR gac SA-30 of 20g.Then, be dissolved in the H of the 2.81g in about 900ml water with dropping in 3-4 hour ₂PtCl ₆Adding H ₂PtCl ₆After the solution, with slurry restir 90 minutes.Use NaOH that the pH of slurry is readjusted 10.5 then, restir 10-14 hour.The gained slurry is filtered, wash with water, reach the constant specific conductivity up to filtrate.With wet cake under 125 ℃ and vacuum dry 10-24 hour.This material has obtained 5% Pt/C after reduction.

Should be realized that above operation also can be used for platinum is deposited to the surface of other carbon support.

The high-temperature hydrogen reduction of embodiment 4 carbon supports

About 5.8g loaded on NUCHAR SA-30 carbon support (Westvaco Corp.Carbon Department by 5% platinum, Covyington, VA) drying of go up forming, raw catalyst are under 135 ℃ in argon gas local dewatered 1 hour, afterwards, are used in the 20%H in the argon gas under 640 ℃ ₂Reduced 11 hours.20%H in argon gas ₂Behind the cool to room temperature, this catalyzer is ready can be used under the atmosphere.

Should be realized that above operation can also be used to heat other carbon support.

Embodiment 5 uses catalyzer that N-((phosphonomethyl)) iminodiethanoic acid is oxidized to N-((phosphonomethyl)) glycine

The present embodiment use high temperature vapour phase reduction of having demonstrated is improved catalyst performance.

The Aldrich catalyzer that to form by 5% platinum/absorbent charcoal carrier (catalog number (Cat.No.) 20,593-1, Aldrich Chemical Co., Inc., Milwaukee is WI) under 640 ℃, at 20%H ₂Heated 4-6 hour down with the existence of 80% argon gas.Subsequently, it is used for the oxidation of N-((phosphonomethyl)) iminodiethanoic acid to glyphosate.Its performance and the performance of Aldrich catalyst sample (sample of pressing Aldrich uses) are compared.

Use N-((phosphonomethyl)) iminodiethanoic acid of 11.48g; 0.5% catalyzer (dry basis); the total reaction material of 140g; 90 ℃ temperature; the pressure of 50psig; the oxygen flow speed of the stirring velocity of 900rpm and 100ml/min is carried out the oxidizing reaction of N-((phosphonomethyl)) iminodiethanoic acid in the 200ml glass reactor.

Table 2 has provided the result.The high-temperature hydrogen reduction catalyzer has leaching still less, better formaldehyde activity, and produced N-methyl-N-((phosphonomethyl)) glycine still less.Also have, when using the high-temperature hydrogen reduction catalyzer, the reaction times shortens 30%.

Table 2

5%Pt/ active C (Aldrich catalog number (Cat.No.) 20, N-593-1) ((phosphonomethyl)) imino-

The oxalic acid oxidation results

Catalyzer	Pressing sample uses	High temperature H 2Reduction
			NPMIDA(％)	0.4619	?0.4430
N-((phosphonomethyl)) glycine (%)	5.58	?5.54
			HCO 2H (mg/g glyphosate product)	46.99	?35.87
CH 2O (mg/g glyphosate product)	32.96	?14.60
			NMG (mg/g glyphosate product)	3.58	?1.32
AMPA(ppm)	172.5	?182.0
			Terminal point (min)	64.67	?44.17
Pt in the solution (μ g/g glyphosate product)	32.26	?10.50
			Pt loses %	0.72	?0.232

Embodiment 6 uses catalyzer N-((phosphonomethyl)) iminodiethanoic acid to be oxidized to other embodiment of N-((phosphonomethyl)) glycine

Present embodiment has been demonstrated, and use high temperature vapour phase reduction is handled and ammonia stripping improves catalyst performance.

Compare the performance of six kinds of catalyzer in catalyzing N-((phosphonomethyl)) iminodiacetic acid (salt) acid oxidase.These catalyzer are: (a) catalyzer of forming by 5% platinum/absorbent charcoal carrier (catalog number (Cat.No.) 33,015-9, Aldrich Chemical Co., Inc., Milwaukee, WI); (b) with this catalyzer behind the ammonia stripping (ammonia stripping uses and to carry out with embodiment 10 described identical technology, be the pH of catalyst slurry be conditioned and remain on 11.0 but not 9.5); (c) under 75 ℃ at 20%H ₂With this catalyzer (75 ℃ of GPR @) of 4-6 hour of heating in 80% argon gas; (d) under 640 ℃ at 20%H ₂With the following heating of the existence of 80% argon gas this catalyzer (640 ℃ of GPR @) after 4-6 hour; (e) with ammonia stripping and then under 640 ℃ at 20%H ₂With the two kind catalyzer of the following heating of the existence of 80% argon gas after 4-6 hour.N-((phosphonomethyl)) iminodiethanoic acid oxidation reaction condition is identical with embodiment 5.

Table 3 has provided the result.Untreated catalyzer has shown the formaldehyde activity of high relatively leaching and difference.At H ₂Existence under caused maximum leaching decline and formaldehyde activity to increase 640 ℃ high temperature vapour phase reduction.Under 75 ℃ at 20%H ₂Middle heatable catalyst is reduced to lower degree with leaching, but does not strengthen the formaldehyde activity.

Table 3

5%Pt / gac (Aldrich catalog number (Cat.No.) 33, NPMIDA oxidation results 015-9)

Catalyzer	Pressing sample uses	NH 3Wash no GPR 1	GPR@ 75℃	?GPR@ ?640℃	NH 3Washing+GPR@640 ℃	NH 3Washing+GPR@640 ℃
							NPMIDA(％)	ND	?ND	?ND	?0.097	?0.083	?ND
Glyphosate (%)	5.87	?5.65	?5.81	?5.89	?5.85	?5.91
							HCO 2H (mg/g glyphosate product)	43.46	?43.65	?38.97	?42.14	?46.91	?52.12
CH 2O (mg/g glyphosate product)	19.39	?22.73	?19.85	?13.78	?15.70	?17.61
							NMG (mg/g glyphosate product)	1.27	?0.89	?0.89	?1.00	?1.31	?1.68
AMPA(ppm)	149.4	?147.6	?134.6	?349.8	?324.8	?283.8
							Terminal point (min)	39.33	?44.33	?38	?31.42	?34.33	?33.33
Pt in the solution (μ g/g glyphosate product)	42.59	?40.71	?27.54	?5.26	?5.30	?4.23
							Pt loses %	1	?0.92	?0.64	?0.12	?0.12	?0.1

1, " GPR " is meant at H ₂Middle reduction

2, " ND " is meant and do not detect

In the experiment below, when catalyzing N-((phosphonomethyl)) iminodiethanoic acid, analyze five kinds of catalyzer.These catalyzer are: (a) by catalyzer that 5% platinum/NUCHAR SA-30 forms (Westvaco Corp., Carbon Department, Covington, VA); (b) use NaBH ₄This catalyzer after the processing (rules are consulted embodiment 12); (c) under 75 ℃ at 20%H ₂With this catalyzer (GPR@75 ℃) of 4-6 hour of heating in 80% argon gas; (d) under 640 ℃ at 20%H ₂With heating this catalyzer (GPR@640 ℃) after 4-6 hour in 80% argon gas; (e) with ammonia stripping (use and embodiment 10 described identical technology) and then under 640 ℃ at 20%H ₂With heating this catalyzer after 4-6 hour in 80% argon gas.Reaction conditions is identical with those conditions among the embodiment 5.

Table 4 has provided the result.Untreated catalyzer has shown high relatively platinum leaching and has hanged down the formaldehyde activity.Use NaBH ₄Catalyzer after the processing has also shown high leaching and low formaldehyde activity, and GPR@75 ℃ catalyzer also is like this.On the contrary, GPR@640 ℃ has shown the active and leaching still less of higher formaldehyde.

Table 4

Use 5%Pt The NPMIDA oxidation results of/NUCHAR SA-30

Catalyzer	Not reduction	NaBH 4Reduction	GPR@75℃	GPR@640 ℃	NH 3Washing+GPR @640 ℃
						Glyphosate (%)	2.50	?5.71	?4.92	?5.17	?5.19
HCO 2H (mg/g glyphosate product)	59.56	?51.14	?57.85	?30.85	?38.21
						CH 2O (mg/g glyphosate product)	115.28	?43.13	?48.52	?19.67	?20.79
NMG (mg/g glyphosate product)	1.64	?2.17	?6.41	?0.37	?1.73
						AMPA(ppm)	58.16	?193.9	?174.0	?138.5	?156.3
Terminal point (min)	62.67	?62.67	?70.67	?50.67	?59.33
						Pt in the solution (μ g/g glyphosate product)	84.00	?54.29	?81.30	?30.95	?19.27
Pt loses %	0.84	?1.24	?1.6	?0.64	0.4

The C/O of embodiment 7 catalyst surfaces and the influence of O/Pt ratio

Use PHI Quantum 2000 ESCA Microprobe Spectrometer (PhysicalElectronics, Eden Prairie, MN) carbon atom and Sauerstoffatom ratio and the Sauerstoffatom and the pt atom ratio on the various live catalysts of analysis surface.Surface analysis is undertaken by electron spectroscopy for chemical analysis (" ESCA "), adopts the instrument postponement pattern, that the analyser (constant resolution) of the logical energy of fixing strip is arranged.This is analyzed needs to use soft X-ray, for example AlK _α(1486.6eV) irradiation sample, its energy is enough to ionization core electron and valence electron.The electronics that penetrates leaves sample (ignoring the work content effect) with the kinetic energy of the difference between " bound energy " that equal exciting radiation and electronics.Because in the photoelectron peak, only measure the elasticity electronics, promptly do not suffer those electronics of power loss by any inelastic interaction, and because the inelastic mean free path of electronics in solid is short, so ESCA is the surface-sensitive technology inherently.The kinetic energy of electronics uses electrostatic analyzer to measure, and the number of electronics uses electron-multiplier to measure.Data provide with the electronic number that the detected bound energy to electronics.Use is used to excite photoelectronic monochromatic AlK _αX ray obtains ESCA measurement spectrum with setting the analyser that is used for the logical energy of 117eV band.X-ray source is operated under 40 watts of power, collects data by 200 μ m points on the irradiated sample.These conditions have obtained highly sensitive, but energy resolution is low.Wave spectrum adopts to be accumulated to 1.0eV step-length and stack (co-adding) multiple scanning in the 0eV zone at 1100eV, so that obtain acceptable signal-to-interference ratio in data.The normal data that has using method that use is provided by retailer is handled and routine analyzer is identified and quantitative element.Obtained the relative atom concentration of element Pt/C/O by the relative intensity at photoelectron peak.Esca analysis uses the tabular response factor of particular instrument configuration, generally has ± 20% precision.

Table 5 has shown the C/O and the O/Pt ratio on each live catalyst surface, and the leaching amount of each catalyzer in single loop N-((phosphonomethyl)) iminodiethanoic acid oxidation reaction process.

Table 5

C /O WithO /Pt The influence of ratio in the NPMIDA oxidising process ¹

Catalyzer	Reduction after the noble metal loading is handled	The C/O ratio	The O/Pt ratio	Pt in the solution (μ g/g) 2	CH 2O (mg/g) 2
						5%Pt/ deoxidation carbon 5	?NaBH 4Reduction	23.7	?3	?ND 4
The same	?Pt(II) 6?640℃ ?/9hr/10％H 2	35.3	?17	?1.2	?24.44
						The same	?NaBH 4Reduction	21.1	?3	?6.9
Aldrich catalog number (Cat.No.) 33015-9	?640℃/6hr/20％H 2	67.9	?3	?5.2	?13.78
						The same	?75℃/6hr/20％H 2	13.4	?10	?27.5	?19.85
The same	Pressing sample uses	13.3	?10	?42.6	?19.39
						Aldrich catalog number (Cat.No.) 20593-1	?640℃/6hr/20％H 2?NH 3Washing/pH=11	45.2	?7	?10.5	?21.90
The same	?640℃/6hr/20％H 2	37.7	?10	?10.5	?14.60
						The same	Pressing sample uses	9.1	?26	?32.3	?32.96
5%Pt/SA-30 Westvaco carbon	?640℃/7hr/20％H 2?NH 3Washing/pH=9.5	67.7	?8	?19.3	?20.79
						The same	?640℃/8hr/20％H 2	63.3	?8	?30.9	?19.67
The same	?75℃/7hr/20％H 2	13.2	?32	?81.3	?48.52

1, reaction conditions is identical with embodiment 5 used those conditions.

2, μ g leaches into the glyphosate that Pt/g produced in the solution.

3, the glyphosate produced of mg formaldehyde/g.

4, " ND " is meant and do not detect.

5, use the carbon support of the single step high-temperature technology #2 deoxidation of embodiment 2.

6, use the sedimentary Pt of two nitrous acid, two ammino platinum (II) as described in example 11 above.

Embodiment 8 uses the catalyst surface analysis of thermogravimetric analysis and online mass spectrometry (TGA-MS)

By thermogravimetric analysis and online mass spectrometry (TGA-MS), under helium, measure the concentration of the oxygen-containing functional group on various live catalysts surface.In order to carry out this analysis, the dry sample (100mg) of live catalyst is put in the ceramic cup on the plum Teller balance.At room temperature reach 10 minutes with the atmosphere around the flow velocity purging sample of 150ml/min then with helium.Temperature rises to 900 ℃ with 10 ℃/minute speed from 20 ℃ subsequently, keeps 30 minutes down at 900 ℃ then.Measure the desorption quantity of carbon monoxide and carbonic acid gas with online mass spectrograph.Mass spectrograph uses caoxalate monohydrate sample to calibrate under identical condition in independent experiment.

Table 6 has provided the CO content that uses each catalyzer institute desorb of every gram that TGA-MS measures, and the leaching amount of each catalyzer in single loop N-((phosphonomethyl)) the iminodiethanoic acid oxidation reaction process that uses the reaction conditions identical with embodiment 5.As shown in table 6, leaching often descends with the decline of CO desorption quantity, and when desorption quantity was not higher than 1.2mmol/g (the CO/g catalyzer of mmol desorb), the leaching amount was low especially.

Table 6

In the TGA-MS process as the influence of CO from the oxygen-containing functional group of catalyst surface desorb

Catalyzer	Reduction is handled	TGA-MS (mmol/g) 1	Pt in the solution (μ g/g) 2	CH 2O (mg/g) 3
					Aldrich catalog number (Cat.No.) 33015-9	640℃/6hr/20％H 2	?0.41	?5.2	?13.78
The same	640℃/6hr/20％H 2， NH 3Washing/pH=9.5	?0.38	?5.3	?15.70
					The same	75℃/6hr/20％H 2	?1.87	?27.5	?19.85
The same	NH 3Washing/pH=9.5	?1.59	?40.7	?22.73
					The same	Pressing sample uses	?1.84	?42.6	?19.39

1, mmol CO/g catalyzer

2, μ g leaches into the glyphosate that precious metal/g produced in the solution

3, the glyphosate produced of mg formaldehyde/g

Embodiment 9 is Temperature Influence in high temperature gas phase reduction process

Present embodiment is for example understood the influence of using all temps when heatable catalyst in the presence of reductive agent.

Raw catalyst with 5% platinum on absorbent charcoal carrier (using the single step high temperature deoxidation technology 2# deoxidation described in the embodiment 2 before the platinum deposition) is at various temperatures at 10%H ₂With about 2 hours of heating in 90% argon gas.Catalyzer is used for catalyzing N-((phosphonomethyl)) iminodiethanoic acid oxidizing reaction then.5gN-((phosphonomethyl)) iminodiethanoic acid is used in reaction, 0.157% catalyzer (dry basis), and the total reaction material of 200g, 80 ℃ temperature, the oxygen flow speed of the pressure of 0psig and 150ml/min is carried out in the 250ml glass reactor.

The result provides in table 7.Reduction temperature is increased to 600 ℃ from 125 ℃ have been reduced precious metal leaching amount and has increased at N-((phosphonomethyl)) iminodiethanoic acid and be oxidized to oxidation of formaldehyde activity the reaction process of glyphosate.

Table 7

The influence of reduction temperature

Reduction temperature (℃)	Pt (normalization method in the solution 1)	CH 2O (normalization method 2)	The C/O ratio	The O/Pt ratio
					?125	?1.00	?0.41	?26	?13
?200	?0.44	?0.80	?27	?14
					?400	?0.18	?0.93	?42	?10
?500	?0.14	?0.95	?32	?14
					?600	?0.06	?1.00	?40	?11

1,1.00 normalized value is corresponding to the highest Pt amount of finding in solution in this experiment.

2,1.00 normalized value is corresponding to the highest formaldehyde activity in this experiment.

Embodiment 10 ammonia stripping catalyzer

In 500ml water, mixed slurry 30 minutes by the raw catalyst (6.22g) that 5% platinum/absorbent charcoal carrier (using at the single step high temperature deoxidation technology #2 deoxidation described in the embodiment 2) is formed before platinum deposits on the carrier.Afterwards, with the pH regulator to 9.5 of weak ammonia, and, wherein regularly add ammoniacal liquor to keep pH 9.5 with slurry stirring 1 hour with slurry.The gained slurry is filtered, with about 300ml water washing 1 time.Wet cake is then vacuum and 125 ℃ dry about 12 hours down.This catalyzer under 640 ℃ at 10%H ₂With heating in 90% argon gas 11 hours, compare with two kinds that form by 5% platinum/NUCHAR gac other catalyzer then: (a) a kind of NaBH that at room temperature uses ₄The reduction (rules are consulted embodiment 12) and (b) a kind of under 640 ℃ at 10%H ₂With heating in 90% argon gas 11 hours.Reaction conditions is identical with those conditions among the embodiment 5.

The result provides in table 8.Before high-temperature hydrogen reduction, use the platinum of the catalyzer of ammonia stripping to leach minimum.

Table 8

The effect of ammonia stripping

Catalyzer	CH 2O(mg/g) 1	HCO 2H(mg/g)	NMG(mg/g)	Pt in the solution (μ g/g)
					NH 3Washing, high temperature H 2Reduction	10.62	?28.79	?0.83	?0.50
High temperature H 2Reduction	14.97	?27.82	?1.?38	?4.64
					Room temperature NaBH 4Reduction	28.51	?70.16	?2.59	?8.64

1, this tittle is based on the glyphosate that every gram is produced.

Embodiment 11: the use of the noble metal precursor of small amounts

Use two nitrous acid, two ammino platinum (II) that platinum is deposited on the absorbent charcoal carrier.Use the single step high temperature deoxidation technology #2 described in the embodiment 2 will about 20g the absorbent charcoal carrier deoxidation.Then, carrier was mixed slurry 2 hours in 2L water.In 3-4 hour process, drip two nitrous acid, two ammino platinum (II), 3.4% solution of the about 51.3g that is diluted with water to 400g then.After interpolation is finished, continue to stir other 90 minutes.By adding rare NaOH aqueous solution pH is readjusted 10.5, and restir 10-14 hour.Filter slurry then,, reach the constant specific conductivity up to filtrate with a large amount of water washings.Wet cake under vacuum at 125 ℃ of dry 10-24 hours.The gained catalyzer under 640 ℃ at 10%H ₂With heating in 90% argon gas 4-6 hour.

Use H ₂PtCl ₆Platinum deposited on the identical carbon prepare contrast.Contrast heats under the condition identical with the catalyzer that uses the preparation of two nitrous acid, two ammino platinum (II).

The oxidizing reaction that compares these catalysts N-((phosphonomethyl)) iminodiethanoic acid.Reaction conditions is identical with those conditions among the embodiment 5.

The catalyzer that uses two nitrous acid, two ammino platinum (II) to prepare is compared with contrast has less leaching.Only the glyphosate produced of 1.21 μ g platinum/g leaches in the solution, and this will get well about 3 times than contrast.

Embodiment 12: use NaBH ₄The reducing catalyst surface

The purpose of present embodiment is that proof is used NaBH ₄The influence of reducing catalyst.

The absorbent charcoal carrier (being used in the single step high temperature deoxidation technology #2 deoxidation described in the embodiment 2 before depositing to platinum on the carrier) of about 5g is mixed slurry with 85ml distilled water in the 250ml round-bottomed flask.Slurry is stir about 1 hour in a vacuum.Then, will be at the 0.706g H in the 28ml distilled water ₂PtCl ₆Speed with about 1ml/100 second joins in the slurry, still applies vacuum simultaneously.After stirring is spent the night in a vacuum, by feeding N ₂Air-flow returns to normal atmosphere with reactor.Allowing after the slurry sedimentation the colourless supernatant liquor of the about 30ml of decantation.To remain slurry transfers in the 100ml teflon round-bottomed flask.At this moment, with 0.3g NaOH pH is transferred to 12.2.Then, the speed with 0.075ml/min adds 2.3ml NaBH ₄14M NaOH solution.Subsequently, the gained slurry was stirred 1 hour, filter, use the 50ml distilled water wash again 5 times.Then with catalyzer under 125 ℃ and 6mmHg dry 12 hours.

The gained catalyzer is used for catalyzing N-((phosphonomethyl)) iminodiacetic acid (salt) acid oxidase.0.5% catalyzer, 8.2%N-((phosphonomethyl)) iminodiethanoic acid, the total reaction material of 180g are used in reaction; the pressure of 65psig, 90 ℃ temperature, the stirring velocity of 900rpm; oxygen delivery rate with 72ml/min carries out in the 300ml stainless steel reactor.

Also using 5.23% platinum/absorbent charcoal carrier (before depositing to platinum on the carrier, being used in the single step high temperature deoxidation technology #2 deoxidation described in the embodiment 2) to carry out control experiment under the identical reaction conditions.

Table 9 has provided use NaBH ₄The result of reducing catalyst, table 10 has provided the result of control experiment.Use NaBH ₄Reduction has reduced precious metal leaching amount.It has also reduced formaldehyde after certain usage period and the amount of NMG.

Table 9

Use and useNaBH ₄ The result of the catalyzer of handling

Circulation #	1	2	3	4	5	6
							Glyphosate (%)	5.79	5.81	5.75	5.74	5.79	5.77
NPMIDA(％)	0.23	0.08	0.13	0.22	0.13	0.13
							CH 2O (mg/g glyphosate)	28.5	31.5	47.8	38.8	41.6	45.8
HCO 2H (mg/g glyphosate)	70.2	90.5	100.5	96.6	98.8	99.0
							AMPA/MAMPA(％)	0.02	0.01	0.01	0.01	0.01	0.01
NMG (mg/g glyphosate)	2.6	3.6	3.6	4.2	4.7	4.7
							Pt in the solution (μ g/g glyphosate)	8.64	8.60	5.22	6.96	6.91	5.20
Pt loses %	0.20	0.20	0.12	0.16	0.16	0.12

Table 10

Use is without NaBH ₄The result of the catalyzer of handling

Circulation #	1	2	3	4	5	6
							Glyphosate (%)	5.36	5.63	5.37	5.50	5.56	5.59
NPMIDA(％)	0.18	0.15	0.25	0.21	0.18	0.23
							CH 2O(％)	20.9	23.6	38.4	44.2	47.7	58.3
HCO 2H(％)	27.8	63.8	96.5	98.4	102.2	102.0
							AMPA/MAMPA(％)	0.04	0.02	0.04	0.02	0.02	0.03
NMG (mg/g glyphosate)	1.5	3.0	5.4	6.9	10.6	7.3
							Pt in the solution (μ g/g glyphosate)	63.6	62.2	44.7	34.6	28.8	28.6
Pt loses %	1.30	1.34	0.92	0.73	0.61	0.61

Embodiment 13: bismuth is as the use of catalyst surface promotor

Preparation is by 10 ^-3In the M formic acid solution 10 ^-3MBi (NO ₃) ₃5H ₂The 500g solution that O forms.This solution is joined in 500g 5% formaldehyde solution that contains 6.0g 5% platinum/absorbent charcoal carrier.With solution under 40 ℃ at N ₂Following stirring is spent the night, and filters with the magnetic leakage bucket then.Dry aliquots containig is used x-ray fluorescence analysis subsequently.Catalyzer has 63% drying loss (" LOD ").Find that the exsiccant catalyzer contains about 3% bismuth and 4% platinum.

Following material is put in the 300ml stainless steel autoclave: 16.4gN-((phosphonomethyl)) iminodiethanoic acid; 4.16g activated-carbon catalyst, 0.68g comprise the above catalyzer of 3% bismuth/4% platinum and the water of 179.4g on its surface.Be reflected at the pressure of 65psig, 90 ℃ temperature is carried out under the oxygen flow speed of 38ml/min and the stirring velocity of 900rpm.It is depleted that reaction proceeds to N-((phosphonomethyl)) iminodiethanoic acid.By filtering separation product solution and catalyzer, solution neutralizes with the 50%NaOH solution of 6g again.With catalyst recirculation 5 times, do not remove.Analyze each round-robin product solution.Two contrasts are just save the Bi/Pt/ C catalyst of 0.68g to carry out with above identical mode.

The result provides in table 11.The formaldehyde that circulates in generation lower level in the product with Bi/Pt/ C catalyst, formic acid and NMG.

Table 11

Use the NPMIDA oxidation results of Pt/Bi/C catalyzer

	Contrast

1#	Contrast	2#	First circulation	Second circulation	The 3rd circulation	The 4th circulation	The 5th circulation
								Glyphosate (%)	5.7	5.59	5.69	5.72	5.87	5.74	5.68
NPMIDA(％)	ND	ND	0.04	0.07	0.085	0.04	0.046
								AMPA(％)	0.034	0.031	0.015	0.009	0.008	DBNQ 1	DBNQ
CH 2O (mg/g glyphosate product)	142	138	28	31	34	38	42
								HCO 2H (mg/g glyphosate product)	56	57	DBNQ	7	14	17	23
AMPA/MAMPA(％)	0.047	0.041	0.021	0.014	0.013	0.014	0.013
								NMG (mg/g glyphosate product)	16.3	19.3	0.7	0.9	1.4	2.3	2.6

1, DBNQ=can detect, but can not be quantitative.

Embodiment 14: tin promotor is deposited on the carbon support

Gac (20g) is mixed slurry in about 2L water.Then, with 0.39g SnCl ₂2H ₂O is dissolved in 500g0.5%HNO ₃In.This drips of solution is added in the carbon slurry.After having added all solution, slurry was stirred 2 hours.Then with pH regulator to 9.5, with slurry restir several hours.Then, filter slurry, wash with massive laundering, till filtrate reaches constant conductance.Wet cake is dry under 125 ℃ and vacuum, has obtained 1%Sn/C.After drying, with 1%Sn/C calcining 6 hours in 500 ℃ and argon gas.

For platinum is deposited on the carbon support, at first 5g1%Sn/C is mixed slurry in about 500ml water.Then with 0.705g H ₂PtCl ₆Be dissolved in about 125ml water, drip again.Adding all H ₂PtCl ₆After the solution, slurry was stirred 2.5 hours.With dilute NaOH solution pH is transferred to 9.5 then, continue again to stir several hours.Filter slurry then, wash, till filtrate reaches constant conductance with massive laundering.Wet cake is dry in a vacuum under 125 ℃.

This technology has produced and has comprised the 5%Pt that loads on the carbon and the catalyzer of 1%Sn.

Embodiment 15: iron promotor is deposited on the carbon support

About 5g gac is mixed slurry in about 500ml water.Then, with 0.25g FeCl ₃6H ₂O is dissolved in the 75ml water.This drips of solution is added in the carbon slurry.After having added all solution, slurry was stirred 2 hours.Filter slurry then, wash, reach constant conductance up to filtrate with massive laundering.Wet cake is dry under 125 ℃ and vacuum, has obtained 1%Fe/C.After drying, 1%Fe/C calcined 8 hours down at about 500 ℃ in argon gas.

For platinum being deposited on the surface of carbon support, at first the 1%Fe/C with 2.5g mixes slurry in about 180ml water.Then, with the H of 0.355g ₂PtCl ₆Be dissolved in about 70ml water, drip again.Adding all H ₂PtCl ₆After the solution, with slurry restir 3 hours.With dilute NaOH solution pH is transferred to approximately 10.0 then, continue again to stir several hours.Next, filter slurry, wash with massive laundering, till filtrate reaches constant conductance.Wet cake is dry in a vacuum under 125 ℃.

This technology has produced and has comprised the 5%Pt that loads on the carbon and the catalyzer of 1%Fe.

Embodiment 16: have the effect of precious metal on the carbon support surface

Present embodiment has shown and has used the advantage that has the carbon support of precious metal in its surface but not do not have the simple C catalyst of precious metal to carry out the oxidation of N-((phosphonomethyl)) iminodiethanoic acid from the teeth outwards.

N-((phosphonomethyl)) iminodiethanoic acid oxidizing reaction is carried out in the presence of simple C catalyst (using at the single step high temperature deoxidation technology #2 deoxidation described in the embodiment 2).0.365% catalyzer, 8.2%N-((phosphonomethyl)) iminodiethanoic acid, the total reaction material of 200g are used in reaction; the pressure of 65psig; 90 ℃ temperature, the oxygen delivery rate of the stirring velocity of 900rpm and 38ml/min carries out in the 300ml stainless steel reactor.

Table 12 has provided 5 round-robin reaction times (that is, at least 98% N-((phosphonomethyl)) iminodiethanoic acid be consumed time) of simple C catalyst.Table 12 gives under embodiment 12 described reaction conditionss, the reaction times of two kinds of Pt/C catalyzer in 6 circulations among the embodiment 12.As can be from seeing the table 12, simple C catalyst deactivating in each circulation be tended to bigger (being that often every circulation increase of reaction times is more) usually than deactivating of the C catalyst that has precious metal from the teeth outwards.With catalyzer NaBH after noble metal loading is to the surface ₄The reductive occasion, it is especially few to deactivate.Be not subjected to the restriction of any particular theory, it is believed that because NaBH ₄Platinum on the reducing catalyst leaches the platinum that is less than on other Pt/C catalyzer and leaches, so use NaBH ₄Deactivating of reductive catalyzer is less than deactivating of other Pt/C catalyzer.Consult embodiment 12, table 9 and 10.

Table 12

Use need notNaBH ₄ The result of the catalyzer of handling

Circulation #	1	2	3	4	5	6
							The cycling time (min) of simple C catalyst	45.4	55.0	64.4	69.8	75.0
Use NaBH 4The cycling time (min) of reductive 5%Pt/C catalyzer	35.1	NA 1	NA	35.2	35.8	35.8
							The cycling time of 5.23%Pt/C catalyzer (min)	40.4	42.0	44.2	44.1	44.9	52.7

1, can not obtain owing to temperature problem.

Embodiment 17: the effect of using the catalyzer of the alloy that comprises precious metal and catalyst surface promotor

Present embodiment has shown the advantage of the catalyzer of the alloy that comprises platinum and iron.

1, the catalyzer that comprises the alloy of platinum and iron

In order to prepare the catalyzer of the alloy that comprises platinum and iron, the gac of about 10g is mixed slurry in about 180ml water.Then, with the FeCl of 0.27g ₃6H ₂The H of O and 1.39g ₂PtCl ₆Hydrate is dissolved in about 60ml water altogether.Through about 30 minutes time this drips of solution is added in the carbon slurry.In the interpolation process, the pH of slurry descends, and is maintained at about 4.4 to about 4.8 with dilute NaOH solution (being 1.0-2.5M NaOH solution).After this, under about 4.7 pH with slurry restir 30 minutes.Then at N ₂Speed with about 2 ℃/min is heated to 70 ℃ with slurry down, keeps pH about 4.7 simultaneously.After reaching 70 ℃, with about 30 minutes pH slowly is increased to 6.0 by adding dilute NaOH solution.Continue 10 minutes time of stir about, be stabilized in about 6.0 up to pH.Then at N ₂Down slurry is cooled to about 35 ℃.Subsequently, filter slurry, filter cake about 800ml water washing 3 times.Then that filter cake is dry under 125 ℃ and vacuum.At 690 ℃ at 20%H ₂With heating among the 80%Ar after 1-6 hour, produced and contained the 5wt%Pt that loads on the carbon and the catalyzer of 0.5wt%Fe.

As among the embodiment 19 in greater detail, with this catalyzer of electron microscopic analysis.The image that obtains by carbon support TEM shows, alloyed metal particle high dispersing and be evenly distributed in (white point is represented metallics, and the variation of background intensity it is believed that the variation of expression porous carbon local density) on the whole carbon support.The mean sizes of particle is about 3.5nm, and the mean distance between particle is about 20nm.Differentiate X-ray wave spectrum from the high energy of the single metal particle of catalyzer and show, have platinum and iron peak (deriving from the copper peak of the scattering of copper grid).The quantitative analysis that the high energy of different single metal particles is differentiated the X ray wave spectrum shows that in the experimental error scope, the composition of particle does not change with the size of the metallics on catalyst surface or the variation of position.

2, Wherein less platinum becomes the catalyzer of alloy with iron

In order to prepare wherein less platinum becomes alloy with iron Pt/Fe/C catalyzer (that is, compare with described first kind of catalyzer in the present embodiment, this catalyzer becomes the platinum of alloy less with iron), platinum and iron phase continued to deposit on the surface of carbon support.The gac of about 5g is mixed slurry in about 500ml water.With 1N HCl pH regulator is arrived about 5.0.Then, with the FeCl of about 0.25g ₃6H ₂O is dissolved in the 75ml water.With about 60 minutes this drips of solution is added in the carbon slurry.After having added all solution, with slurry stir about 2 hours.With dilute NaOH solution with pH regulator to 9.5, with slurry restir several hours.Afterwards, filter slurry and wash with massive laundering.Wet cake has produced 1wt%Fe/C dry under vacuum under 125 ℃.After drying, this 1wt%Fe/C is with containing 20%H ₂Reduced 1-6 hour at 635 ℃ with the atmosphere of 80%Ar.This 1wt%Fe/C of about 2.5g is mixed slurry in the water of 250ml.Next, will about 0.36g H ₂PtCl ₆Hydrate is dissolved in the 65ml water, with after it was added drop-wise in this slurry in about 60 minutes.After having added all solution, slurry was stirred 2 hours.Filter slurry then and wash with massive laundering.Filter cake is mixed slurry again in 450ml water.After with the pH regulator to 9.5 of dilute NaOH solution, with slurry stir about 45 minutes with slurry.Then, filter slurry, once with the 450ml water washing.Wet cake is dry under 125 ℃ and vacuum.By containing 20%H ₂After being heated to 660 ℃ temperature in the atmosphere of 80%Ar and keeping reducing in 1-6 hour, the 5wt%Pt that loads on the carbon and the catalyzer of 1wt%Fe have been obtained to contain.

3, The comparison of two kinds of catalyzer

The oxidizing reaction that compares this two kinds of catalyst N-((phosphonomethyl)) iminodiethanoic acid.Those of reaction conditions and embodiment 5 are identical.Table 13 has provided the result.With regard to CH ₂O and HCO ₂H is active and discuss, described in the present embodiment first kind of catalyzer (promptly comprising the relatively large catalyzer that becomes the platinum of alloy with iron) has higher stability, and described in the present embodiment second kind of catalyzer (promptly comprising more a spot of catalyzer that becomes the platinum of alloy with iron) deactivates fast.In addition, first kind of catalyzer keeps almost half of its iron level after 25 circulations, and second kind of catalyzer just lost its most of iron in first circulation.

Table 13 has the catalyzer and the comparison with catalyzer of less Pt/Fe alloy of Pt/Fe alloy

Alloying Pt and Fe	Circulation	1	Circulation 2	Circulation 3	Circulation 4	Circulation 5	Circulation 6	Circulation 7	Circulation 8	Circulation 9	Circulation 10	Circulation 11	Circulation 12	Circulation 13
															CH 2O (mg/g glyphosate product)	10.49		9.23		6.04		4.92		4.44		5.08		5.24
HCO 2H (mg/g glyphosate product)	19.91		29.64		27.84		25.62		27.99		29.73		28.95
														NMG (mg/g glyphosate product)	0.22		0.44		0.28		0		0		0		0
Pt in the solution (μ g/g glyphosate product)	5.08		4.87		3.6		3.06
														Fe loses %	44		1.9		1.2		0.8
														Less alloying Pt and Fe	Circulation	1	Circulation 2	Circulation 3	Circulation 4	Circulation 5	Circulation 6	Circulation 7	Circulation 8	Circulation 9	Circulation 10	Circulation 11	Circulation 12	Circulation 13
CH 2O (mg/g glyphosate product)	10.16	10.7	12.24	13.56	14.68
														HCO 2H (mg/g glyphosate product)	27.23	37.72	45.01	54.57	61.14
NMG (mg/g glyphosate product)	0	0.98	1.23	1.77	2
														Pt in the solution (μ g/g glyphosate product)	3.83	3.36	3.54	3.44	3.32
Fe loses %	86	3.2	1.4	1.8	1.4

Embodiment 18:Pt/Fe/Sn/C Preparation of catalysts

The gac of about 10g is mixed slurry in about 90ml water.Then, with the SnCl of about 0.2g ₃2H ₂O is dissolved among the 250ml0.025M HCl.Drips of solution is added in the carbon slurry.After having added all solution, slurry was stirred 3 hours.Use dilute NaOH solution (being the 1.0-2.5M solution of NaOH) that pH slowly is adjusted to 9.0 then, with slurry restir several hours.Then, filter slurry, wash, reach constant conductance up to filtrate with massive laundering.Wet cake is dry under 125 ℃ and vacuum.This has produced 0.9wt%Sn/C.This 0.9wt%Sn/C of about 6g is mixed slurry in about 500ml water.Then will about 0.23g Fe (NO ₃) ₃9H ₂O and 0.85gH ₂PtCl ₆Be dissolved in jointly in about 150ml water, be added drop-wise in the slurry again.After having added all solution, slurry was stirred 4 hours, filter then, with remove excessive Fe (～80wt%).Wet cake is mixed slurry again in 480ml water.With dilute NaOH solution with the pH regulator of slurry after 9-10, with slurry restir several hours.Then, filter this slurry and wash, reach constant conductance up to filtrate with massive laundering.Wet cake is dry under 125 ℃ and vacuum.Passing through under 700-750 ℃ at 20%H ₂After 1-6 hour high temperature reduction of heating among the 80%Ar, produced and contained the 4.9wt%Pt that loads on the carbon, the catalyzer of 0.9wt%Sn and 0.1wt%Fe.

Embodiment 19: the electron microscope method of catalyzer characterizes

Use Electron Microscopy to analyze size, spatial distribution and the composition of the metallics of the catalyzer of preparation in embodiment 17.Before analyzing this catalyzer, at first this catalyzer is implanted in EM Bed 812 resins (Electron Microscopy Sciences, FortWashington, PA).Resin is then about 24 hours of about 60 ℃ of following polymerizations.Gained solidifies block is cut into the about 50nm of thickness with ultramicrotome section.200 order copper grids are transferred in these sections then, are used for electron microscope observation.

With picture resolution less than the Vaccum Generator dedicated scan transmission electron microscope of 0.3nm (model VG HB501, Vacuum Generators, East Brinstead, Sussex England) carries out high accuracy analysis submicroscopy experiment.Microscope is operated under 100kV.Vacuum tightness in the zone, sample chamber is about 10 ^-6Below the Pa.Digital image obtain system (ESVision Data Acquisition System, EmiSpec Sys., Inc., Tempe AZ) is used to obtain the high resolution electron microscope (HREM) image.Windowless energy dispersive X-ray spectrometer (LinkLZ-5EDS Windowless Detector, Model E5863, High Wycombe, Bucks England) is used for obtaining high energy resolution X ray spectrum from the single metal particle.Because have high atomicity sensitivity, use angle of elevation annular dark-field (HAADF) microscopy observation metallics.Use obtains the HAADF image less than the electronic probe size of about 0.5nm, and uses and obtain high energy resolution X ray spectrum less than the probe size of about 1nm.

Implement 20: the effect of supplemental promoter

Present embodiment has shown that the oxide catalyst blended of the precious metal of supplemental promoter and carbon containing load uses and advantage.

A, Mix with the bismuth in various amounts and source by catalyzer and to draw the precious metal of carbon containing load The comparison that rises to the influence of NPMIDA oxidizing reaction

Carry out several single batch N-((phosphonomethyl)) iminodiethanoic acid oxidizing reaction.In each reaction, the bismuth of different sources with different amounts joined in the reaction medium.The source of bismuth is (BiO) ₂CO ₃, Bi (NO ₃) ₃5H ₂O or Bi ₂O ₃One of.The consumption of bismuth is corresponding to 1: 10, and 000; 1: 2,000; Or 1: 1,000 bismuth and N-((phosphonomethyl)) iminodiethanoic acid mass ratio.Also wherein do not add the controlled trial of bismuth.

Each N-((phosphonomethyl)) iminodiethanoic acid oxidizing reaction is carried out in the presence of the catalyzer that contains 5wt% platinum and 0.5wt% iron (this catalyzer uses and the similar method preparation of method described in the embodiment 17).Be reflected at 1000ml stainless steel reactor (Autoclave Engineers; Pittsburgh; PA) carry out in; use 2.5g catalyzer (0.5wt% of total reaction material), 60.5g N-((phosphonomethyl)) iminodiethanoic acid (12.1wt% of total reaction material), 1000ppm formaldehyde; 5000ppm formic acid; the total reaction material of 500g, the pressure of 110psig, 100 ℃ temperature and the stirring velocity of 1000rpm.Preceding 22 minutes oxygen delivery rate is 392ml/min, is 125ml/min then, till N-((phosphonomethyl)) iminodiethanoic acid exhausts substantially.

Table 14 has provided the result.Add therein in all tests of bismuth compound, formaldehyde, formic acid and NMG level are lower than those that find in controlled trial.

Table 14

The direct interpolation of the bismuth of various sources and amount

The amount of the Bi that is added and source	Glyphosate (%) * *	NPMIDA (％) **	CH 2O (mg/g) ***	HCO 2H (mg/g) ***	AMPA/ MAMPA (mg/g) ***	NMG (mg/g) ***	Cycling time (min)
								0 (contrast)	8.2	ND	4.0	22.5	9.4	2.0	39.3
0.0074g (BiO) 3CO 3 (100ppm′)	8.1	ND	2.6	3.8	10.9	ND	54.1
								0.037g (BiO) 2CO 3 (500ppm)	7.8	ND	1.8	1.4	14.5	ND	58.2
0.074g (BiO) 2CO 3 (1000ppm)	7.7	ND	2.0	1.3	16.4	ND	60.2
								0.0141g Bi(NO 3) 3·5H 3O (100ppm)	8.1	ND	2.4	3.0	11.2	ND	53.2
0.070g Bi(NO 3) 3·5H 2O (500ppm)	7.7	ND	1.9	1.4	14.4	ND	58.5
								0141g Bi(NO 3) 3·5H 3O (1000ppm)	7.6	ND	2.0	1.2	16.2	ND	59.2
0.0067g Bi 2O 3?(100ppm)	8.1	ND	2.5	3.5	13.9	ND	48
								0.034g Bi 2O 3 (500ppm)	7.6	ND	2.0	1.4	15.1	ND	58.7
0.067g Bi 2O 3 (1000ppm)	7.6	ND	2.0	1.2	17.3	ND	60.6

^*Ppm is meant and equals 1: 1, the ratio of 000,000 Bi and N-((phosphonomethyl)) iminodiethanoic acid

* (quality ÷ total reaction material quality) * 100%

The glyphosate that * * mg ÷ g is produced

" ND " is meant and do not detect

B, Add the influence of the bismuth pair follow-up NPMIDA oxidation that contacts with catalyzer batch

Carry out four 6 circulation experiments (promptly, in each of 4 experiments, carry out 6 batch reactions successively), add other bismuth is added in effect and (2) of the reaction cycle after the initial bismuth interpolation in one or more subsequent reactions circulations effect to measure (1) initial bismuth.

Whole 4 experiments use the catalyzer (this catalyzer uses and the similar method preparation of embodiment 17 described methods) that contains 5wt% platinum and 0.5wt% iron to carry out.In each 6 circulation experiment, 6 round-robin each use identical catalyzer (that is, after a loop ends; reaction product isolated solution; discharge catalyzer, N-((phosphonomethyl)) iminodiethanoic acid that will be newly a collection of and this catalyzer merge then, begin a new circulation).Be reflected in the 1000ml stainless steel reactor (Autoclave Engineers) and carry out; use 2.5g catalyzer (0.5wt% of total reaction material); (60.5gN-(phosphonomethyl)) iminodiethanoic acid (12.1wt% of total reaction material); 1000ppm formaldehyde; 5000ppm formic acid; the total reaction material of 500g, the pressure of 110psig, 100 ℃ temperature and the stirring velocity of 1000rpm.Preceding 22 minutes oxygen delivery rate is 392ml/min, is 125ml/min then, till N-((phosphonomethyl)) iminodiethanoic acid is by basic consumption.

In control experiment, do not introduce bismuth at reaction zone in once in that 6 round-robin are any.In other three experiments, (be Bi at the bismuth oxide (III) that begins 0.034g of first reaction cycle ₂O ₃) be incorporated in the reaction medium.These the experiment one of in, only first reaction cycle begin bismuth oxide is incorporated into reaction zone.In another experiment, in the beginning of the first and the 4th reaction cycle, (III) is incorporated in the reaction medium with the 0.034g bismuth oxide.In the end in experiment,, the bismuth oxide (III) of 0.034g is incorporated in the reaction medium in the beginning of all 6 reaction cycle.

Table 15,16,17 and 18 has provided the result.The once interpolation of bismuth oxide (data that provide in table 16) often obtains and per three circulations (data that provide in table 17) or even the identical beneficial effect of each circulation (data that provide in table 18) interpolation once oxidation bismuth.

Table 15

Control experiment: 6 circulation NPMIDA oxidizing reactions of not adding bismuth

Sample (after all NPMIDA consume approximately, gathering unless otherwise prescribed)	Circulation 1	Circulation 2	Circulation 3	Circulation 4	Circulation 5	Circulation 6
							Glyphosate (%) *	8.2	8.4	8.4	8.5	8.5	8.4
NPMIDA(％)*	ND	0.006	0.008	ND	ND	ND
							CH 2O(mg/g)**	3.1	2.4	2.0	2.6	3.2	3.8
HCO 2H(mg/g)**	16	23	22	25	30	40
							AMPA/MAMPA(mg/g)**	7.5	6.9	6.3	5.5	5.8	5.9
NMG(mg/g)**	0.5	1.7	1.4	1.6	2.8	4.9
							Time (min)	48.5	43.5	54.5	52.8	54.1	51.7

* (quality ÷ total reaction material quality) * 100%

The glyphosate that * mg ÷ g is produced

" ND " is meant and do not detect

Table 16

The 6 circulation NPMIDA oxidizing reactions of when the first circulation beginning, adding bismuth

Sample (after all NPMIDA consume approximately, gathering unless otherwise prescribed)	Circulation 1	Circulation 2	Circulation 3	Circulation 4	Circulation 5	Circulation 6
							Glyphosate (%) *	7.8	8.6	8.5	8.6	8.6	7.7
NPMIDA(％)*	ND	ND	ND	ND	ND	0.005
							CH 2O(mg/g)**	2.4	2.7	2.1	2.6	3.1	3.9
HCO 2H(mg/g)**	DBNQ	DBNQ	DBNQ	DBNQ	DBNQ	DBNQ
							AMPA/MAMPA(mg/g)**	15	11	10	9.9	8.6	10
NMG(mg/g)**	ND	ND	ND	ND	ND	ND
							Time (min)	60.1	62.4	64.1	62.6	66.9	62

* (quality ÷ total reaction material quality) * 100%

The glyphosate that * mg ÷ is produced

" ND " is meant and do not detect

" DBNQ " be meant and can detect, but can not be quantitative

Table 17

When beginning, adds the first and the 4th round-robin 6 circulation NPMIDA oxidizing reactions of bismuth

Sample (after all NPMIDA consume approximately, gathering unless otherwise prescribed)	Circulation 1	Circulation 2	Circulation 3	Circulation 4	Circulation 5	Circulation 6
							Glyphosate (%) *	7.8	8.4	8.5	8.5	8.5	8.6
NPMIDA(％)*	ND	ND	ND	ND	ND	ND
							CH 2O(mg/g)**	2.3	2.6	2.6	3.2	3.6	3.5
HCO 2H(mg/g)**	3.4	3.1	3.2	2.9	3.3	3.5
							AMPA/MAMPA(mg/g)**	14	11	10	11	9.3	8.9
NMG(mg/g)**	ND	ND	ND	ND	ND	ND
							Time (min)	57.4	63.2	64.3	64.9	66	64.5

* (quality ÷ total reaction material quality) * 100%

The glyphosate " ND " that * mg ÷ g is produced is meant and does not detect

Table 18

When beginning, adds each round-robin 6 circulation NPMIDA oxidizing reactions of bismuth

Sample (after all NPMIDA consume approximately, gathering unless otherwise prescribed)	Circulation 1	Circulation 2	Circulation 3	Circulation 4	Circulation 5	Circulation 6
							Glyphosate (%) *	7.8	8.5	8.2	8.3	8.3	8.3
NPMIDA(％)*	ND	ND	ND	ND	ND	ND
							CH 2O(mg/g)**	2.4	2.8	3.2	2.9	3.4	4.0
HCO 2H(mg/g)**	ND	ND	ND	ND	ND	ND
							AMPA/MAMPA (mg/g)**	14	12	11	12	10	9.7
NMG(mg/g)**	ND	ND	ND	ND	ND	ND
							Time (min)	56.4	62.4	64.8	62.8	66	66.1

* (quality ÷ total reaction material quality) * 100%

The glyphosate that * mg ÷ g is produced

" ND " is meant and do not detect

C, UsePt /Fe /C Catalyzer is disposable interpolation bismuth in 20 NPMIDA oxidation cycle Influence

Carry out 2 20 circulation experiments, once adding bismuth with mensuration influences 20 N-((phosphonomethyl)) iminodiethanoic acid oxidizing reaction round-robin.

The catalyzer that two experiments are all used to contain 5wt% platinum and 0.5wt% iron (this catalyzer uses with the similar method of method described in the embodiment 17 and prepares) carries out.In each experimentation, all use identical catalyzer each time at 20 round-robin.Be reflected in the 1000ml stainless steel reactor (Autoclave Engineers) and carry out; use 2.5g catalyzer (0.5wt% of total reaction material); 60.5g N-((phosphonomethyl)) iminodiethanoic acid (12.1wt% of total reaction material); 1000ppm formaldehyde; 5000ppm formic acid; the total reaction material of 500g, the pressure of 110psig, 100 ℃ temperature and the stirring velocity of 1000rpm.Preceding 22 minutes oxygen delivery rate is 392ml/min, is 125ml/min then, till N-((phosphonomethyl)) iminodiethanoic acid is by basic consumption.In control experiment, do not introduce bismuth in any one to reaction zone at 20 round-robin.In another experiment, when first reaction cycle begins, 0.034g bismuth oxide (III) is incorporated in the reaction medium.

Figure 15 has compared gained formic acid concn change curve.Once introduce bismuth to reaction zone and reduced formic acid concn in all 20 circulations.

D, UsePt /Sn /C Catalyzer is disposable interpolation bismuth in 30 NPMIDA oxidation cycle Influence

Carry out two 30 circulation experiments, 30 N-((phosphonomethyl)) iminodiethanoic acid oxidizing reaction round-robin is influenced to measure disposable interpolation bismuth.

The catalyzer that two experiments are all used to contain 5wt% platinum and 1wt% tin (this catalyzer uses with the similar method of embodiment 18 described methods and prepares) carries out.In each experimentation, all use identical catalyzer in each at 30 round-robin.Respectively circulating in the 300ml reactor (is made by alloy; HastelloyC; Autoclave Engineers) carries out in; use 1.35g catalyzer (0.75wt% of total reaction material), 21.8g N-((phosphonomethyl)) iminodiethanoic acid (12.1wt% of total reaction material), 1000ppm formaldehyde; 5000ppm formic acid; the total reaction material of 180g, the pressure of 90psig, 100 ℃ temperature and the stirring velocity of 900rpm.Preceding 26 minutes oxygen delivery rate is 141ml/min, is 45ml/min then, till N-((phosphonomethyl)) iminodiethanoic acid is by basic consumption.In control experiment, do not introduce bismuth in any one to reaction zone at 30 round-robin.Another the experiment in, first reaction cycle begin 0.012g bismuth oxide (III) is incorporated in the reaction medium.

Figure 16 has compared the change curve of gained formic acid concn, and Figure 17 has compared the change curve of gained concentration of formaldehyde and the change curve that Figure 18 has compared gained NMG concentration.Even after 30 circulations, the disposable reaction zone that is incorporated into of bismuth is reduced formic acid concn and reaches 98%, reduce concentration of formaldehyde and reach 50% and reduce NMG concentration and reach 90%.

E, Bismuth is joined before used in 132 batches of NPMIDA oxidizing reactionsPt /Fe /C Effect in the catalyzer

Carry out 14 circulation experiments, to measure effect with bismuth and exhausted Pt/Fe/C catalyst mix.Before carrying out this experiment, catalyzer has been used for 129 crowdes of N-of catalysis ((phosphonomethyl)) iminodiethanoic acid oxidizing reaction.Live catalyst (that is, the catalyzer before using in 129 crowdes of N-((phosphonomethyl)) iminodiethanoic acid oxidation cycle in front) adopts and the similar method preparation of embodiment 17 described methods, and contains 5wt% platinum and 0.5wt% iron.

14 N-((phosphonomethyl)) iminodiethanoic acid oxidizing reaction circulates in the 300ml reactor and (is made by alloy; Hastelloy C; Autoclaye Engineers) carries out in; use 0.9g used catalyst (0.5wt%), 21.8g N-((phosphonomethyl)) iminodiethanoic acid (12.1wt%), 1000ppm formaldehyde; 5000ppm formic acid; the total reaction material of 180g, the pressure of 90psig, 100 ℃ temperature and the stirring velocity of 900rpm.Preceding 26 minutes oxygen delivery rate is 141ml/min, is 45ml/min then, till N-((phosphonomethyl)) iminodiethanoic acid is by basic consumption.Begin at the 4th round-robin, (III) is incorporated into reaction zone with the 0.012g bismuth oxide.

Figure 19 has shown the influence that formic acid, formaldehyde and NMG by product is produced at the 4th circulation interpolation bismuth.

F, Bismuth is joined before used in 30 batches of NPMIDA oxidizing reactionsPt /Sn /C Effect in the catalyzer

Carry out 11 circulation experiments, to measure effect with bismuth and exhausted Pt/Sn/C catalyst mix.This catalyzer before had been used for 30 crowdes of N-of catalysis ((phosphonomethyl)) iminodiethanoic acid oxidizing reaction.Live catalyst (that is, the catalyzer before using in 30 N-((phosphonomethyl)) iminodiethanoic acid oxidation cycle in front) uses with the similar method of embodiment 18 described methods and prepares, and contains 5wt% platinum and 1wt% tin.

11 N-((phosphonomethyl)) iminodiethanoic acid oxidizing reaction circulates in the 300ml reactor and (is made by alloy; Hastelloy C; Autoclave Engineers) carries out in; use 1.35g used catalyst (0.75wt% of total reaction material), 21.8g N-((phosphonomethyl)) iminodiethanoic acid (12.1wt% of total reaction material), 1000ppm formaldehyde; 5000ppm formic acid; the total reaction material of 180g, the pressure of 90psig, 100 ℃ temperature and the stirring velocity of 900rpm.Preceding 26 minutes oxygen delivery rate is 141ml/min, is 45ml/min then, till N-((phosphonomethyl)) iminodiethanoic acid is by basic consumption.Begin at the 4th round-robin, (III) is incorporated into reaction zone with the 0.012g bismuth oxide.

Figure 20 has shown the influence that formic acid, formaldehyde and NMG by product is produced at the 4th circulation interpolation bismuth.

G, Add the bismuth pair follow-up NPMIDA oxidation more than 100 times that contacts with this catalyzer batch Influence

Carry out two 125 circulation experiments, add bismuth to using the influence of subsequent reactions round-robin more than 100 times of same catalyzer to measure.

The catalyzer that two experiments are all used to contain 5wt% platinum and 1wt% tin (this catalyzer uses with embodiment 18 described similar methods and prepares) carries out.In each experimentation, in all circulations, use same catalyzer.Be reflected in the stirred-tank reactor and use 0.75% catalyzer (by total reaction material weight), 12.1%N-((phosphonomethyl)) iminodiethanoic acid (by total reaction material weight), the temperature of the pressure of 128pisg and 100 ℃ is carried out.(the definite time changes in 14.9 to 20.3 minutes with the difference of each batch the oxygen delivery rate of the first part of each batch reaction; wherein near time of 14.9 minutes be used for the front batch; near 20.3 minutes times be used for the back batch) be 1.3 (mg/min)/g total reaction materials; be 0.35 (mg/min)/g total reaction material then, till N-((phosphonomethyl)) iminodiethanoic acid is by basic consumption.To evaporate from a part of reaction product of each batch, and turn back to reactor, as the sacrifice reductive agent in the next batch reaction as the source of formaldehyde and formic acid.Be recycled to the formaldehyde of reactor and amount of formic acid in 100-330ppm and 0ppm-2300ppm scope (after adding afterwards 25 batches of bismuth oxide (III)) respectively with the formic acid of 0-200ppm.

In control experiment, do not introduce bismuth in once in that 125 round-robin are any to reaction zone.In another experiment, catalyzer at first is used for N-((phosphonomethyl)) iminodiethanoic acid of 17 batches of catalysis.After 17th batch of catalysis, catalyzer is separated with reaction product substantially, and the gained catalyst mixture is transferred in the catalyst stores jar, be incorporated in the catalyst mixture at this bismuth oxide (III)/g catalyzer 9.0mg.This catalyzer is used for the oxidation of N-((phosphonomethyl)) iminodiethanoic acid of 107 follow-up batch of catalysis then.

Figure 21 has compared gained formic acid concn change curve, and Figure 22 has compared gained concentration of formaldehyde change curve, and Figure 23 has compared gained NMG concentration curve.Even after 107 circulations, with bismuth disposable be incorporated into to contain also reduced formic acid in the mixture of catalysts and NMG concentration reaches about 90%.

Embodiment 21: NPMIDA is oxidized to glyphosate continuously with part used catalyst and use supplemental promoter

Present embodiment is for example understood utilization used catalyst and supplemental promoter in the past; in continuous oxidation reaction device system, N-((phosphonomethyl)) iminodiethanoic acid (" NPMIDA ") is oxidized to N-((phosphonomethyl)) glycine (" glyphosate ") continuously.This experimental design is used to simulate at first reaction zone and accounts for leading condition, especially is recycled to the occasion of reaction zone at the crystallizer mother liquor that contains reaction product.

Be reflected at and utilize 2 liters of Hastelloy C autoclaves (Autoclave Engineers Inc., Pittsburgh carry out in flow reactor system PA).Reactor is equipped with has 1.25 " agitator of 6 turbo wheels of diameter, it is operated under 1600RPM.Use has the Drexelbrook Universal III of the sensing member of polytetrafluorethylecoatings coatings ^TMSmart Level ^TMFluid level in the monitoring reactor.Utilize inner spiral coil cooling tube to control the temperature in the reactor in the reaction process.

In operating process, in reactor, feed the aqueous slurries raw material and the Oxygen Flow that contain NPMIDA continuously.Oxygen is incorporated into reaction medium by near the sintered glass that is arranged in the impeller.The liquid product stream that contains product N-((phosphonomethyl)) glycine (" glyphosate ") is discharged from reactor continuously by glass filter, and this filter is retained in the reaction medium any catalyzer that is added in this reactor.Product gas flow (contains CO ₂With unreacted oxygen) discharge continuously from the reactor head space.

By being joined, aqueous slurries raw material (1420g) and catalyzer (about 2wt% catalyzer of 29.3g or reactive material) begin reaction in the reactor.This aqueous slurries raw material contains NPMIDA (7.53wt%), glyphosate (2.87wt%), formaldehyde (2127 ppm by weight) and formic acid (3896 ppm by weight).Feed slurry also contains NaCl (about 450 ppm by weight), to imitate the low-level chloride impurity that exists usually in being purchased NPMIDA.The catalyzer for preparing by the method that is similar to method described in the above embodiment 17 comprises platinum (5wt%) and iron (0.5wt%) on the granulated carbon carrier.Catalyzer used being similar under those conditions described in the embodiment 20 in advance.

Sealed reactor inputs or outputs stream so that prevent any liquid.Reaction mixture is heated to about 105 ℃ and rise to the pressure of about 100psig with nitrogen.Starting oxygen flow (1000sccm), being reflected at does not have liquid to input or output under the situation of stream operation about 15 minutes.After these initial 15 minutes, starting slurry feed (70.4g/min), and, discharge reaction liquid continuously according to the indication of above-mentioned Drexelbrook level indicator, to keep the constant reactor level.After about 55 minutes, oxygen flow is reduced to 800sccm slightly.After under the oxygen flow of 800sccm, operating about 280 minutes, with Bi ₂O ₃(0.0336g) promotor is injected in the reactor as a supplement.Product liquid is analyzed with HPLC.The analytical results of continuous oxidation reaction provides in following table 19.Also have, Figure 24 has shown formaldehyde and the distribution of formic acid in product liquid when oxygen flow is 800sccm.

Table 19

The oxidation results that the HPLC of embodiment 21 analyzes

Time (min) 1	NPMIDA(wt％)	Glyphosate (wt%)	Formaldehyde (ppm)	Formic acid (ppm)
					55	0.85	7.74	3977	4758
172	1.43	7.48	3078	5338
					270	1.37	7.52	3137	5545
347	2.41	6.87	2872	1395
					405	2.42	6.97	2801	1385
464	2.48	6.99	2887	1474
					492	2.27	7.01	2881	1472

¹Time after beginning slurry feed

Embodiment 22: NPMIDA is oxidized to glyphosate continuously under the existence of former exhausted Pt/Fe/C catalyzer

The heterogeneous beaded catalyst of exhausted was oxidized to glyphosate continuously with NPMIDA before present embodiment was for example understood use.This experimental design is used to simulate in the flow reactor system and accounts for leading condition, especially is recycled to the occasion of reaction zone at the crystallizer mother liquor that will contain reaction product.

Experiment is carried out being similar in the flow reactor system described in the above embodiment 21.Begin reaction by aqueous slurries raw material (1424g) and heterogeneous beaded catalyst (about 2wt% catalyzer of 29.3g or reactive material) being added to reactor.This aqueous slurries raw material contains NPMIDA (7.01wt%), glyphosate (2.88wt%), formaldehyde (2099.9 ppm by weight) and formic acid (4690 ppm by weight).The slurry raw material also contains NaCl (about 450 ppm by weight), is present in the low-level chloride impurity that is purchased among the NPMIDA usually to simulate.This catalyzer prepares by being similar to method described in the above embodiment 17, and is included in platinum (5wt%) and iron (0.5wt%) on the granulated carbon carrier.Catalyzer is previous to be used being similar under those conditions described in the embodiment 20.

Sealed reactor inputs or outputs stream to prevent any liquid.Reaction mixture is heated to about 107 ℃ and rise to the pressure of about 100psig with nitrogen.Starting oxygen flow (900sccm), being reflected at does not have liquid to input or output under the situation of stream operation about 13 minutes.After these initial 13 minutes, starting slurry feed (70.4g/min), and, discharge reaction liquid continuously according to indication at Drexelbrook level indicator described in the above embodiment 21, to keep the constant reactor level.Product liquid is analyzed with HPLC.The analytical results of continuous oxidation reaction provides in following table 20.Glyphosate of being produced and the distribution that is retained in the NPMIDA reactant in the product liquid in Figure 25, have been shown.

Table 20

The oxidation results of embodiment 22

Time (min) 1	NPMIDA(wt％)	Glyphosate (wt%)
			94	0.67	7.10
138	0.55	7.02
			192	0.50	7.12
274	0.46	7.09
			358	0.47	7.06

¹Time after beginning slurry feed

Embodiment 23: NPMIDA is oxidized to glyphosate continuously in the presence of the Pt/Fe/C catalyzer

Present embodiment understands that for example (under low relatively catalyst concn) is oxidized to glyphosate continuously with NPMIDA in long time period in the presence of the heterogeneous beaded catalyst of fresh Pt/Fe/C.This experimental design is used to simulate at first reaction zone and may accounts for leading condition, especially is recycled to the occasion of reaction zone at the crystallizer mother liquor that contains reaction product.

Experiment with similarly carry out in the flow reactor system described in the above embodiment 21.Begin to react by in reactor, adding aqueous slurries raw material (1447g) and heterogeneous beaded catalyst (catalyzer of about 0.25wt% of 3.63g or reactive material).This aqueous slurries raw material contains NPMIDA (3.45wt%), glyphosate (1.55wt%), formaldehyde (1140 ppm by weight) and formic acid (2142 ppm by weight).Feed slurry also contains NaCl (about 450ppm), is present in the low-level chloride impurity that is purchased among the NPMIDA usually to simulate.This catalyzer by with described in the above embodiment 17 similarly method prepare, and be included in platinum (5wt%) and iron (0.5wt%) on the granulated carbon carrier.This catalyzer did not use in the past.

Sealed reactor inputs or outputs stream to prevent any liquid.Reaction mixture is heated to about 100 ℃ and rise to the pressure of about 100psig with nitrogen.Starting oxygen flow (300sccm), being reflected at does not have liquid to input or output under the situation of stream to carry out about 22 minutes.After these initial 22 minutes, starting slurry feed (70.4g/min), and, discharge reaction liquid continuously according to indication at Drexelbrook level indicator described in the above embodiment 21, to keep the constant reactor level.Allow reactor assembly turn round about 4300 minutes, after this, flow rate of liquid is increased doubly, so that the liquid reactor residence time is effectively reduced half.Product liquid is analyzed with HPLC.The analytical results of oxidation provides in following table 21 continuously.Glyphosate of being produced and the distribution that is retained in the NPMIDA reactant in the product liquid in Figure 26, have been shown.

Table 21

The oxidation results of embodiment 23

Time (min) 1	NPMIDA(wt％)	Glyphosate (wt%)
			66	0.72	3.59
130	0.76	3.61
			488	0.85	3.67
994	0.89	3.68
			1343	0.73	3.65
1476	0.76	3.63
			1918	0.89	3.61
2458	0.81	3.59
			2679	0.81	3.65
2807	0.80	3.63
			3072	0.98	3.67
3893	0.88	3.62
			4113	0.89	3.54
4215	0.86	3.56
			4314	1.99	2.73
4334	2.11	2.82

¹Time after beginning slurry feed

Embodiment 24: NPMIDA is oxidized to glyphosate continuously in placed in-line two stirred-tank reactors

Present embodiment understands that for example NPMIDA is oxidized to glyphosate continuously in the flow reactor system that comprises two stirred-tank reactors of series connection fractionated.

With reference to Figure 27, experiment is carried out in the flow reactor system that comprises two reactors and a crystallizer.Two reactors (respectively naturally available from Autoclave Engineers, Inc., Pittsburgh, 1 gallon of stainless steel autoclave of PA) are as placed in-line stirred-tank reactor operate continuously.The flow reactor system is arranged in such a way: the aqueous slurries raw material is incorporated into first reaction zone (reactor R1) continuously.Expel liquid effluent from R1 continuously, and be incorporated into second reaction zone (reactor R2).From the continuous expel liquid effluent of R2, and be incorporated into crystallizer, the product that is used for the glyphosate slurry reclaims.Independently oxygen is given to each reaction zone, independent of simultaneously each reactor discharge product gas.By near the glass filter that is positioned at the agitator paddle (2 " turbo wheel sheet) oxygen is incorporated into R1.Oxygen is incorporated into head space more than the R2 fluid level, and utilizes DISPERSIMAX type 2.5 " impeller, effectively with the back mixing of head space gas to reaction zone.The temperature of the reactive material in each reactor is controlled by inner cooling spiral.From R1 expel liquid effluent, this filter is retained among the R1 heterogeneous catalyst through glass filter.Equally, from R2 expel liquid effluent, keep the inside of heterogeneous catalyst through glass filter at R2.It is constant that reactive material in each reactor/volume keeps.

The flow reactor system is to start with similar mode described in the above embodiment 21, and wherein reactor starts with intermittent mode, starts the liquid flow by system afterwards soon.Raw material is to contain NPMIDA (about 7.6wt%), glyphosate (about 2.8wt%), the aqueous slurries of formaldehyde (about 2200 ppm by weight) and formic acid (about 4500 ppm by weight).Also low-level NaCl (about 450ppm) is joined in this raw material, be present in the chloride impurity that is purchased among the NPMIDA usually to simulate.Catalyzer prepares by the similar approach described in the above embodiment 17, and is included in platinum (5wt%) and iron (0.5wt%) on the granulated carbon carrier.Aqueous slurries raw material and catalyzer are joined in each reactor, obtained the catalyst concn of about 2wt% in each reactor, wherein the target total reactor material of R1 and R2 is respectively 2693g and 1539g.

Operational condition is summarised in the following table 22.In following table 23, provided the analytical results of aqueous slurries raw material composition, R1 liquids and gases effluent and the R2 liquids and gases effluent analyzed with HPLC.

Table 22

The summary of the operational condition of embodiment 24

	R1	R2
			Catalyst concn in the reactor:	2wt％	2wt％
Agitator RPM:	1000	1200
			Liquid flow rate:	128mL/min	128mL/min
Pressure:	116psig	90psig
			Oxygen flow speed:	～1840sccm	～390sccm
Temperature:	100℃	105℃
			The reactant quality:	2693g	1539g
Impeller-type:	Radial (2 ")	DISPERSIMAX(2.5”)

Table 23

The oxidizing reaction result of embodiment 24

The reactor feed
					Elapsed time (hr)	NPMIDA(wt％)	Glyphosate (wt%)	Formaldehyde (ppm)	Formic acid (ppm)
	8.13	2.98	?2348.5	?5562.6
					1.3	7.50	2.84	?2290.0	?4620.9
2.5	7.45	2.74	?2244.2	?4515.9
					3.6	7.45	2.74	?2244.2	?4515.9
4.5	7.45	2.74	?2244.2	?4515.9
					5.5	7.79	2.84	?2271.0	?4590.0
6.5	7.79	2.84	?2271.0	?4590.0
					7.5	7.57	2.81	?2286.8	?4584.9
8.8	7.57	2.81	?2286.8	?4584.9
					First reactor (R1) outlet
Elapsed time (hr)	NPMIDA(wt％)	Glyphosate (wt%)	Formaldehyde (ppm)	Formic acid (ppm)
					1.3	0.38	7.15	?385.4	?6115.1
2.5	0.41	6.65	?328.1	?4297.7
					3.6	1.18	6.83	?300.2	?4841.8
4.5	0.79	6.56	?307.2	?4746.3
					5.5	1.07	6.81	?317.1	?5193.0
6.5	0.88	6.48	?323.6	?5045.8
					7.5	0.90	6.50	?315.6	?4976.0
8.8	1.38	6.42	?323.0	?5305.2
					Second reactor (R2) outlet
Elapsed time (hr)	NPMIDA(wt％)	Glyphosate (wt%)	Formaldehyde (ppm)	Formic acid (ppm)
					1.3	0.03	6.84	?475.9	?3680.4
2.5	0.00	6.96	?194.7	?1048.1
					3.6	0.02	7.23	?424.0	?3702.4
4.5	0.00	6.97	?534.4	?3006.4
					5.5	0.00	7.27	?1025.5	?6176.5
6.5	0.00	6.89	?1524.2	?5471.0
					7.5	0.01	6.97	?1663.9	?5468.1
8.8	0.03	7.07	?1883.0	?5808.2

Embodiment 25:NPMIDA is oxidized to glyphosate continuously in placed in-line two stirred-tank reactors

Present embodiment understands that for example NPMIDA is oxidized to glyphosate continuously in comprising the flow reactor system of placed in-line two stirred-tank reactors, is sent to from the liquid efflunent of second reactor wherein that crystallizer is used to reclaim glyphosate and a mother liquid obtained part as reactor feedstocks is recycled to first reactor from crystallizer.

With reference to Figure 28, embodiment 25 with similarly carry out in the flow reactor system described in the above embodiment 24, just the mother liquor from crystallizer is recycled to the first reactor R1.The flow reactor system with above embodiment 21 described similar mode entrys into service, wherein reactor starts with intermittent mode, starts the liquid flow by system afterwards soon.At first in crystallizer (30L), add and comprise NPMIDA (0.16wt%), glyphosate (2.0wt%), the aqueous slurries raw material of formaldehyde (2754 ppm by weight) and formic acid (5637 ppm by weight), and under about 60 ℃ and 1 normal atmosphere, operate.In the slurry feeding system, add the aqueous slurries raw material that comprises NPMIDA (about 25wt%).Employed catalyzer is similar to the heterogeneous beaded catalyst that uses in embodiment 24.

Aqueous slurries and catalyzer are joined each reactor, obtain about 2wt% catalyst concn in each reactor, wherein the target total reactor material of R1 and R2 is respectively 2693g and 1539g.After the initial batch running, starting is by the liquid flow of system.The liquid that enters R1 comprises aqueous slurries raw material (about 40ml/min) and from the mother liquor recirculation (about 80ml/min) of crystallizer.Fluid level in this operation process in each reactor of control, so that in each reactor, keep constant reactant quality, in R1 and R2, reach the water retention time of 21 minutes and 12.2 minutes respectively, and the total liquid flow of passing through system that obtains about 120ml/min.

Operational condition is summarised in the following table 24.Product liquid is analyzed with HPLC.The aqueous slurries raw material is formed, and the analytical results of R1 liquid efflunent and R2 liquid efflunent provides in following table 25.Elapsed time is meant the time after the starting continuous liq stream.

Table 24

The summary of the operational condition of embodiment 25

	R1	R2
			Catalyst concn in the reactor:	2wt％	2wt％
Agitator RPM:	1015	1005
			Total liquid flow rate by system:	121mL/min	121mL/min
Pressure:	116pisg	89psig
			Oxygen flow speed:	～1660sccm	～280sccm
Temperature:	100℃	106℃
			The reactant quality:	2545g	1592g
Impeller-type:	Radial (2 ")	DISPERSIMAX(2.5”)

Table 25

The oxidation results of embodiment 25

First reactor (R1) outlet
					Elapsed time (hr)	NPMIDA(wt％)	Glyphosate (wt%)	Formaldehyde (ppm)	Formic acid (ppm)
1.3	1.50	6.99	849.8	3202.0
					2.9	0.45	8.16	1053.5	2789.3
4.1	0.62	8.40	1199.4	3178.0
					5.0	0.65	8.07	1240.8	3348.6
6.1	1.21	7.51	1294.7	3701.1
					Second reactor (R2) outlet
Elapsed time (hr)	NPMIDA(wt％)	Glyphosate (wt%)	Formaldehyde (ppm)	Formic acid (ppm)
					1.3	2.11	6.50	374.2	1682.3
2.9	0.27	8.02	501.0	2171.4
					4.1	0.15	8.55	451.0	2678.0
5.0	0.12	8.49	564.4	3107.5
					6.1	0.19	8.02	577.3	3505.7

Embodiment 26:NPMIDA is oxidized to glyphosate continuously in the presence of the Pt/Sn/C catalyzer

Present embodiment understands that for example NPMIDA is oxidized to glyphosate continuously in the presence of the heterogeneous beaded catalyst of Pt/Sn/C in stirred-tank reactor.This experimental design is used for simulating and may accounts for leading condition at second reaction zone of flow reactor system.

(Pittsburgh carries out in flow reactor system PA) for Autoclave Engineers, Inc. comprising 500mL Hastelloy C autoclave in experiment.Reactor is equipped with has 1.25 " agitator of radial six turbo wheels of diameter.Fluid level described in use and the above embodiment 21 in the similar level indicator monitoring reactor.Utilize inner cooling spiral to control the temperature in the reactor in the reaction process.

In operating process, in reactor, feed Oxygen Flow and the aqueous slurries raw material that contains NPMIDA continuously.Oxygen is incorporated into reaction medium by near the glass filter that is arranged in the impeller.The liquid product stream that contains the glyphosate product is discharged from reactor continuously by glass filter, and this filter is retained in the reaction medium any catalyzer that is added in the reactor.Liquid product stream of being discharged and the alkaline solution on-line mixing that can dissolve glyphosate.Product gas flow (contains CO ₂With unreacted oxygen) discharge continuously from the reactor head space.

The flow reactor system with similarly mode entry into service described in the above embodiment 21, wherein reactor starts with intermittent mode, starts the liquid flow by system afterwards soon.The aqueous slurries raw material comprises NPMIDA (2.46wt%), glyphosate (3.72wt%), formaldehyde (1381 ppm by weight) and formic acid (6485 ppm by weight).This catalyzer is by preparing with above embodiment 14 described similar methods, and comprises platinum (5wt%) and the tin (1.0wt%) that loads on the granulated carbon carrier.

Operational condition is summed up in following table 26.Product liquid is analyzed with HPLC.The analytical data of oxidizing reaction provides in following table 27.

Table 26

The summary of the operational condition of embodiment 26

Catalyst concn in the reactive material:	1wt％
		Agitator RPM:	1000
Liquid flow rate:	30.8mL/min
		Pressure:	100pisg
Gas flow rate:	270sccm
		Temperature:	100℃
The reactant quality:	300g

Table 27

The oxidation results of embodiment 26

Raw material is formed
			?-	NPMIDA(wt％)	Glyphosate (wt%)
?-	2.46	3.72
			Reactor effluent
Elapsed time (min)	?NPMIDA(wt％)	Glyphosate (wt%)
			?120	0.07	5.47
?1200	0.09	5.58
			?2500	0.12	5.45
?3500	0.15	5.47

Embodiment 27:NPMIDA is oxidized to glyphosate continuously in the presence of the Pt/Sn/C catalyzer

Present embodiment understands that for example NPMIDA is oxidized to glyphosate continuously in the presence of the heterogeneous beaded catalyst of Pt/Sn/C in stirred-tank reactor.This experimental design is used for simulating and may accounts for leading condition at second reaction zone of flow reactor system.Also have, change oxygen flow speed so that the influence of various oxygen flow speed to transformation efficiency to be described.

This experiment with the similar flow reactor of the reactor assembly system described in the above embodiment 26 in.In operating process, continuous feed Oxygen Flow and the aqueous slurries raw material that contains NPMIDA in reactor.Oxygen is incorporated into reaction medium by near the glass filter that is arranged in the impeller.The liquid product stream that contains the glyphosate product is discharged from reactor continuously by glass filter, and this filter is retained in the reaction medium any catalyzer that is added in the reactor.Liquid product stream of being discharged and the alkaline solution on-line mixing that can dissolve glyphosate.Product gas flow (contains CO ₂With unreacted oxygen) discharge continuously from the reactor head space.

The flow reactor system with similarly mode entry into service described in the above embodiment 21, wherein reactor starts with intermittent mode, starts the liquid flow by system afterwards soon.The aqueous slurries raw material comprises NPMIDA (about 2.8wt%), glyphosate (about 4.2wt%), formaldehyde (about 1425 ppm by weight) and formic acid (about 6570 ppm by weight).This catalyzer by with described in the above embodiment 14 similarly method prepare, and comprise platinum (5wt%) and the tin (1.0wt%) that loads on the granulated carbon carrier.

Operational condition is summed up in following table 28.In the process of this experiment, the oxygen flow speed that is given to reactor rises and descends in the scope of 300sccm 75.Product liquid is analyzed with HPLC.The analytical data of oxidation provides in following table 29 continuously.

Table 28

The operational condition of embodiment 27

Catalyst concn in the reactor:	1wt％
		Agitator RPM:	1000
Liquid flow rate:	30mL/min
		Pressure:	100pisg
Gas flow rate:	Variable (75-300sccm)
		Temperature:	100℃
The reactant quality:	300g
		Impeller-type:	Radial (1.25 ")

Table 29

The oxidation results of embodiment 27

Raw material is formed
							NPMIDA (wt％)	Glyphosate (wt%)	Formaldehyde (ppm)	Formic acid (ppm)
	2.83	4.17	1425.1	?6569.8
						The reactor discharge is formed
Elapsed time (hr)	NPMIDA (wt％)	Glyphosate (wt%)	Formaldehyde (ppm)	Formic acid (ppm)	O 2Flow (sccm)
						0.0	1.1	4.59	1699.5	?5463.1	74.7
0.4	1.8	4.86	1543.7	?6067.0	49.7
						0.7	1.98	4.74	1431.7	?6020.5	49.8
1.0	2.02	4.90	1478.1	?6105.2	52.7
						1.4	1.97	4.80	1474.0	?6209.0	54.7
1.7	1.91	4.73	1441.3	?5806.0	54.7
						2.0	1.67	4.93	1588.8	?6006.9	74.7
2.4	1.54	5.03	1590.2	?6135.3	74.7
						2.7	1.63	5.20	1625.7	?6280.1	74.7

Table 29 (continuing)

Elapsed time (brs)	NPMIDA (wt％)	Glyphosate (wt%)	Formaldehyde (ppm)	Formic acid (ppm)	O 2Flow (sccm)
						3.0	1.64	5.19	1591.5	6015.1	74.8
3.4	1.61	5.00	1547.8	5834.7	74.7
						3.7	1.61	5.12	1541.0	5864.8	74.7
4.0	1.58	5.15	1566.9	5791.0	74.7
						4.4	1.61	5.23	1565.6	6274.6	74.7
4.7	0.66	6.01	2099.7	6337.5	149.8
						5.0	0.51	6.20	2109.3	6036.9	149.6
5.4	0.46	5.81	1976.8	5688.5	149.8
						5.7	0.47	6.04	2094.3	5849.7	149.8
6.0	0.45	6.04	2109.3	5785.5	149.8
						6.4	0.45	6.15	2157.1	6101.1	149.8
6.7	0.41	5.70	2016.4	5489.1	149.8
						7.0	0.38	5.38	1907.1	5213.1	149.8
7.4	0.41	5.79	2056.0	5531.4	149.8
						7.7	0.44	6.26	2230.9	5949.5	149.8
8.0	0.35	6.43	2337.4	6083.4	166.0
						8.4	0.48	6.09	2356.6	6147.6	210.6
8.7	0.33	6.37	2665.3	6464.5	224.9
						9.0	0.34	6.24	2684.4	6308.8	224.9
9.4	0.36	6.30	2741.8	6412.6	224.9
						9.7	0.19	6.58	2680.3	6340.2	224.7
10.0	0.22	6.54	2530.1	6367.5	224.7
						10.4	0.20	6.52	2560.1	6256.9	224.7
10.7	0.18	5.51	2163.9	5241.8	224.7
						11.0	0.22	6.37	2502.7	6202.2	224.7

Table 29 (continuing)

Elapsed time (hrs)	NPMIDA (wt％)	Glyphosate (wt%)	Formaldehyde (ppm)	Formic acid (ppm)	O 2Flow (sccm)
						l1.4	0.23	6.73	2648.9	6449.5	224.7
11.7	0.20	6.35	2517.8	6131.2	224.7
						12.0	0.16	5.11	1987.7	4889.4	224.7
12.4	0.20	6.04	2430.3	5877.1	224.7
						12.7	0.13	6.67	2777.3	6276.0	299.7
13.0	0.13	6.73	2844.3	6349.8	299.7
						13.4	0.15	6.61	2808.8	6204.9	299.7
13.7	0.08	5.57	2323.8	5144.8	299.7
						14.0	0.10	6.61	2704.9	6215.9	299.8
14.4	0.14	6.80	2774.6	5810.1	299.8
						14.7	0.13	6.89	2845.6	6147.6	299.8
15.0	0.12	6.86	2871.6	6232.3	299.8
						15.3	0.11	6.53	2745.9	5874.3	299.8
15.7	0.13	6.28	2668.0	5654.4	299.8
						16.0	0.15	6.86	2923.5	6360.7	299.8
16.3	0.16	6.86	2970.0	6702.2	299.8
						16.7	0.17	6.57	2874.3	6459.0	224.8
17.0	0.23	6.53	2789.6	6508.2	224.8
						17.3	0.24	6.57	2822.4	6403.0	224.8
17.7	0.25	6.63	2822.4	6580.2	224.8
						18.0	0.23	6.39	2736.3	6385.3	224.8
18.3	0.22	6.19	2668.0	6189.9	224.8
						18.7	0.23	6.53	2811.5	6546.5	224.8
19.0	0.24	6.52	2792.4	6445.4	224.8
						19.3	0.24	6.20	2655.7	6138.0	224.8

Table 29 (continuing)

Elapsed time (hrs)	NPMIDA (wt％)	Glyphosate (wt%)	Formaldehyde (ppm)	Formic acid (ppm)	O 2Flow (sccm)
						19.7	0.35	6.49	2752.7	6278.7	224.8
20.0	0.48	6.23	2572.4	6460.4	149.8
						20.3	0.53	6.15	2513.7	6030.1	149.8
20.7	0.50	6.34	2542.4	6143.5	149.8
						21.0	0.51	6.31	2527.3	6113.4	149.8
21.3	0.48	6.31	2527.3	6050.6	149.8
						21.7	0.48	6.42	2523.2	5885.3	149.8
22.0	0.46	6.16	2430.3	5655.8	149.8
						22.3	0.48	6.38	2521.9	6032.8	149.8
22.7	0.45	6.12	2426.2	5695.4	149.8
						23.0	0.46	6.26	2480.9	5868.9	149.8
23.3	1.18	6.20	2117.5	6220.0	74.8
						23.7	1.30	5.87	1956.3	5970.0	74.8
24.0	1.61	5.68	1916.7	5909.9	74.8
						24.3	1.50	5.61	1795.1	5720.0	74.8
24.7	1.61	5.85	1847.0	5862.0	74.8
						25.0	1.68	5.87	1908.5	6599.8	74.8
25.3	1.69	5.83	1868.9	6653.0	74.8
						25.7	1.60	5.57	1773.2	6460.4	74.8
26.0	1.71	5.75	1837.4	6577.9	748
						26.3	1.60	5.46	1751.4	6299.2	74.8
26.7	1.65	5.71	1827.9	6416.7	74.8
						27.0	1.64	5.60	1811.5	6433.1	74.8
27.3	1.63	5.63	1826.5	6297.8	74.8

Embodiment 28:NPMIDA is oxidized to glyphosate continuously in placed in-line two stirred-tank reactors

Present embodiment understands that for example NPMIDA is oxidized to glyphosate continuously in comprising the flow reactor system of placed in-line two stirred-tank reactors.In the present embodiment, the particle heterogeneous catalyst is transferred to second reactor from first reactor.The catalyzer of discharging from second reactor separates with the second liquid reactor effluent by filtering, and is recycled to first reaction zone.

With reference to Figure 29, be reflected in the flow reactor system that comprises two stirred-tank reactors, slurry feeding system and catalyzer filtering system and carry out.Two reactors (respectively naturally available from Autoclave Engineers, Inc., Pittsburgh, 1 gallon of stainless steel autoclave of PA) are as placed in-line stirred-tank reactor operate continuously.Oxygen is given to each reactor.Liquid efflunent is discharged from first reactor (R1) by dip-tube, and this dip-tube makes catalyzer be brought into second reactor (R2) together from the liquid efflunent of R1.Some reaction product gas also are entrained in the dip-tube from R1 to R2, and the reaction product gas among other R1 is discharged from reactor.Similarly, from R2 expel liquid effluent, this dip-tube makes catalyzer and some reaction product gas be removed with effluent by dip-tube.The R2 liquid efflunent that will contain catalyzer is transferred to the catalyzer filtering system.This catalyzer filtering system has produced the Continuous Flow of filtrate of catalyst-free as product.Filter backflushing liquid is given to the catalyzer filtering system, washes in a continuous manner with the catalyzer that will filter out and get back to R1.Oxygen is incorporated into R1 and R2 by glass filter, this filter be arranged in separately near the agitator paddle (R1 and R2 2 " the turbine blade impeller).Use inner cooling spiral to control temperature in each reactor.

The aqueous slurries raw material that will contain the 25wt%NPMIDA that has an appointment is given to reactor with the speed of about 50ml/min.Filter backflushing liquid contains NPMIDA (about 3wt%), glyphosate (about 0.1wt%), formaldehyde (about 3000 ppm by weight) and formic acid (about 7000 ppm by weight).Filter backflushing liquid turns back to R1 with the speed of about 100ml/min.Catalyzer by with described in the above embodiment 17 similarly method prepare, and on the granulated carbon carrier, comprise platinum (5wt%) and iron (0.5wt%).Catalyzer is joined reactor assembly, so that the catalyzer starting point concentration of about 1wt% to be provided.Reactor assembly with embodiment 24 described similar mode entrys into service, wherein reactor starts with intermittent mode, shortly after that the liquid flow of starting by this system.

Operational condition is summed up in following table 30.Product liquid is analyzed by HPLC.Oxidation results provides in following table 31.Table 31 has provided the data that the liquid efflunent of data (comprising the binding substances that filters backwashings and aqueous slurries raw material from catalyzer) that the inlet stream that is given to R1 forms and R1 and R2 is formed.

Table 30

The summary of the operational condition of embodiment 28

	R1	R2
			Catalyst concn in the reactor:	～1wt％	～1wt％
Agitator RPM:	～1000	～1000
			Liquid flow rate (by the total amount of reactor):	～150mL/min	～150mL/min
Pressure:	120-140pisg	120-140psig
			Oxygen flow speed:	2000-2500sccm	～400sccm
Temperature:	～100-105℃	～105℃
			The reactive material quality:	～2950g	～1726g
Impeller-type:	Radial (2 ")	Radial (2 ")

Table 31

The oxidation results of embodiment 28

Raw material is formed
					Elapsed time (hr)	NPMIDA(wt％)	Glyphosate (wt%)	Formaldehyde (ppm)	Formic acid (ppm)
20.9	8.08	1.81	1778.0	4650.0
					23.8	8.38	1.80	1757.2	4400.5
30.3	8.54	1.77	1518.5	4560.5
					33.8	8.55	1.78	1522.8	4573.5
First reactor (R1) discharge
					20.9	3.50	7.87	668.0	4384.2
23.8	3.44	7.32	651.6	4425.4
					30.3	2.87	8.43	756.7	5057.3
33.8	2.71	8.39	798.8	5206.4
					Second reactor (R2) discharge
20.9	2.55	8.04	302.5	3382.5
					23.8	3.27	7.71	258.7	3791.2
30.3	0.40	6.98	-	4017.3
					33.8	1.81	8.24	312.5	3945.7

Embodiment 29:NPMIDA is oxidized to glyphosate continuously in the presence of the Pt/Sn/C catalyzer

Present embodiment understands that for example NPMIDA is oxidized to glyphosate continuously in the presence of the heterogeneous beaded catalyst of Pt/Sn/C.This experimental design is used for simulating and may accounts for leading reaction conditions at the first stirring tank reaction zone of flow reactor system.

Experiment with similarly carry out in the flow reactor system described in the embodiment 26, only be to use 1000ml Hastelloy C autoclave.Reactor is equipped with has 1.25 " agitator of radial six turbo wheels of diameter.Used similar level indicator is monitored among fluid level use in the reactor and the embodiment 21.Utilize inner cooling spiral to control the temperature in the reactor in the reaction process.

In operating process, continuous feed Oxygen Flow and the aqueous slurries raw material that contains NPMIDA in reactor.Oxygen is incorporated into reaction medium by near the glass filter that is arranged in the impeller.The liquid product stream that contains the glyphosate product is discharged from reactor continuously by glass filter, and this filter is retained in the reaction medium any catalyzer that is added to reactor.The liquid product stream of being discharged then with the alkaline solution on-line mixing that can dissolve glyphosate.Product gas flow (is contained CO ₂With unreacted oxygen) discharge from the reactor head space continuously.

The aqueous slurries raw material comprises NPMIDA (about 7.7wt%), formaldehyde (about 3000 ppm by weight) and formic acid (about 6100 ppm by weight).Catalyzer by with described in the above embodiment 14 similarly method prepare, and comprise platinum (5wt%) and the tin (1.0wt%) that loads on the granulated carbon carrier.The flow reactor system is to come entry into service with similar mode described in the embodiment 21, and wherein reactor starts with intermittent mode, and shortly after that starting is through the liquid flow of system.Operational condition is summed up in following table 32.The analytical data of oxidation provides in following table 33 continuously.

Table 32

The summary of the operational condition of embodiment 29

Catalyst concn in the reactor:	1wt％
		Agitator RPM:	1000
Liquid flow rate:	30.8mL/min
		Pressure:	100pisg
Oxygen gas flow rate:	647sccm
		Temperature:	100℃
The reactant quality:	725g
		Impeller-type:	Radial (1.25 ")

Table 33

The oxidation results of embodiment 29

Raw material is formed
				NPMIDA(wt％)	Glyphosate (wt%)
	7.73	0.00
			The reactor discharge
Elapsed time (hr)	NPMIDA(wt％)	Glyphosate (wt%)
			0.0	0.04	1.35
0.5	0.29	4.42
			1.0	0.34	4.91
1.5	0.41	5.18
			2.0	0.58	5.55
2.5	0.97	6.50

Embodiment 30:NPMIDA is oxidized to glyphosate continuously in the presence of the Pt/Sn/C catalyzer

Present embodiment understands that for example NPMIDA in the presence of the heterogeneous beaded catalyst of Pt/Sn/C, is oxidized to glyphosate continuously in having the flow reactor system in single reaction district.

Experiment is with above (Pittsburgh carries out in flow reactor system PA) for Autoclave Engineers, Inc. similarly comprising 500mL Hastelloy C autoclave described in the embodiment 27.Reactor is equipped with has 1.25 " agitator of radial six turbo wheels of diameter.Fluid level in the reactor is used with above and is monitored at similar level indicator described in the embodiment 21.Utilize inner cooling spiral to control the temperature in the reactor in the reaction process.

In operating process, continuous feed Oxygen Flow and the aqueous slurries raw material that contains NPMIDA in reactor.Oxygen is incorporated into reaction medium by near the glass filter that is arranged in the impeller.The liquid product stream that contains the glyphosate product is discharged from reactor continuously by glass filter, and this filter is retained in the reaction medium any catalyzer that is added to reactor.Product gas flow (is contained CO ₂With unreacted oxygen) discharge from the reactor head space continuously.

The flow reactor system is to come entry into service with similar mode described in the embodiment 21, and wherein reactor starts with intermittent mode, and shortly after that starting is through the liquid flow of system.The aqueous slurries raw material comprises NPMIDA (about 2.9wt%).Catalyzer by with described in the above embodiment 14 similarly method prepare, and comprise platinum (5wt%) and the tin (1.0wt%) that loads on the granulated carbon carrier.Operational condition is summed up in following table 34.Product liquid is analyzed with HPLC.The analytical data of oxidation provides in following table 35 continuously.

Table 34

The summary of the operational condition of embodiment 30

Catalyst concn in the reactor:	1wt％
		Agitator RPM:	1000
Liquid flow rate:	15.3mL/min
		Pressure:	100pisg
Oxygen gas flow rate:	150sccm
		Temperature:	95℃
The reactant quality:	300g
		Impeller-type:	Radial (1.25 ")

Table 35

The oxidation results of embodiment 30

Elapsed time (hrs)	NPMIDA (wt％)	Glyphosate (wt%)	Formaldehyde (ppm)	Formic acid (ppm)
					0.0	2.87	0.00	4.6	14.9
0.3	2.94	0.01	13.4	18.9
					0.7	2.01	0.79	760.4	563.1
1.0	0.12	2.07	1893.6	1566.6
					1.3	0.07	2.32	1953.6	1713.4
1.7	0.01	2.27	2111.1	1497.2
					2.0	0.00	2.27	2167.1	1487.9
2.3	0.00	2.26	2155.1	1509.2
					2.7	0.00	2.26	2183.1	1495.9
3.0	0.00	2.27	2189.8	1549.3
					3.3	0.00	2.27	2195.1	1535.9
3.7	0.00	2.28	2196.5	1538.6
					4.0	0.04	2.26	2184.5	1522.6
4.3	0.03	2.26	2184.5	1474.5
					4.4	0.00	2.26	2177.8	1478.5

Embodiment 31:NPMIDA is oxidized to the glyphosate present embodiment continuously and understands that for example NPMIDA is oxidized to glyphosate continuously in the presence of the heterogeneous beaded catalyst of Pt/Sn/C in the presence of the Pt/Sn/C catalyzer.This experimental design is used to illustrate the influence to NPMIDA-glyphosate transformation efficiency of pressure, liquids and gases flow.

Experiment with the described flow reactor system that similarly comprises 500mL Hastelloy C autoclave (Autoclave Engineers Inc.) of embodiment 30 in carry out.Reactor is equipped with has 1.25 " agitator of radial six turbo wheels of diameter.Used similar level indicator is monitored among fluid level use in the reactor and the embodiment 21.Utilize inner cooling spiral to control the temperature in the reactor in the reaction process.

In operating process, continuous feed Oxygen Flow and the aqueous slurries raw material that contains NPMIDA in reactor.Oxygen is incorporated into reaction medium by near the glass filter that is arranged in the impeller.The liquid product stream that contains the glyphosate product is discharged from reactor continuously by glass filter, and this filter is retained in the reaction medium any catalyzer that is added to reactor.Product gas flow (is contained CO ₂With unreacted oxygen) discharge from the reactor head space continuously.

The aqueous slurries raw material comprises NPMIDA (about 3.0wt%), formaldehyde (about 1000 ppm by weight) and formic acid (about 5100 ppm by weight).Catalyzer by with described in the above embodiment 14 similarly method prepare, and comprise platinum (5wt%) and the tin (1.0wt%) that loads on the granulated carbon carrier.

The flow reactor system is to come entry into service with similar mode described in the embodiment 21, and wherein reactor starts with intermittent mode, and shortly after that starting is through the liquid flow of system.In experimentation, the oxygen flow speed that is given to reactor fluctuates in 75 to 300sccm scope.Operational condition is summed up in following table 36.Product liquid is analyzed with HPLC.The analytical data of oxidation provides in following table 37 continuously.

Table 36

The summary of the operational condition of embodiment 31

Catalyst concn in the reactor:	1wt％
		Agitator RPM:	1000
Liquid flow rate:	Variable (consulting data)
		Pressure:	Variable (consulting data)
Oxygen gas flow rate:	Variable (consulting data)
		Temperature:	100℃
The reactant quality:	300g
		Impeller-type:	Radial (1.25 ")

Table 37

The oxidation results of embodiment 31

Time (min)	Liquid feeding speed (ml/min)	Pressure (psig)	O 2Flow velocity (sccm)	GI (wt％)	Gly (wt％)	HCHO (ppm)	HCOOH (ppm)	NMG (ppm)	NFG (ppm)	AMPA (ppm)	MAMPA (ppm)	CO in the exhaust 2 ％
													0	50	100.2	149.6	0.69	1.40	1713	4901	26	167	20	11	66
21	50	100.1	149.6	0.88	1.35	1756	5247	31	139	12	12	74
													42	50	99.9	149.6	0.92	1.34	1709	5342	19	136	9	8	76
63	50	99.9	149.6	0.90	1.34	1671	5293	23	133	9	12	78
													84	50	100.1	149.6	0.91	1.40	1709	5411	23	135	9	13	79
105	50	100	149.6	0.81	1.41	1685	5311	21	128	12	12	82
													126	50	99.9	149.6	0.84	1.42	1686	5416	24	128	11	12	84
147	50	100	149.6	0.85	1.42	1685	5365	21	126	9	12	84
													168	50	100	149.6	0.88	1.41	1650	5357	20	120	9	12	85
189	50	100	149.6	0.87	1.42	1651	5344	19	117	9	9	85
													210	50	100.1	149.6	0.94	1.36	1607	5312	20	115	8	9	83
231	35	100	149.6	0.38	1.56	1312	4661	21	136	15	12	87
													252	35	100.6	149.6	0.45	1.84	1799	5456	24	173	18	11	83
273	35	100	149.6	0.33	1.93	1794	5456	33	213	29	19	80
													294	35	99.9	149.6	0.32	1.88	1785	5335	13	199	27	-	85
315	35	100.1	149.6	0.31	1.90	1834	5388	30	205	27	13	85
													336	35	100.2	149.6	0.30	1.90	1866	5398	32	184	26	19	84
357	35	100	149.6	0.36	1.92	1887	5421	35	182	26	19	84

Time (min)	Liquid feeding speed (ml/min)	Pressure (psig)	O 2Flow velocity (sccm)	GI (wt％)	Gly (wt％)	HCHO (ppm)	HCOOH (ppm)	NMG (ppm)	NFG (ppm)	AMPA (ppm)	MAMPA (ppm)	CO in the exhaust 2 ％
													378	35	100	149.6	0.33	1.92	1884	5322	31	175	27	17	83
399	35	100	149.6	0.36	1.92	1906	5366	33	176	26	18	83
													420	35	99.8	149.6	0.35	1.95	1932	5386	33	177	27	19	83
441	35	100	149.6	0.34	1.93	1950	5331	33	174	29	18	83
													462	35	100.1	149.6	0.33	1.90	1956	5248	33	170	31	18	83
483	20	100.2	149.6	0.04	2.18	1547	4205	9	233	188	-52	77
													504	20	100.2	149.6	0.01	2.15	1656	4325	10	231	304	75	68
525	20	100	149.6	0.01	2.19	1756	4613	12	239	329	80	66
													546	20	99.9	149.6	0.01	2.15	1799	4703	12	233	324	84	64
567	20	100	149.6	0.01	2.13	1822	4743	15	226	319	79	63
													588	20	100	149.6	0.02	2.10	1839	4750	16	229	309	80	62
614	-	99.9	149.6			-	-	-	-	-	-	61
													635	-	100.1	149.6				-	-	-	-	-	61
656	-	99.9	149.6			-	-	-	-	-	-	60
													677	50	100	149.6	0.52	1.79	2379	5668	27	181	66	23	64
698	35	99.8	149.6	0.66	1.14	1563	4079	20	88	12	13	70
													719	35	100	149.6	0.29	1.95	2271	5382	34	180	38	18	80
740	35	99.5	149.6	0.27	2.00	2334	5428	35	183	39	19	79
													761	35	100.8	0			-	-	-	-	-	-	54
782	35	100.1	0	2.76	0.10	980	4930	12	13	0	8	53
													803	35	99.7	150	1.67	1.07	1344	4074	8	97	5	9	17

Time (min)	Liquid feeding speed (ml/mn)	Pressure (psig)	O 2Flow velocity (sccm)	GI (wt％)	Gly (wt％)	HCHO (ppm)	HCOOH (ppm)	NMG (ppm)	NFG (ppm)	AMPA (ppm)	MAMPA (ppm)	CO in the exhaust 2 ％
													824	35	100.2	150	0.65	1.71	2002	5269	20	148	17	12	59
845	35	100.2	150	0.55	1.79	2218	5499	24	151	23	14	68
													979	35	99.6	199.8	0.02	1.93	2271	4947	20	174	832	32	44
1047	35	100	199.8	0.38	1.90	2342	5881	29	152	25	20	43
													1067	35	100	199.8	0.19	2.05	2532	5723	34	162	50	22	56
1086	35	99.9	199.8	0.17	2.02	2663	5615	35	164	57	25	57
													1106	35	100	199.8	0.19	2.02	2703	5584	36	163	55	25	56
1126	35	100.2	199.8	0.19	2.05	2797	5672	37	165	54	26	55
													1145	35	100.1	199.8	0.22	1.99	2783	5551	37	158	48	24	54
1165	35	100.1	199.8	0.23	1.99	2813	5567	36	161	45	26	54
													1186	35	100.1	199.8	0.24	2.01	2835	5605	35	158	44	25	53
1205	35	100	199.8	0.25	2.01	2880	5592	36	162	45	25	53
													1225	35	100.2	199.8	0.25	2.00	2839	5535	35	158	43	24	52
1244	35	100.1	199.8	0.25	1.96	2809	5478	35	156	43	23	53
													1274	20	100.1	199.8	0.00	2.05	1740	4227	8	197	444	92	52
1296	20	100	199.8	0.00	2.07	1955	4675	16	208	439	86	48
													1317	20	100	199.8	0.00	2.05	1872	4701	12	172	439	92	48
1337	20	99.8	199.8	0.00	2.05	1688	4991	15	213	402	87	47
													1354	20	100.2	199.8	0.00	2.07	2005	4982	14	217	417	86	46
1374	20	100.3	199.8	0.00	2.10	2122	5160	19	219	418	72	46
													1444	20	99.9	199.8	0.00	2.09	2183	5228	21	220	369	93	44

Time (min)	Liquid feeding speed (ml/min)	Pressure (psig)	O 2Flow velocity (sccm)	GI (wt％)	Gly (wt％)	HCHO (ppm)	HCOOH (ppm)	NMG (ppm)	NFG (ppm)	AMPA (ppm)	MAMPA (ppm)	CO in the exhaust 2 ％
													1464	20	99.5	199.8	0.00	2.10	2127	5183	17	224	407	89	44
1484	35	100	199.8	0.22	2.05	2966	5982	50	184	69	30	47
													1504	35	100.1	199.8	0.28	1.95	2930	5759	37	163	38	28	49
1524	35	99.8	199.8	0.34	1.93	3041	5728	48	158	38	22	47
													1544	35	100	199.8	0.36	1.99	3003	5685	30	150	38	22	47
1564	35	99.4	199.8	0.15	2.15	2965	5668	34	162	63	27	57
													1584	35	100	199.8	0.26	2.00	3027	5687	45	167	46	27	52
1604	35	100.2	199.8	0.26	2.00	3020	5647	39	165	44	26	50
													1624	35	129.7	199.8	0.15	2.07	3116	5613	42	168	68	30	51
1644	35	130	199.8	0.14	2.07	3146	5571	41	169	70	30	51
													1664	35	130.1	199.8	0.16	2.06	3166	5599	41	168	63	30	50
1684	35	129.9	199.8	0.15	2.07	3199	5626	41	170	64	30	50
													1704	35	129.8	199.8	0.16	2.07	3179	5640	41	168	58	30	49
1724	35	130	199.8	0.17	2.06	3189	5674	40	165	58	27	48
													1744	35	129.8	199.8	0.19	2.02	3178	5669	41	164	54	28	48
1764	35	129.8	199.8	0.20	2.00	3179	5625	41	163	52	26	47
													1784	35	130	199.8	0.30	1.99	2839	5551	31	161	55	22	52
1804	35	130.2	199.8	0.20	2.01	2657	5350	30	159	68	31	56
													1824	35	130	199.8	0.10	2.14	2844	5516	31	177	100	38	56
1844	35	130	199.8	0.10	2.13	2822	5474	30	337	99	37	57
													1864	35	130	150	0.20	2.05	2711	5517	35	313	64	29	62

Time (min)	Liquid feeding speed (ml/min)	Pressure (psig)	O 2Flow velocity (sccm)	GI (wt％)	Gly (wt％)	HCHO (ppm)	HCOOH (ppm)	NMG (ppm)	NFG (ppm)	AMPA (ppm)	MAMPA (ppm)	CO in the exhaust 2 ％
													1884	35	129.9	150	0.23	2.08	2754	5580	30	314	42	23	65
1904	35	130.4	150	0.36	1.90	2561	5336	32	274	36	20	66
													1924	35	129.4	150	0.43	1.89	2691	5498	31	275	33	18	64
1944	35	130	150	0.22	2.09	2583	5419	40	314	77	31	73
													1964	35	130	150	0.28	1.99	2789	5505	35	294	42	22	68
1984	35	130.2	150	0.27	1.98	2885	5510	35	292	43	23	65
													2004	35	129.9	150	0.27	1.99	2926	5529	34	295	42	25	64
2024	35	130.1	150	0.24	2.02	2960	5525	37	301	44	27	63
													2044	35	130.2	150	0.25	2.04	2989	5607	35	313	44	25	62
2064	35	129.7	150	0.30	1.98	2995	5549	34	299	40	21	62
													2084	35	129.9	150	0.28	1.99	3033	5588	35	305	40	23	61
2104	20	130.4	200	0.18	2.10	2637	5240	25	307	229	62	54
													2124	20	130	200	0.00	2.12	2078	4637	13	283	634	93	48
2144	20	129.7	200	0.00	2.20	2171	4975	14	332	686	114	46
													2164	20	129.8	200	0.00	2.12	2299	5001	24	219	606	100	45
2184	20	129.7	200	0.00	2.13	2237	4955	20	230	692	110	46
													2204	20	130.1	200	0.00	2.14	2260	5044	19	238	695	123	46
2224	20	130.4	200	0.00	2.12	2319	5014	23	230	662	111	45
													2244	20	129.7	200	0.00	2.14	2386	5142	25	235	644	116	44
2264	20	129.9	200	0.00	2.12	2525	5172	34	231	516	124	42
													2284	20	130	150	0.00	2.19	2428	5249	24	244	595	116	49

Time (min)	Liquid feeding speed (ml/min)	Pressure (psig)	O 2Flow velocity (sccm)	GI (wt％)	Gly (wt％)	HCHO (ppm)	HCOOH (ppm)	NMG (ppm)	NFG (ppm)	AMPA (ppm)	MAMPA (ppm)	CO in the exhaust 2 ％
													2304	20	130.3	150	0.01	2.10	2396	5058	31	225	460	89	53
2324	20	129.8	150	0.03	1.89	2401	4766	40	182	285	72	52
													2344	20	129.7	150	0.01	2.15	2565	5195	37	231	377	84	51
2364	20	129.9	150	0.01	2.13	2490	5064	34	225	403	89	54
													2384	20	129.9	150	0.01	2.10	2382	4983	30	224	444	88	55
2404	20	129.7	150	0.01	2.17	2409	5063	26	228	450	84	54
													2424	20	129.7	150	0.01	2.18	2501	5178	30	234	418	83	54
2444	20	130.3	150	0.01	2.14	2668	5358	47	231	328	75	52

Embodiment 32:NPMIDA is oxidized to glyphosate continuously in the presence of the Pt/Fe/C catalyzer

Present embodiment understands that for example NPMIDA is oxidized to glyphosate continuously in the presence of the heterogeneous beaded catalyst of Pt/Fe/C in stirred-tank reactor.This experimental design is used for simulating and may accounts for leading condition at first reaction zone of continuous oxidation reaction device system.

Experiment with embodiment 29 in carry out in the used similar flow reactor system, wherein reactor comprises 1000mL Hastelloy C autoclave.Reactor is equipped with has 1.25 " agitator of radial six turbo wheels of diameter.Used similar level indicator is monitored among fluid level use in the reactor and the embodiment 21.Utilize inner cooling spiral to control the temperature in the reactor in the reaction process.

In operating process, continuous feed contains aqueous slurries raw material and the Oxygen Flow of NPMIDA in reactor.Oxygen is incorporated into reaction medium by near the glass filter that is arranged in the impeller.The liquid product stream that contains the glyphosate product is discharged from reactor continuously by glass filter, and this filter is retained in the reaction medium any catalyzer that is added to reactor.Product gas flow (is contained CO ₂With unreacted oxygen) discharge from the reactor head space continuously.

The aqueous slurries raw material that is given to reactor comprises NPMIDA (9.9wt%), glyphosate (1.3wt%), formaldehyde (3600 ppm by weight) and formic acid (6200 ppm by weight).Catalyzer by with described in the above embodiment 17 similarly method prepare, and comprise platinum (5wt%) and the iron (0.5wt%) that loads on the granulated carbon carrier.The flow reactor system is to come entry into service with similar mode described in the embodiment 21, and wherein reactor starts with intermittent mode, and shortly after that starting is through the liquid flow of system.Operational condition is summed up in following table 38.Product liquid is analyzed with HPLC.The analytical data of oxidation provides in following table 39 continuously.

Table 38

The summary of the operational condition of embodiment 32

Catalyst concn in the reactor:	1wt％
		Agitator RPM:	1000
Liquid flow rate:	35mL/min
		Pressure:	100psig
Oxygen gas flow rate:	630sccm
		Temperature:	100℃
The reactant quality:	725g
		Impeller-type:	Radial (1.25 ")

Table 39

The oxidation results of embodiment 32

Time (min)	NPMIDA (wt％)	Glyphosate (wt%)
			60	0.12	5.16
90	0.05	6.34
			151	0.03	3.64
181	0.32	6.06
			211	0.35	6.33
241	0.34	6.23
			271	0.27	6.06
301	0.32	6.22
			331	0.31	6.22
362	0.28	6.25
			392	0.29	6.08
422	0.30	6.22
			452	0.25	6.17
482	0.03	5.59
			512	0.01	4.03
542	0.04	4.42
			573	0.18	4.84
603	0.15	5.69
			633	0.23	5.85
663	0.32	6.37

Embodiment 33:NPMIDA is oxidized to glyphosate continuously in the presence of the Pt/Fe/C catalyzer

Present embodiment understands that for example NPMIDA is oxidized to glyphosate continuously in the presence of the heterogeneous beaded catalyst of Pt/Fe/C in stirred-tank reactor.This experimental design is used for simulating and may accounts for leading condition at second reaction zone of flow reactor system.

Experiment with embodiment 29 in carry out in the used similar flow reactor system, wherein reactor comprises 1000mL Hastelloy C autoclave.Reactor is equipped with has 1.25 " agitator of radial six turbo wheels of diameter.Used similar level indicator is monitored among fluid level use in the reactor and the embodiment 21.Utilize inner cooling spiral to control the temperature in the reactor in the reaction process.

In operating process, the aqueous slurries raw material and the Oxygen Flow that will contain NPMIDA are incorporated into reactor assembly continuously.Oxygen is incorporated into reaction medium by near the glass filter that is arranged in the impeller.The liquid product stream that contains the glyphosate product is discharged from reactor continuously by glass filter, and this filter is retained in the reaction medium any catalyzer that is added to reactor.Product gas flow (is contained CO ₂With unreacted oxygen) discharge from the reactor head space continuously.

The aqueous slurries raw material contains NPMIDA (1.9wt%), glyphosate (6.7wt%), formaldehyde (2400 ppm by weight), formic acid (4600 ppm by weight), NMG (280 ppm by weight), AMPA (400 ppm by weight) and MAMPA (200 ppm by weight).Catalyzer by with described in the above embodiment 17 similarly method prepare, and comprise platinum (5wt%) and the iron (0.5wt%) that loads on the granulated carbon carrier.The flow reactor system is to come entry into service with similar mode described in the embodiment 21, and wherein through starting with intermittent mode before the liquid flow of system, shortly after that start by this liquid flow in starting for reactor.Operational condition is summed up in following table 40.Product liquid is analyzed with HPLC.The analytical data of oxidation provides in following table 41 continuously.

Table 40

The summary of the operational condition of embodiment 33

Catalyst concn in the reactor:	1wt％
		Agitator RPM:	1000
Liquid flow rate:	60.4mL/min
		Pressure:	Variable (consulting data)
Oxygen gas flow rate:	Variable (consulting data)
		Temperature:	100℃
The reactant quality:	725g
		Impeller-type:	Radial (1.25 ")

Table 41

The oxidation results of embodiment 33

Time min	Pressure (psig)	?O 2Flow (sccm)	NPMIDA (wt％)	Glyphosate (wt%)	HCHO (ppm)	HCOOH (ppm)
							0	100	225	1.52	5.72	951	2822
60	100	225	0.48	7.55	1127	4404
							121	100	225	0.47	7.62	1219	4419
181	100	225	0.46	7.57	1272	4442
							241	100	225	0.45	7.63	1301	4434
302	100	225	0.45	7.74	1351	4590
							362	100	315	0.19	7.68	1467	4230
422	100	315	0.10	7.65	1518	3739
							482	100	315	0.10	7.77	1633	3756
543	100	315	0.10	7.77	1684	3714
							603	100	315	0.11	7.75	1671	3741
663	99	315	0.10	7.78	1724	3721
							724	100	292	0.13	7.75	1706	3840
784	100	292	0.13	7.84	1758	3905
							844	100	292	0.13	7.76	1748	3908
904	100	292	0.11	7.81	1608	3884
							965	100	292	0.11	7.75	1659	3901
1025	100	292	0.11	7.91	1703	3973
							1085	100	292	0.11	8.05	1819	4108
1145	100	270	0.15	7.82	1681	4120
							1206	100	270	0.14	7.74	1687	4438
1266	100	270	0.16	7.52	1850	4063
							1326	100	270	0.13	7.42	1754	3962
1748	100	247	0.64	6.77	1566	4025
							1809	100	247	0.65	7.70	1572	4266
1869	100	247	0.65	7.52	1545	4313
							1929	100	247	0.67	7.54	1612	4473
1989	100	247	0.63	7.50	1620	4436
							2050	100	247	0.59	7.59	1640	4500
2110	100	225	0.59	7.18	1562	4321
							2170	100	225	0.68	7.50	1639	4517
2261	100	225	0.66	7.60	1659	4551
							2351	100	225	0.59	7.41	1677	4519
2411	100	360	0.16	7.86	1907	4157
							2472	100	360	0.16	7.86	2039	4040
2532	100	360	0.10	7.89	2028	3664
							2592	100	360	0.09	7.98	2045	3635
2653	100	360	0.10	7.82	2150	3628
							2713	70	360	0.11	8.47	2036	4008
2773	71	360	0.08	7.55	1338	2920

Embodiment 34:NPMIDA is oxidized to glyphosate continuously in the presence of the Pt/Fe/C catalyzer

Present embodiment understands that for example NPMIDA is oxidized to glyphosate continuously in the presence of the heterogeneous beaded catalyst of Pt/Fe/C in fixed-bed reactor.This experimental design is used to simulate the little initial segment of fixed-bed reactor, and wherein gas and liquid starting material enter in the same way.

Experiment is carried out (2.2cm internal diameter in the flow reactor system that comprises vertical stainless steel tubular type reactor; 61.5cm length; The 215mL volume).Gas and liquid starting material enter tubular reactor and the reactor of flowing through downwards on top.The mixture of catalyst filling in reactor (50g) and glass Raschig ring (6mm).Catalyzer comprises 2wt% platinum and 0.2wt% iron on 1/8 inch carbon granule carrier.With the hot water raw material reactor is heated to about 90 ℃ and rise to the pressure of about 100psig with nitrogen.After reactor reaches 90 ℃ temperature, stop water and nitrogen gas stream, restart liquid starting material and oxygen feed.

Liquid starting material is given to the top of reactor under 90 ℃, comprise the aqueous slurries raw material that contains NPMIDA (3.00wt%) and formic acid (0.54wt%).Oxygen is given to the top of reactor, and wherein reactor pressure remains on 100psig.Liquid and oxygen delivery rate change in four experimentalists and technicians shown in the following table 42.In each experiment, allow system balancing half an hour at least, collect sample and analyze formic acid and glyphosate at column outlet afterwards.

Table 42

The effluent analysis under the different operating condition of embodiment 34

Liquid flow rate (ml/min)	Oxygen flow (sccm)	The % glyphosate	% formic acid	% formaldehyde
					100	100	0.11	0.47	～0.011
100	200	0.13	0.46	～0.014
					50	100	0.24	0.38	～0.018
25	100	0.41	0.33	～0.026

Embodiment 35:NPMIDA is oxidized to glyphosate continuously in having placed in-line two stirred-tank reactors of catalyst recycle and crystallizer recirculation

Present embodiment understands that for example NPMIDA in the flow reactor system that comprises two stirred-tank reactors of series connection fractionated, is oxidized to glyphosate continuously in the presence of heterogeneous beaded catalyst slurry.Reactor assembly is similar to the reactor assembly shown in Figure 30.Two stirred-tank reactors (R1 and R2) are as described in the embodiment 24, and just the impeller configuration of R2 is not operated with the DISPERSIMAX pattern.Use comprises the back-flushing filter system of filters in parallel body, flows out continuous filtration catalyzer the thing from the reaction mixture of being discharged by R2, more isolating catalyst recirculation is arrived R1.In crystallizer (30L), from filtrate, reclaim crystalline N-((phosphonomethyl)) glycine product, will arrive R1 from the Recycling Mother Solution of crystallizer again.

By with described in the above embodiment 17 similarly method prepare heterogeneous beaded catalyst, and comprise platinum (5wt%) and the iron (0.5wt%) that loads on the granulated carbon carrier.In this embodiment, the particle heterogeneous catalyst is transferred to R2 from R1, comprise the gas that some are carried secretly from the effluent of R1.The catalyzer that leaves R2 with reactor effluent separates in back-flushing filter, and is recycled to R1.The recoil catalyst filter also is used as the liquid-gas separator from the effluent of R2.To be transported to crystallizer from the filtrate of recoil catalyst filter, be used to reclaim crystalline N-((phosphonomethyl)) glycine product.From crystallizer mother liquid obtained be used to recoil the catalyst filter body and with isolating catalyst recycle to R1.

The operational condition of R1 and R2 is summarised in the table 43.R1 and R2 are reinforced at first as shown in table 43, and oxygen and NPMIDA raw material are introduced simultaneously.The NPMIDA raw material comprises and contains about 12.5% to the aqueous slurries raw material of about 15%NPMIDA with from the recirculation mother liquor of catalyst filter, and acquisition is given to effective total raw material of R1.At first introduce the effective total raw material that is given to R1, be increased to 5.2wt% later on 4.3wt%.In whole test, add bismuth oxide, destroy speed to increase formic acid.Bismuth oxide joins R1 (the each interpolation～5mg) and by joining in the NPMIDA slurry raw material (4-25mg/20kg NPMIDA slurry) add in a continuous manner with intermittent mode.Frequency and amount that bismuth oxide adds in the slurry raw material are listed in the table 44.Analyze the aqueous slurries raw material (comprising) that is given to R1, R1 reactor effluent and R2 reactor effluent by HPLC from the component in the crystallizer mother liquor of catalyzer recirculation.The HPLC analytical results provides in table 45.

Table 43

The operational condition of the continuous oxidation reaction device system of embodiment 35

Initial reactor is reinforced	R1	R2
			Catalyzer	0.8wt％	0.8wt％
NPMIDA	0.8wt％	0.3wt％
			Glyphosate	5.0wt％	5.0wt％
Formaldehyde	500ppm	500ppm
			Formic acid	2000ppm	2000ppm
Water	2700ml	1500ml
			Operational condition
Catalyst concn 1	0.8-1.4wt％	0.8-1.4wt％
			Agitator RPM	1000	600
Be given to total liquid flow rate of R1	147.4g/min	147.4g/min
			Pressure	100psig	100psig
Oxygen	900-1700sccm	120-700sccm
			Temperature	95℃-100℃	95℃-100℃
The reactant quality	2950g	1725g
			Impeller-type	Radial (2 ") 2	Radial (2 ") 2
The NPMIDA slurry flow rate	50g/min	NA
			The RML flow velocity 3	97.4ml/min	NA

1, primary catalyst is reinforced is 0.8wt%.In operational process, catalyst loading was increased to 1.0wt% at 69 hours, was increased to 1.2wt% at 119 hours and was increased to 1.4wt% at 143 hours.

2, downward pumping impeller is installed on the stirrer shaft at the about half way place that makes progress along fluid column.

3, crystallizer mother liquor (RML) be used for recoiling catalyst filter and filtering catalyzer turned back to R1 with RML.

Table 44

Be added to the frequency and the amount of the bismuth oxide of reactor assembly

Elapsed time (hr)	Bismuth oxide adds
		19.4	L2.5mg and 50mL H 2O is added to R1 together
19.6	4.2mg be added in the 20kg NPMIDA slurry raw material
		46.2	12.7mg with 50ml H 2O is added among the R1 together
102.3	12.8mg with 50ml H 2O is added to together that 4.7mg is added in the 20kg NPMIDA slurry raw material among the R1
		139.3	12.4mg with 50ml H 2O is added to together that 4.1mg is added in the 20kg NPMIDA slurry raw material among the R1
159.3	13.3mg with 50ml H 2O is added to together that 4.0mg is added in the 20kg NPMIDA slurry raw material among the R1
		165.7	16.4mg with 50ml H 2O is added to together that 16.9mg is added in the 20kg NPMIDA slurry raw material among the R1
172.0	25mg is added in the 20kg NPMIDA slurry raw material
		215.9	12.3mg be added in the 20kg NPMIDA slurry raw material
370.7	16.7mg be added in the 20kg NPMIDA slurry raw material

The analytical results of table 45 embodiment 35

Elapsed time (hr)	Effectively total R1 raw material				The R1 discharge				The R2 discharge
													NPMIDA (wt％)	Gly (wt％)	HCHO ?(ppm)	HCOOH (ppm)	NPMIDA (wt％)	Gly (wt％)	HCHO (ppm)	HCOOH (ppm)	NPMIDA (wt％)	Gly (wt％)	HCHO (ppm)	HCOOH (ppm)
	9.0 12.1 16.9 18.0 20.5 22.0 27.0 30.0 30.7 34.5 36.0 39.0 46.0 47.3 48.3 50.7 56.5 59.0 62.1 65.0 69.5 71.5	4.4 4.31 4.30 4.30 4.33 4.34 4.31 4.32 4.31 4.27 4.29 4.30 4.36 4.42 4.39 4.44 4.35 4.37 4.32 4.29 5.18 5.20	1.07 1.08 1.12 1.03 1.03 1.13 2.27 2.54 2.57 2.43 2.42 2.44 2.55 2.46 2.44 2.76 2.59 2.51 2.51 2.54 2.53 2.65	417 408 497 492 480 494 269 310 311 406 432 459 483 429 405 552 518 591 649 704 577 600	1775 1857 2179 2179 1853 2082 1368 1491 1646 1882 1887 1969 2176 1677 1864 2225 1827 2165 2284 2213 1805 1898	0.62 0.36 0.32 0.34 0.57 0.52 0.45 0.48 0.44 0.12 0.18 0.19 0.52 0.74 0.64 0.45 0.09 0.15 0.22 0.17 0.21 0.35	3.86 3.88 4.10 4.04 4.35 4.20 4.62 5.31 5.34 5.51 5.37 5.67 5.65 5.88 5.44 5.50 5.35 5.21 5.18 5.22 5.42 5.74	841 927 984 951 1010 943 1035 1196 1178 1282 1332 1049 1660 1567 1382 1505 1566 1700 1760 1890 1402 1574	3058 3446 3507 3664 2941 2790 3147 3331 3369 3156 3299 3704 4224 3528 2809 3417 2807 3368 3495 3634 2211 2468	0.54 0.24 0.18 0.19 0.29 0.32 0.23 0.26 0.21 0.09 0.14 0.19 0.41 0.62 0.54 0.26 0.00 0.06 0.10 0.06 0.19 0.22	3.96 3.98 4.13 3.80 3.81 4.18 4.53 5.54 5.61 5.41 5.40 5.45 5.88 5.55 5.47 5.61 5.64 5.32 5.36 5.42 5.38 5.88	449 417 418 401 354 406 445 596 567 824 920 1017 1106 909 819 805 724 993 1087 1178 710 881													3147 3448 3416 3414 2213 3058 2911 3364 3347 3364 3381 3684 4447 2608 3297 3245 2113 3359 3520 3718 2215 2735
75.0 77.5 80.8													5.27 5.25 5.25	2.74 2.74 2.63	612 612 616	2134 1828 1802	0.56 0.44 0.46	5.08 5.84 5.75	1577 1666 1717	3240 3256 3406	0.40 0.27 0.26	6.06 6.06 5.90	958 952 961	3704 2503 2436

Elapsed time (hr)	Effectively total R1 raw material				The R1 discharge				The R2 discharge
													NPMIDA (wt％)	Gly (wt％)	HCHO (ppm)	HCOOH (ppm)	NPMIDA (wt％)	Gly (wt％)	HCHO (ppm)	HCOOH (ppm)	NPMIDA (wt％)	Gly (wt％)	HCHO (ppm)	HCOOH (ppm)
	84.0 87.0 91.0 93.0 97.7 105.0 107.0 109.0 111.0 116.0 129.5 134.0 135.5 140.3 142.0 144.6 152.5 153.5 156.5 158.3 160.5	5.27 5.27 5.26 5.26 5.24 5.23 5.24 5.24 5.24 5.19 5.27 5.27 5.41 5.23 5.21 5.20 5.23 5.19 5.19 5.19 5.24	2.85 2.63 2.47 2.74 2.69 2.61 2.64 2.63 2.59 2.68 2.66 2.58 2.65 2.84 2.78 2.84 2.62 2.63 2.72 2.61 2.71	663 656 687 752 898 968 1001 1031 1031 1213 1328 1332 1310 1268 1248 849 1026 1046 1135 1168 1150	2114 2004 1933 2122 2684 2210 2388 2242 2242 2620 3239 2880 2872 3477 3364 3154 3065 2580 2962 2920 2696	0.50 0.46 0.45 0.45 0.45 0.42 0.48 0.52 0.52 0.46 0.70 0.76 1.14 0.52 0.39 0.25 0.34 0.37 0.46 0.48 0.63	5.84 5.92 6.03 6.10 5.94 5.79 5.77 5.80 5.80 6.02 5.91 5.72 5.62 6.34 6.07 6.29 5.67 5.67 5.84 5.85 5.86	1680 1735 1924 1967 2248 2195 2265 2255 2255 2634 2952 3014 2848 3494 3429 1751 2330 2317 2729 2747 2750	3328 3288 3173 3706 4651 3791 3935 3697 3697 4379 6163 5731 4719 5613 5113 4150 3998 4048 5120 5363 5035	0.31 0.29 0.23 0.23 0.19 0.21 0.24 0.26 0.26 0.14 0.42 0.43 0.96 0.15 0.09 0.03 0.16 0.14 0.16 0.14 0.32	6.47 5.56 5.37 6.37 6.20 6.11 5.95 6.16 6.03 6.15 6.05 5.78 6.02 6.53 6.30 6.52 5.70 5.75 6.07 5.66 6.06	1089 979 1012 1251 1569 1478 1558 1629 1629 1976 2400 2415 2336 2604 2529 1058 1711 1724 2011 2132 2066													3437 2897 2906 3605 4428 3276 3403 3480 3480 4163 6449 5125 5095 5308 4891 4117 3788 3726 5137 4980 4156
161.5 163.5 167.1 170.0 173.0 176.3													5.19 5.18 5.22 5.14 5.12 5.15	2.78 2.89 2.73 2.77 2.64 2.68	1135 1192 1261 1431 1484 1528	2729 3068 3250 3625 3346 3489	0.51 0.54 0.67 0.45 0.28 0.56	6.09 6.13 5.50 5.93 5.27 5.50	2670 2844 2659 3133 3099 3175	4389 5696 5220 5555 4459 5094	0.15 0.10 0.28 0.03 0.01 0.12	6.32 6.73 6.14 6.45 5.73 5.95	2010 2219 2476 2474 2564 2649	4277 5528 6197 5485 4327 5136

Elapsed time (hr)	Effectively total R1 raw material				The R1 discharge				The R2 discharge
													NPMIDA (wt％)	Gly (wt％)	HCHO (ppm)	HCOOH (ppm)	NPMIDA (wt％)	Gly (wt％)	HCHO (ppm)	HCOOH (ppm)	NPMIDA (wt％)	Gly (wt％)	HCHO (ppm)	HCOOH (ppm)
	179.8 183.5 188.0 189.5 190.5 196.0 199.0 201.5 203.5 205.5 207.5 209.5 211.5 219.5 221.5 223.5 225.5 227.5	5.15 5.17 5.15 5.14 5.14 5.14 5.14 5.14 5.13 5.14 5.13 5.14 5.14 5.14 5.14 5.15 5.16 5.15	2.74 2.73 2.64 2.60 2.62 2.60 2.62 2.70 2.65 2.63 2.90 2.77 2.69 2.64 2.91 2.64 2.71 2.79	1280 1306 1244 1624 1601 1624 1601 1559 1525 1517 1448 1492 1453 1287 1273 1272 1262 1254	3225 3247 3043 2184 1858 2184 1858 1600 1522 1439 1130 1010 932 585 538 530 489 473	0.55 0.74 0.54 0.37 0.38 0.37 0.38 0.28 0.29 0.30 0.23 0.28 0.27 0.28 0.37 0.35 0.42 0.39	5.78 5.93 5.61 5.97 5.99 5.97 5.99 5.74 6.01 5.95 5.95 6.10 5.64 5.81 5.86 5.95 5.98 5.78	3222 3308 3143 3165 3109 3165 3109 2889 3001 2871 2819 2929 2774 2554 2605 2558 2573 2500	4716 4556 3924 3278 3059 3278 3059 2528 2260 2104 1786 1839 1736 1234 1227 1146 1144 1122	0.11 0.19 0.14 0.09 0.09 0.09 0.09 0.08 0.07 0.10 0.06 0.10 0.10 0.07 0.10 0.09 0.12 0.10	6.16 6.13 5.78 6.12 6.03 6.12 6.03 6.24 6.11 6.05 6.15 6.34 6.05 6.02 6.03 5.97 6.12 6.40	2587 2684 2455 2481 2417 2481 2417 2305 2241 2210 2065 2224 2082 1858 1860 1846 1869 1841													4164 4245 3491 3057 2358 3057 2358 2110 1898 1590 1319 1275 986 819 748 751 688 629
229.5 231.5 233.5 242.5 244.0 245.5 248.0 249.3 250.3													5.12 5.15 5.16 5.16 5.16 5.20 5.14 5.16 5.17	2.58 2.82 2.81 2.64 2.50 2.82 2.81 2.81 2.79	1222 1222 1214 1131 1105 1186 1150 1165 1162	165 429 425 326 313 314 303 304 303	0.36 0.39 0.40 0.51 0.56 0.71 0.48 0.45 0.52	5.95 6.09 6.05 5.91 5.98 6.07 5.95 5.74 6.10	2505 2550 2514 2372 2416 2441 2458 2310 2409	1028 948 902 867 791 791 746 699 787	0.08 0.11 0.12 0.09 0.11 0.25 0.03 0.10 0.13	5.70 6.36 6.32 5.85 5.36 6.43 6.41 6.41 6.34	1806 1844 1816 1597 1499 1796 1660 1717 1707	608 595 581 495 450 469 432 432 429

Elapsed time (hr)	Effectively total R1 raw material				The R1 discharge				The R2 discharge
													NPMIDA (wt％)	Gly (wt％)	HCHO (ppm)	HCOOH (ppm)	NPMIDA (wt％)	Gly (wt％)	HCHO (ppm)	HCOOH (ppm)	NPMIDA (wt％)	Gly (wt％)	HCHO (ppm)	HCOOH (ppm)
	251.5 256.0 258.0 260.0 262.0 267.0 270.0 271.0 273.2 273.8 275.5 277.0 278.2 281.5 284.5	5.18 5.16 5.17 5.16 5.15 5.30 5.25 5.20 5.21 5.21 5.21 5.18 5.19 5.20 5.19	2.75 2.88 2.87 2.83 2.79 2.70 2.84 2.87 2.87 2.83 2.90 2.87 2.89 2.79 2.71	1150 1101 1108 1093 1091 1062 1080 1069 1071 1076 1107 1100 1163 1186 1162	287 254 310 300 249 213 222 224 247 231 237 270 240 281 244	0.58 0.60 0.81 0.73 0.71 1.33 1.12 0.95 0.90 0.90 0.93 0.91 0.94 0.92 0.87	5.72 5.66 5.91 5.78 5.77 5.29 5.88 5.91 5.93 5.82 5.68 6.28 5.95 6.08 6.04	2250 2166 2239 2234 2270 2049 2226 2243 2207 2235 2167 2240 2339 2505 2630	701 625 651 612 640 531 587 685 586 640 596 590 632 729 708	0.16 0.03 0.11 0.06 0.07 0.55 0.35 0.19 0.20 0.23 0.20 0.12 0.11 0.12 0.07	6.17 6.43 6.50 6.35 6.41 6.00 6.51 6.60 6.61 6.48 6.72 6.61 6.76 6.39 6.09	1663 1619 1693 1638 1674 1645 1710 1669 1675 1696 1809 1785 1852 1936 1847													370 391 429 394 395 315 349 358 440 383 406 527 422 571 437
287.5 292.5 301.0 335.5 339.8 344.0 347.5 351.5 353.8 357.5 359.5 368.0													5.19 5.13 5.27 5.50 5.10 5.11 5.12 5.12 5.11 5.16 5.13 5.15	2.69 2.64 2.65 1.14 1.34 1.41 1.44 1.42 1.44 2.94 2.83 2.70	1179 1177 979 191 226 235 285 297 314 807 789 881	269 241 166 82 74 38 68 69 75 216 192 201	0.84 0.20 0.92 1.85 0.15 0.48 0.33 0.28 0.30 0.44 0.29 0.34	6.02 5.87 5.30 3.64 4.84 5.25 4.96 5.18 5.11 6.34 6.27 5.96	2693 2679 1839 1200 1654 1824 1867 2003 2115 2417 2553 2792	745 653 406 505 518 480 528 474 753 757 943 694	0.07 0.07 0.45 1.48 0.01 0.04 0.09 0.07 0.05 0.16 0.04 0.13	6.03 5.96 5.86 4.21 4.92 5.20 5.30 5.24 5.29 6.74 6.34 5.85	1908 1718 1259 703 833 868 1050 1096 1157 1558 1490 1831	529 378 200 302 273 142 252 255 276 364 278 309

Elapsed time (hr)	Effectively total R1 raw material				The R1 discharge				The R2 discharge
													NPMIDA (wt％)	Gly (wt％)	HCHO (ppm)	HCOOH (ppm)	NPMIDA (wt％)	Gly (wt％)	HCHO (ppm)	HCOOH (ppm)	NPMIDA (wt％)	Gly (wt％)	HCHO (ppm)	HCOOH (ppm)
	370.5 373.5 375.0 378.3 380.5 383.5 387.5 389.5 391.0 392.0 395.0 398.0	5.14 5.17 5.17 5.14 5.14 5.34 5.20 5.22 5.28 5.26 5.19 5.16	2.91 2.95 2.78 2.76 2.79 2.87 2.86 2.82 2.91 2.91 2.83 2.76	894 986 1425 1437 1425 1853 1868 1953 2002 2061 2101 2153	227 224 270 238 226 272 275 308 334 286 324 344	0.34 0.51 0.43 0.32 0.21 0.95 0.25 0.53 0.72 0.59 0.31 0.34	6.65 6.49 6.46 6.05 6.13 6.57 6.09 5.89 6.05 6.41 6.19 6.17	2897 3084 3131 3273 3229 3829 3652 3833 4118 4047 4022 4219	950 542 976 940 1021 1031 842 1370 1358 1336 1036 1519	0.09 0.19 0.12 0.03 0.00 0.59 0.07 0.22 0.42 0.32 0.10 0.09	6.64 6.77 6.44 6.34 6.48 6.55 6.55 6.43 6.74 6.73 6.62 6.47	1877 2216 2291 2334 2290 3052 2787 3115 3295 3273 3221 3353													406 394 563 444 402 397 476 476 574 485 582 649
399.5 401.5 405.0 407.0 409.6 412.0 413.5 416.5													5.16 5.15 5.21 5.20 5.20 5.14 5.15 5.13	2.78 2.78 2.88 2.87 2.70 2.66 2.67 2.68	2184 2265 2383 2409 2493 2438 2497 2553	396 494 563 635 708 723 747 985	0.33 0.38 0.65 0.61 0.53 0.27 0.36 0.39	6.13 6.19 6.21 6.30 6.40 5.66 5.71 5.78	4262 4323 4337 4492 4498 4230 4355 4371	1286 1570 1470 1922 1926 1874 2236 2351	0.07 0.09 0.27 0.25 0.17 0.02 0.07 0.06	6.53 6.37 6.63 6.58 5.84 6.04 6.09 6.17	3466 3609 3731 3830 3854 3601 3819 3911	840 1005 937 1202 1360 1387 1477 1804

Embodiment 36:NPMIDA is oxidized to glyphosate continuously in having placed in-line two stirred-tank reactors of catalyst recycle and crystallizer recirculation

Present embodiment understands that for example in the flow reactor system that comprises two stirred-tank reactors of series connection fractionated that utilize heterogeneous beaded catalyst slurry, NPMIDA is oxidized to N-((phosphonomethyl)) glycine continuously.Reactor assembly shown in reactor assembly and Figure 31 is similar.Two stirred-tank reactors (R1 and R2) are as described in the above embodiment 35.Use comprises the back-flushing filter system of filters in parallel body, flows out thing continuous filtration catalyzer from the reaction mixture of being discharged by R2, more isolating catalyst recycle is arrived R1.In crystallizer (30L), reclaim crystalline N-((phosphonomethyl)) glycine product, will be recycled to R1 from the mother liquor of crystallizer again from filtrate.In addition, a part of crystallizer mother liquor is joined in the effluent from R2 as effluent dilution logistics (75-100mL/min),, thereby reduce possible crystallisation problems so that reduce glyphosate concentration in the R2 effluent that is incorporated into back-flushing filter.Also have, reactive system also comprises catalyzer and deposits jar (having the upwards 500mL Hastelloy C autoclave of pumping impeller), and it is collected and is reintroduced to R1 isolating catalyzer before.Catalyzer is deposited jar and is operated under the situation that does not have level control, and catalyst slurry can be discharged from the top of container.

Heterogeneous beaded catalyst prepares by being similar to the method described in the above embodiment 17, and comprises platinum (5wt%) and the iron (0.5wt%) that loads on the granulated carbon carrier.In the present embodiment, the particle heterogeneous catalyst is transferred to R2 from R1, comprises the gas that some are carried secretly from the effluent of R1.The catalyzer that leaves R2 with reactor effluent separates in back-flushing filter, and delivers to catalyzer and deposit jar and be recycled to R1.The recoil catalyst filter also is used as the liquid-gas separator of R2 effluent.Filtrate from the recoil catalyst filter is sent to crystallizer, is used to reclaim crystalline N-((phosphonomethyl)) glycine product.From the mother liquid obtained catalyst filter body that is used to recoil of crystallizer,, and be recycled to R1 with isolating catalyzer as the diluent of the R2 effluent that feeds the catalyst filter body.

The operational condition of R1 and R2 is summed up in table 46.At first R1 and R2 are reinforced as shown in table 46, and oxygen and NPMIDA raw material are introduced simultaneously.The NPMIDA raw material comprises and contains about 20 to the aqueous slurries raw material of about 20.5%NPMIDA with from the recirculation mother liquor of catalyst filter, obtains being given to effective total raw material of R1.7.7wt% is at first introduced and be increased to afterwards to the effective total raw material that is given to R1 with 7wt%.In whole service, add bismuth oxide, destroy speed to increase formic acid.Bismuth oxide adds in a continuous manner by joining in the NPMIDA slurry raw material (3-12mg/20kg NPMIDA slurry).Bismuth oxide adds the frequency and the amount of slurry raw material to and lists in the table 47.Analyze the aqueous slurries raw material (comprising) that is given to R1, R1 reactor effluent and R2 reactor effluent by HPLC from the component in the crystallizer mother liquor of catalyzer recirculation.The HPLC analytical results provides in table 48.

Table 46

The operational condition of embodiment 36

Initial reactor is reinforced	R1	R2
			Catalyzer	1.6wt％	1.6wt％
Water	2400ml	2400ml
			Operational condition
Catalyst concn 1	1.6-2.2wt％	1.6-2.2wt％
			Agitator RPM	1000	1000
Be given to total liquid flow rate of R1	147.4g/min	147.4g/min
			Pressure	100psig	100psig
Oxygen	1200-2750sccm	350-1200sccm
			Temperature
	105℃-110℃	105℃-110℃
			The reactant quality	2950g	2950g
Impeller-type	Radial (2 ") 2	Radial (2 ") 2
			The NPMIDA slurry flow rate	50g/min	NA
The RML flow velocity 3	97.4ml/min	NA

1, primary catalyst is reinforced is 1.6wt%.In operational process, catalyst loading was increased to 1.7wt% at 344 hours, be increased to 1.8wt% at 354 hours, was increased to 1.9wt% at 356 hours, be increased to 2.0wt% at 359 hours, be increased to 2.1wt% at 363 hours and be increased to 2.2wt% at 366 hours.

2, downward pumping impeller is installed on the stirrer shaft at the about half way place that makes progress along fluid column.

3, use recoil catalyst filter and filtering catalyzer turned back to R1 with RML of crystallizer mother liquor (RML).

Table 47

Bismuth oxide is added to frequency and the amount in the NPMIDA slurry raw material

Elapsed time (hr)	Bismuth oxide addition (being added in the 20kg NPMIDA slurry raw material)
		9.8	3mg
20.5	6mg
		34.3	9mg
44.0	18mg
		89.4	12mg
98.0	3mg
		204.9	6mg
225.1	3mg
		274.3	12mg

The analytical results of table 48 embodiment 36

Elapsed time (hr)	Effectively total R1 raw material				The R1 discharge				The R2 discharge
													NPMIDA (wt％)	Gly (wt％)	HCHO (ppm)	HCOOH (ppm)	NPMIDA (wt％)	Gly (wt％)	HCHO (ppm)	HCOOH (ppm)	NPMIDA (wt％)	Gly (wt％)	HCHO (ppm)	HCOOH (ppm)
	2.2 5.5 8.5 11.5 14.5 17.5 20.5 23.5 26.5 28.0 30.0 31.0 33.0 35.0 36.5 37.5 40.0 43.0 44.8 46.3 48.0 51.0	8.03 6.85 6.86 6.85 6.84 7.01 7.12 7.13 7.01 6.99 7.00 6.92 6.89 6.87 6.87 6.87 7.73 7.75 7.75 7.77 7.79 7.84	1.84 1.71 2.55 2.85 2.28 2.67 2.72 2.87 3.00 2.93 2.96 2.80 2.76 2.75 2.66 2.78 2.72 2.87 2.86 2.79 2.89 3.69	185 53 71 97 95 146 188 213 201 193 204 215 217 226 270 299 423 419 726 761 768 1033	1338 515 742 1044 1079 1441 1746 2115 1854 1827 1941 1888 1721 1888 1885 2138 2844 3330 3316 3106 3357 4607	3.50 1.00 1.10 1.01 0.64 1.44 1.60 1.30 1.06 1.04 1.01 1.31 1.09 0.99 0.94 0.88 1.35 1.45 1.28 1.72 1.44 1.22	4.47 6.14 6.33 7.05 6.89 6.38 6.22 6.82 7.39 6.79 6.88 6.81 6.45 6.78 6.67 6.92 6.84 6.78 6.69 6.99 7.00 7.16	682 712 743 842 817 849 837 892 904 951 973 1022 975 1198 1422 1617 1867 1871 2207 2216 2309 2348	3378 3816 3742 4090 3927 4142 4323 4732 4871 4147 4621 6357 4210 4748 4872 5403 6272 6615 6247 6140 6196 5807	3.03 0.20 0.22 0.17 0.12 0.74 0.70 0.49 0.13 0.06 0.10 0.18 0.13 0.06 0.05 0.05 0.21 0.20 0.19 0.29 0.35 0.16	4.54 6.88 6.84 7.56 7.48 7.06 6.86 7.43 7.67 7.38 7.50 7.57 7.36 7.50 7.10 7.62 6.99 7.57 7.50 7.20 7.64 7.92	456 215 230 247 216 399 388 385 298 267 311 385 345 392 576 694 727 696 1262 1405 1437 1379													3303 2073 2564 2609 2398 3494 3458 3674 2414 2303 2779 3050 2629 2761 2747 3804 5318 5672 5180 4303 5353 4709
53.0 54.8 56.0													7.83 7.94 7.90	3.64 3.46 3.00	1002 1066 933	4423 4513 3216	1.29 1.94 2.04	6.66 8.07 6.92	2323 2234 2304	5481 5273 5384	0.09 0.57 0.57	7.70 7.24 7.84	1249 1497 1557	3940 3870 4666

Elapsed time (hr)	Effectively total R1 raw material				The R1 discharge				The R2 discharge
													NPMIDA (wt％)	Gly (wt％)	HCHO (ppm)	HCOOH (ppm)	NPMIDA (wt％)	Gly (wt％)	HCHO (ppm)	HCOOH (ppm)	NPMIDA (wt％)	Gly (wt％)	HCHO (ppm)	HCOOH (ppm)
	57.0 58.5 60.5 62.5 64.0 65.5 67.0 68.0 69.0 71.0 73.3 75.5 77.8 79.5 81.0 82.5 84.0 86.8 88.5 90.0 91.5	7.85 7.86 7.85 7.81 7.82 7.87 7.78 7.79 7.81 7.74 7.75 7.75 7.73 7.71 7.72 7.73 7.73 7.73 7.72 7.75 7.75	2.89 3.14 3.40 3.05 3.02 3.22 2.75 2.96 3.00 3.10 3.14 3.14 3.12 3.17 3.01 3.17 3.07 3.11 3.27 3.48 3.08	915 941 940 923 934 986 866 910 920 890 906 953 933 940 937 997 1003 1010 1092 1109 1159	2927 3065 3010 2729 2564 2829 2291 2616 2476 1969 1988 1960 1994 1725 1558 1709 1546 1509 1500 1518 1529	1.60 1.81 1.35 1.34 1.69 1.63 0.51 0.99 1.16 1.18 1.46 1.53 1.21 1.29 1.41 1.46 1.49 1.57 1.46 2.04 1.91	7.19 7.14 7.30 7.34 8.50 7.69 6.94 7.33 6.93 7.18 7.73 7.15 7.28 7.16 7.95 7.07 7.89 8.16 7.44 7.73 7.44	2307 2357 2399 2448 2420 2364 2377 2498 2543 2528 2547 2398 2424 2448 2438 2445 2459 2497 2608 2696 2671	5030 5248 4871 4730 4719 4381 3248 3884 3938 3862 4093 3595 3353 3237 2738 3090 2579 2442 2896 2969 2935	0.36 0.34 0.30 0.16 0.20 0.42 0.02 0.09 0.15 0.12 0.18 0.17 0.08 0.07 0.10 0.13 0.15 0.11 0.09 0.21 0.20	7.34 8.04 9.24 8.00 7.87 8.80 6.64 7.58 7.78 8.12 8.31 8.29 8.23 7.96 7.23 8.12 7.67 7.84 8.57 9.50 7.86	1473 1470 1468 1349 1401 1642 1085 1289 1334 1415 1493 1534 1441 1436 1421 1590 1616 1648 1739 1818 1907													3327 4184 3927 3329 2564 3791 1293 2801 2151 2796 2881 2773 2932 2264 1490 2294 1536 1364 2048 2129 2219
93.0 94.5 98.5 100.0 101.5 104.5													7.74 7.73 7.66 7.65 7.65 7.65	3.23 3.71 1.67 1.54 1.54 1.45	1152 1192 264 160 146 122	1340 1425 233 166 153 151	1.74 1.56 1.28 1.02 0.97 0.71	8.07 7.77 6.26 6.42 6.58 6.01	2971 3039 2256 1807 1718 1591	2964 2883 1985 1496 1927 1739	0.14 0.10 0.05 0.02 0.01 0.02	8.54 9.01 7.73 7.16 7.13 6.73	1874 1893 1227 742 678 566	1342 1899 1082 769 709 699

Elapsed time (hr)	Effectively total R1 raw material				The R1 discharge				The R2 discharge
													NPMIDA (wt％)	Gly (wt％)	HCHO (ppm)	HCOOH (ppm)	NPMIDA (wt％)	Gly (wt％)	HCHO (ppm)	HCOOH (ppm)	NPMIDA (wt％)	Gly (wt％)	HCHO (ppm)	HCOOH (ppm)
	107.5 111.5 113.0 114.2 115.5 118.5 121.5 124.5 127.5 133.5 136.5 139.5 142.5 145.5 149.0 152.0 155.0 158.5	7.68 7.75 7.75 7.84 7.75 7.77 7.79 7.73 7.82 7.71 7.70 7.77 7.88 7.77 7.72 7.71 7.72 7.71	1.42 1.54 2.70 3.10 3.23 3.25 3.48 3.09 3.61 3.22 3.40 3.55 3.50 3.60 3.52 3.34 3.62 3.98	118 130 190 237 305 288 555 507 719 835 906 1124 1045 1055 1100 1138 1165 1195	175 196 164 310 349 243 756 677 1064 1021 1090 1181 1064 1194 1359 1302 1354 1164	1.10 1.39 1.23 1.98 1.15 1.50 1.56 1.46 1.57 1.53 1.29 1.48 1.68 1.53 1.32 1.25 1.79 1.35	5.71 6.20 5.67 7.39 7.32 7.49 7.82 8.01 7.64 7.75 7.78 6.26 7.72 8.07 7.62 7.62 8.32 8.02	1439 1429 1337 1605 1662 1701 2111 2239 2283 2507 2634 2718 2733 2836 2949 3032 2989 3162	1698 1854 1717 2358 2044 1973 2604 2757 2755 2738 2961 1929 2985 2997 2913 2408 3128 2902	0.14 0.46 0.08 0.48 0.07 0.21 0.28 0.16 0.49 0.11 0.09 0.36 0.54 0.07 0.06 0.11 0.19 0.10	6.59 7.15 6.71 8.55 8.32 8.99 8.81 9.04 8.99 8.55 8.72 8.74 8.75 9.05 8.81 8.79 9.16 8.92	549 603 520 740 694 750 1093 1122 1249 1400 1494 2267 1690 1655 1773 1811 1864 1933													811 909 479 1156 833 647 1395 1404 1530 1583 1626 2129 1569 1557 1666 1602 1584 1641
161.5 164.5 167.5 172.0 175.0 178.0 181.0 184.0 186.5													7.70 7.73 7.71 7.74 7.72 7.69 7.69 7.70 7.78	3.47 3.13 3.38 2.93 3.07 2.91 2.91 3.01 2.81	1276 1324 1311 1427 1480 1474 1505 1525 1802	1193 1059 918 1173 1050 1159 1044 1058 2335	1.34 1.40 1.47 1.44 1.48 1.39 1.42 1.39 2.69	7.75 7.82 7.99 7.50 7.51 6.89 7.79 7.41 6.32	3174 3264 3378 3428 3555 3347 3573 3572 3714	3005 2969 3102 2731 2653 2254 2669 2670 6849	0.12 0.13 0.12 0.14 0.10 0.09 0.10 0.11 0.51	8.89 7.42 8.61 8.31 8.57 8.48 8.43 8.81 7.87	2071 2135 2089 2223 2314 2319 2322 2268 3550	1691 1263 1528 1511 1479 1506 1452 1499 7428

Elapsed time (hr)	EfEffectively total R1 raw material				The R1 discharge				The R2 discharge
													NPMIDA (wt％)	Gly (wt％)	HCHO (ppm)	HCOOH (ppm)	NPMIDA (wt％)	Gly (wt％)	HCHO (ppm)	HCOOH (ppm)	NPMIDA (wt％)	Gly (wt％)	HCHO (ppm)	HCOOH (ppm)
	188.3 203.5 205.8 209.5 212.0 213.5 215.0 216.5 218.0 221.0 225.0 228.5 232.0 236.5 238.5	8.02 7.76 7.79 7.66 7.72 7.74 7.75 7.76 7.74 7.73 7.72 7.65 7.68 7.70 7.71	2.47 2.59 2.74 1.53 2.60 2.61 2.72 2.86 2.75 2.77 2.96 1.44 2.54 2.98 2.95	1418 1303 1397 544 1454 1439 1819 1769 1959 2080 1808 535 1208 2767 2962	3234 2043 2401 523 1788 1954 2043 2046 2623 2861 2461 407 524 1236 1256	4.05 1.76 2.04 0.91 1.51 2.24 1.85 1.93 1.50 1.68 1.59 0.76 1.12 1.20 1.51	6.45 6.65 7.25 6.13 6.92 7.04 7.01 7.02 6.88 6.91 6.99 6.99 7.01 7.53 7.51	3407 3365 3564 3720 3834 3462 4071 3577 4035 4039 3427 3674 2708 2934 3748	8082 4733 5706 4459 4230 4683 4994 4998 5101 5394 5187 2202 2686 3346 3631	1.24 0.15 0.29 0.04 0.11 0.19 0.22 0.25 0.13 0.15 0.14 0.03 0.13 0.11 0.17	7.99 7.53 8.20 7.09 7.55 7.59 7.03 7.70 8.13 7.94 7.43 6.71 7.24 8.46 8.31	3294 2552 2988 2525 2802 2732 3126 2892 3122 3284 2706 2484 1619 1820 2728													8694 3664 5327 2427 2741 3513 3839 3852 3909 4107 3819 1888 1724 2154 2246
242.0 245.5 248.0 250.0 252.3 255.0 258.0 261.0 262.5 264.0 270.0 273.0													7.73 7.74 7.72 7.72 7.69 7.70 7.72 7.72 7.73 7.73 7.73 7.71	2.93 3.00 3.00 2.96 3.08 3.17 2.92 2.98 2.97 2.92 2.93 3.01	1404 1778 1831 1834 1995 2045 1919 1909 1853 1905 1978 1646	1146 1657 1739 1733 1421 1699 1898 2016 2044 2125 2269 1713	1.48 1.44 1.47 1.57 1.47 1.60 1.57 1.54 1.76 1.83 1.86 1.81	7.14 7.19 7.24 8.02 7.53 7.64 7.39 7.24 7.30 7.41 7.15 6.97	3231 3758 3781 3875 4141 4102 3914 3935 3296 3858 3840 3081	3767 3684 3763 3928 4229 3635 4148 4109 4404 4367 4415 4619	0.17 0.13 0.14 0.15 0.13 0.15 0.14 0.13 0.15 0.16 0.15 0.13	7.55 8.22 8.39 8.20 8.50 8.74 8.08 8.09 8.06 8.22 8.30 7.97	2192 2782 2867 2882 3190 3076 2778 2747 2490 2720 3062 2492	2064 2247 2397 2372 2405 2601 2428 2603 2731 2828 3498 3091

Elapsed time (hr)	Effectively total R1 raw material				The R1 discharge				The R2 discharge
													NPMIDA (wt％)	Gly (wt％)	HCHO (ppm)	HCOOH (ppm)	NPMIDA (wt％)	Gly (wt％)	HCHO (ppm)	HCOOH (ppm)	NPMIDA (wt％)	Gly (wt％)	HCHO (ppm)	HCOOH (ppm)
	276.0 279.0 282.0 285.0 288.0 291.0 294.0 297.0 300.0 303.0 306.0 309.0	7.72 7.72 7.74 7.69 7.70 7.69 7.69 7.70 7.69 7.71 7.71 7.68	2.95 2.94 2.99 2.96 2.98 2.92 2.89 2.88 2.89 2.86 2.85 2.80	1637 1646 1973 1807 1781 1809 1823 1836 1828 1889 1875 1874	1751 2020 1741 1438 1464 1371 1357 1377 1358 1468 1453 1356	1.87 1.95 1.67 1.53 1.46 1.55 1.52 1.82 1.71 1.93 1.72 1.60	6.95 6.90 7.02 7.23 7.13 7.10 7.13 6.98 6.85 6.87 6.65 6.70	3062 3049 3093 3444 3498 3520 3666 3632 3525 3617 3538 3573	4531 4576 3462 3660 3683 3793 3750 3747 3640 3802 3657 3731	0.16 0.14 0.16 0.08 0.10 0.11 0.10 0.14 0.11 0.14 0.11 0.09	7.99 7.99 8.05 8.11 7.97 8.03 7.96 7.92 7.95 7.78 7.71 7.72	2471 2514 2450 2547 2654 2756 2790 2849 2815 2868 2803 2904													3038 2600 2548 2352 2359 2450 2399 2492 2406 2505 2435 2512
312.0 315.0 318.0 321.0 324.0 327.0 330.0 333.0 337.0 339.5 342.5 344.0 346.0 348.0 350.3													7.70 7.70 7.72 7.72 7.73 7.73 7.74 7.78 7.75 7.75 7.75 7.75 7.71 7.72 7.71	2.80 2.89 2.85 2.84 2.82 2.94 2.95 3.05 3.07 2.97 3.07 3.07 2.97 3.01 2.97	2117 2106 2115 2150 2173 2187 2382 2777 2848 2798 2782 2776 2462 2506 2386	2129 1744 2025 2177 2207 2244 1790 1942 1987 2025 2105 2564 2316 2515 2328	1.90 1.85 2.21 2.24 2.21 2.27 2.46 2.52 2.19 2.35 2.39 2.37 1.56 1.98 1.90	6.83 6.94 6.89 6.73 6.69 6.69 6.76 6.67 7.20 6.66 6.98 6.90 7.34 7.00 7.19	3902 3946 3933 3864 3857 3805 4069 4864 5059 4770 4905 4860 4418 4454 4624	3753 3545 3772 3918 3817 4088 4402 4586 4908 4719 4929 5242 4337 5019 4795	0.13 0.10 0.16 0.16 0.15 0.17 0.23 0.21 0.15 0.20 0.18 0.17 0.08 0.12 0.11	8.04 8.96 8.23 8.20 8.27 8.19 8.14 8.48 8.35 8.06 8.36 8.43 8.16 8.34 8.17	3223 3459 3299 3313 3321 3317 3536 4232 4237 4152 4240 4198 3386 3593 3614	2603 2368 2731 2989 2920 3221 3297 3341 3434 3552 3636 3899 2732 3655 3321

Elapsed time (hr)	Effectively total R1 raw material				The R1 discharge				The R2 discharge
													NPMIDA (wt％)	Gly (wt％)	HCHO (ppm)	HCOOH (ppm)	NPMIDA (wt％)	Gly (wt％)	HCHO (ppm)	HCOOH (ppm)	NPMIDA (wt％)	Gly (wt％)	HCHO (ppm)	HCOOH (ppm)
	352.3 354.3 356.3 358.3 365.0 367.0 368.0	7.71 7.70 7.68 7.67 7.68 7.65 7.65	3.00 3.05 2.97 3.04 3.48 3.91 3.87	2441 2531 2289 2021 1358 1266 1217	2387 1888 1874 1415 998 1063 1101	1.95 2.13 1.39 1.05 1.13 1.13 1.24	6.96 7.03 7.62 8.15 8.47 8.33 8.31	4594 4941 4250 4080 3195 2825 2475	4764 4936 4101 3814 3102 3149 3257	0.13 0.14 0.06 0.03 0.02 0.02 0.02	8.27 8.27 8.53 8.49 7.95 8.94 9.08	3869 3839 3191 2685 1949 1612 1737													3596 3312 2754 2026 1597 1647 1898

Embodiment 37:NPMIDA is oxidized to glyphosate continuously in the fixed-bed reactor that use the Pt/Fe/C catalyzer

Present embodiment understands that for example NPMIDA in the presence of the heterogeneous beaded catalyst of Pt/Fe/C, is oxidized to glyphosate continuously in fixed-bed reactor.This experimental design is used for a bit of of fixed-bed reactor that analog gas and liquid starting material enter in the same way.

Experiment is carried out in the flow reactor system that comprises vertical stainless steel tubular type reactor (1.56cm internal diameter, 60.5cm length, 116ml volume).Gas and liquid raw materials flow enter tubular reactor and the reactor of flowing through downwards at the top.Reactor contains Pt/Fe/C catalyzer (42.3g), and this catalyzer comprises and loads on length and be extrude platinum (2wt%) and the iron (0.2wt%) carbon support on of about 1mm to about 9mm, diameter 1.2mm.With the water raw material of heating reactor is heated to 90 ℃ and rise to the pressure of 150psig with nitrogen.Reach after 90 ℃ at temperature of reactor, stop water and nitrogen gas stream, restart liquid and oxygen feed.

Liquid starting material (50ml/min) comprises and contains NPMIDA (1.92wt%), glyphosate (1.89wt%), the aqueous slurries raw material of formic acid (0.26wt%) and formaldehyde (0.15wt%).Oxygen (200sccm) is given to the top of reactor, and pressure remains on 150psig.After operate continuously 10 days, the analysis of reactor product shows formaldehyde 0.15%, formic acid 0.26% and glyphosate 2.53%.

Embodiment 38:NPMIDA uses the Pt/Fe/C catalyzer to be oxidized to glyphosate continuously in fixed-bed reactor

Present embodiment is for example understood NPMIDA in the presence of the heterogeneous beaded catalyst of Pt/Fe/C, is oxidized to glyphosate continuously in the fixed-bed reactor at upper reaches in the same way at gas and liquid reactants.

Experiment is carried out in the continuous oxidation reaction device system that comprises as embodiment 37 described vertical stainless steel tubular type reactors, just the reactant reaction zone of upwards flowing through.Reactor contains Pt/Fe/C catalyzer (42.3g), and this catalyzer comprises and loads on length and be extrude platinum (2wt%) and the iron (0.2wt%) carbon support on of about 1mm to about 9mm, diameter 1.2mm.With the water raw material of heating reactor is heated to 90 ℃ and rise to the pressure of 150psig with nitrogen.Reach after 90 ℃ at temperature of reactor, stop water and nitrogen gas stream, restart liquid and oxygen feed.

Liquid starting material (50ml/min) comprises and contains NPMIDA (1.80wt%), glyphosate (2.19wt%), and the aqueous slurries raw material of formic acid (0.26wt%) and formaldehyde (0.14wt%), and under 90 ℃, be given to the bottom of reactor.Oxygen (200sccm) is given to the bottom of reactor, and pressure remains on 150psig.After operate continuously 19 hours, the analysis of reactor product shows formaldehyde 0.13%, formic acid 0.16% and glyphosate 2.42%.

Embodiment 39:NPMIDA sylvite is oxidized to glyphosate potassium in the fixed-bed reactor at upper reaches in the same way continuously at the liquids and gases reactant that uses the Pt/Fe/C catalyzer

Present embodiment is for example understood NPMIDA sylvite in the presence of the heterogeneous beaded catalyst of Pt/Fe/C, is oxidized to glyphosate potassium continuously in the fixed-bed reactor at upper reaches in the same way at the liquids and gases reactant.

Experiment is carried out in the continuous oxidation reaction device system that comprises vertical stainless steel tubular type reactor as described in example 37 above, just the reactant reaction zone of upwards flowing through.Reactor contains Pt/Fe/C catalyzer (42.3g), and this catalyzer comprises and loads on length and be extrude platinum (2wt%) and the iron (0.2wt%) carbon support on of about 1mm to about 9mm, diameter 1.2mm.With the water raw material of heating reactor is heated to 90 ℃ and rise to the pressure of 150psig with nitrogen.Reach after 90 ℃ at temperature of reactor, stop water and nitrogen gas stream, restart liquid and oxygen feed.

Liquid starting material (50ml/min) comprises and contains NPMIDA sylvite (22.9wt%), glyphosate (0.09wt%), and the aqueous slurries raw material of formic acid (0.20wt%) and formaldehyde (0.14wt%), and under 90 ℃, be given to the bottom of reactor.Oxygen (500sccm) is given to the bottom of reactor, and pressure remains on 150psig simultaneously.The analysis of reactor product shows formaldehyde 0.35%, formic acid 0.20% and glyphosate potassium 1.56%.

The comparison of embodiment 40:Pt/Fe catalyzer and Pt/Fe and Pt/Fe/Te mixture of catalysts

Present embodiment has compared the conversion of the NPMIDA-glyphosate in the continuous oxidation reaction device system that uses the heterogeneous beaded catalyst of Pt/Fe and the conversion of the NPMIDA-glyphosate in the continuous oxidation reaction device system of the mixture that uses Pt/Fe and the heterogeneous beaded catalyst of Pt/Fe/Te.

Be reflected at and utilize 2L Hastelloy C autoclave (Autoclave Engineers Inc, Pittsburgh carry out in flow reactor system PA).Reactor is equipped with has 1.25 " agitator of 6 turbo wheels of diameter, it is operated under 1600RPM.Use has the Drexelbrook Universal III of the sensing member of polytetrafluorethylecoatings coatings ^TMSmart Level ^TMFluid level in the monitoring reactor.Utilize inner cooling spiral to control the temperature in the reactor in the reaction process.

In first experiment, in reactor, add heterogeneous beaded catalyst of Pt/Fe (2.18g) and aqueous slurries raw material (1448g).Catalyst pack platiniferous (5wt%) and iron (0.5wt%).The aqueous slurries raw material comprises NPMIDA (3.5wt%), glyphosate (1.5wt%), formaldehyde (1200 ppm by weight), and formic acid (2500 ppm by weight).The slurry raw material also contains NaCl (580 ppm by weight), with simulation NaCl impurity.

With nitrogen reactor is pressurized to 100psi, and is heated to 100 ℃.In case reach this temperature, passing through under the situation of system continuous flow of oxygen feeding reactor without any liquid flow.After 9 minutes, start continuous slurry raw material with the flow rate of 70.4g/min, and as continuing the feeding Oxygen Flow described in the following table 49.From reactor, discharge the liquid product stream that contains the glyphosate product continuously, analyze by HPLC.Oxidation results also provides in table 49.

In second experiment, in reactor, add the heterogeneous beaded catalyst of Pt/Fe (1.09g), the heterogeneous beaded catalyst of Pt/Fe/Te (1.09g) and aqueous slurries raw material (1455g).Pt/Fe catalyst pack platiniferous (5wt%) and iron (0.5wt%), and Pt/Fe/Te catalyst pack platiniferous (5wt%), iron (0.5wt%) and tellurium (0.2wt%).The aqueous slurries raw material comprises NPMIDA (3.5wt%), glyphosate (1.5wt%), formaldehyde (1200 ppm by weight), and formic acid (2500 ppm by weight).The slurry raw material also contains NaCl (580 ppm by weight), with simulation NaCl impurity.

With nitrogen reactor is pressurized to 100psi, and is heated to 100 ℃.In case reach this temperature, passing through under the situation of system continuous flow of oxygen feeding reactor without any liquid flow.After 19 minutes, start continuous slurry raw material with the flow rate of 70.4g/min, and as continuing the feeding Oxygen Flow described in the following table 50.From reactor, discharge the liquid product stream that contains the glyphosate product continuously, analyze by HPLC.The oxidation results of second experiment also provides in table 50.

The oxidation results (experiment 1) of table 49Pt/Fe catalyzer

Elapsed time (min)	O 2Flow (sccm)	Feed NPMIDA (wt%)	Discharge NPMIDA (wt%)	Feed glyphosate (wt%)	Discharge glyphosate (wt%)	Feed CH 2O (ppm)	Discharge CH 2O (ppm)	Feed HCOOH (ppm)	Discharge HCOOH (ppm)
										77.0	300.0	3.49	0.82	1.51	3.47	1098.9	2083.9	2118.7	4385.0
147.0	300.0	3.49	0.52	1.51	3.23	1098.9	1674.8	2118.7	4653.9
										205.0	300.0	3.49	0.80	1.51	3.49	1098.9	2195.2	2118.7	4206.5
280.0	300.0	3.49	0.84	1.51	3.48	1098.9	2215.4	2118.7	4167.7
										1212.0	300.0	3.49	1.07	1.51	3.40	1098.9	2344.2	2118.7	3991.1
1378.0	300.0	3.49	1.18	1.51	3.40	1098.9	2361.3	2118.7	3973.1
										1447.0	300.0	3.49	1.17	1.51	3.38	1098.9	2347.3	2118.7	4008.4
1618.0	300.0	3.49	1.26	1.51	3.35	1098.9	2323.1	2118.7	3985.8
										1795.0	300.0	3.49	1.35	1.51	3.31	1098.9	2356.2	2118.7	3896.4
2683.0	300.0	3.49	1.39	1.51	3.27	1098.9	2316.2	2118.7	3861.0
										2789.0	300.0	3.49	1.45	1.51	3.30	1098.9	2353.9	2118.7	3871.0
2885.0	300.0	3.49	1.53	1.51	3.25	1098.9	2310.5	2118.7	3796.1
										3071.0	450.0	3.49	0.98	1.51	3.43	1098.9	2520.4	2118.7	3935.2
3180.0	700.0	3.49	0.88	1.51	3.55	1098.9	2653.0	2118.7	4086.1

The oxidation results of table 50 Pt/Fe and Pt/Fe/Te catalyzer (experiment 2)

Elapsed time (min)	O 2Flow (sccm)	Feed NPMIDA (wt%)	Discharge NPMIDA (wt%)	Feed glyphosate (wt%)	Discharge glyphosate (wt%)	Feed CH 2O (ppm)	Discharge CH 2O (ppm)	Feed HCOOH (ppm)	Discharge HCOOH (ppm)
										48.0	315.0	3.25	0.82	1.60	3.18	1222.1	940.17	2299.6	3757.3
156.0	330.0	3.25	0.75	1.60	3.15	1222.1	1087.2	2299.6	3975.6
										210.0	365.0	3.25	0.57	1.60	3.27	1222.1	1200.9	2299.6	4114.4
281.0	410.0	3.25	0.46	1.60	3.39	1222.1	1306.9	2299.6	4182.9
										339.0	410.0	3.25	0.67	1.60	3.35	1222.1	1306.5	2299.6	4191.2
626.0	400.0	3.25	0.92	1.60	3.30	1222.1	1385.2	2299.6	4081.0
										1295.0	425.0	3.25	1.10	1.60	3.15	1222.1	1289.0	2299.6	3910.2
1424.0	450.0	3.25	1.16	1.60	3.14	1222.1	1341.6	2299.6	3951.3
										1548.0	450.0	3.25	1.13	1.60	3.07	1222.1	1292.0	2299.6	3948.4
1648.0	450.0	3.25	1.16	1.60	3.17	1222.1	1264.6	2299.6	3916.0
										1762.0	450.0	3.25	1.26	1.60	3.11	1222.1	1234.7	2299.6	3964.7
1820.0	500.0	3.25	1.08	1.60	3.08	1222.1	1200.8	2299.6	4065.8
										2749.0	500.0	3.25	1.78	1.60	2.76	1222.1	1079.1	2299.6	3927.5
2857.0	500.0	3.25	1.92	1.60	2.75	1222.1	1065.1	2299.6	3926.3
										2986.0	500.0	3.25	1.69	1.60	2.68	1222.1	1031.1	2299.6	3910.7
3118.0	500.0	3.25	1.81	1.60	2.64	1222.1	1009.7	2299.6	3892.2

The present invention is not limited to above embodiment, and can carry out various variations.Above preferred embodiment comprises the narration of embodiment, only be used for making those skilled in the art to be familiar with the present invention, its principle and its practical application, make those skilled in the art can adopt and use the present invention with the various ways that is suitable for most the specific end use requirement.

Comprise as for the word that uses in the whole specification sheets (comprising following claims), the applicant it is to be noted, unless requirement is arranged in the literary composition in addition, these words are clearly understood according to fundamental sum and are used, they should be interpreted as open including, and non-enclosed exclusive, and the applicant wishes that in these words in whole specification sheets each all so explains.

Claims (17)

1, prepare the method for N-((phosphonomethyl)) glycine product by oxidation N-((phosphonomethyl)) iminodiethanoic acid substrate, this method comprises:

N-((phosphonomethyl)) iminodiethanoic acid substrate is incorporated in the interior liquid reaction medium of oxidation reaction zone, oxidation reaction zone basic back mixing and contain the catalyst for oxidation reaction that contacts with liquid reaction medium in liquid phase, liquid reaction medium comprises N-((phosphonomethyl)) glycine product;

Oxygenant is incorporated into oxidation reaction zone;

Continuous oxidation N-((phosphonomethyl)) iminodiethanoic acid substrate in oxidation reaction zone forms N-((phosphonomethyl)) glycine product; With

Discharge the reaction mixture that comprises N-((phosphonomethyl)) glycine product continuously from oxidation reaction zone and flow out thing.

2, prepare the method for N-((phosphonomethyl)) glycine product by oxidation N-((phosphonomethyl)) iminodiethanoic acid substrate, this method comprises:

N-((phosphonomethyl)) iminodiethanoic acid substrate is incorporated in the interior liquid reaction medium of oxidation reaction zone, and liquid reaction medium comprises N-((phosphonomethyl)) glycine product and the particle heterogeneous catalyst that is used for oxidizing reaction that is suspended in wherein;

Oxygenant is incorporated into oxidation reaction zone;

Continuous oxidation N-((phosphonomethyl)) iminodiethanoic acid substrate in the liquid reaction medium in oxidation reaction zone forms N-((phosphonomethyl)) glycine product;

The continuous blow-down reaction mixture flows out thing from described oxidation reaction zone, and reaction mixture flows out thing and comprises N-((phosphonomethyl)) glycine product;

Flow out continuous separating particles catalyzer the thing from reaction mixture, form the catalyst recycle logistics that comprises isolating catalyzer; With

At least a portion beaded catalyst that will contain in the catalyst recycle logistics is recycled to described oxidation reaction zone.

3, prepare the method for N-((phosphonomethyl)) glycine product by oxidation N-((phosphonomethyl)) iminodiethanoic acid substrate in reactor assembly, this method comprises:

The water-containing material stream that will comprise N-((phosphonomethyl)) iminodiethanoic acid substrate is incorporated into first oxidation reaction zone;

Oxygenant is incorporated into first oxidation reaction zone;

In first oxidation reaction zone,, form N-((phosphonomethyl)) glycine product with the continuous oxidation of N-((phosphonomethyl)) iminodiethanoic acid substrate;

Discharge the intermediate reaction mixture that comprises N-((phosphonomethyl)) glycine product and unreacted N-((phosphonomethyl)) iminodiethanoic acid substrate continuously from first oxidation reaction zone and flow out thing;

Middle water-containing material stream is incorporated into second oxidation reaction zone continuously, and described middle water-containing material stream is included in the intermediate reaction mixture and flows out N-((phosphonomethyl)) glycine product and unreacted N-((phosphonomethyl)) the iminodiethanoic acid substrate that obtains in the thing;

Oxygenant is incorporated into second oxidation reaction zone;

In second oxidation reaction zone,, form other N-((phosphonomethyl)) glycine product with the continuous oxidation of N-((phosphonomethyl)) iminodiethanoic acid substrate; With

From second oxidation reaction zone, discharge the reaction mixture that comprises N-((phosphonomethyl)) glycine product continuously and flow out thing.

4, remove from the initial aqueous solution that comprises N-((phosphonomethyl)) glycine product and anhydrate and make therefrom crystalline method of N-((phosphonomethyl)) glycine product, this method comprises:

Moisture evaporation raw mix is incorporated into evaporating area, and described raw mix comprises the described initial aqueous solution;

In the presence of solid particulate N-((phosphonomethyl)) glycine product, in described evaporating area, from described raw mix, water is evaporated, thereby produce the vapor phase that comprises water vapour, from aqueous liquid phase, be settled out N-((phosphonomethyl)) glycine product, and generation comprises N-((phosphonomethyl)) glycine product solid and N-((phosphonomethyl)) glycine product is saturated substantially or the evaporate of oversaturated mother liquor; With

The ratio that keeps particle N-((phosphonomethyl)) glycine product solid and mother liquor in described evaporating area is greater than the ratio of the N-that is produced gradually by evaporative effect ((phosphonomethyl)) glycine product solid with the mother liquor that produces gradually thus.

5, be used for removing from the initial aqueous solution that comprises N-((phosphonomethyl)) glycine product and anhydrate and make therefrom crystalline method of N-((phosphonomethyl)) glycine product, this method comprises:

The evaporation raw mix that will comprise the described initial aqueous solution is incorporated into vapour/liquid disengaging zone, wherein pressure is lower than the vapour pressure of described mixture, thereby water flash distillation from the evaporation raw mix is come out, produced the vapor phase that comprises water vapour, and make N-((phosphonomethyl)) glycine product be increased to concentration above N-((phosphonomethyl)) glycine product solubleness in the concentration of residue in the liquid phase, thereby N-((phosphonomethyl)) glycine product is precipitated out from liquid phase, has produced the first slurry logistics of particle N-((phosphonomethyl)) the glycine product that is included in saturated or the supersaturation mother liquor;

Described vapor phase is separated with the described first slurry logistics;

The described first slurry logistics is incorporated into the decantation district, in this district, the upper strata liquid that comprises described mother liquor fraction separates with the second slurry logistics that comprises sedimentary N-((phosphonomethyl)) glycine product and mother liquor, described decantation district has the import of described first slurry, be positioned at the decanting liq outlet that is used for described upper strata liquid on the described import, and vertically be positioned on the described import but the outlet of described second slurry under the outlet of described upper strata liquid; With

Keep described first slurry is incorporated into described decantation district; the speed of relative movement that described second slurry is discharged by described second slurry outlet and described upper strata liquid is discharged by described decanting liq outlet; make the upward flow speed in the lower region in the described decantation district under described second slurry outlet be enough to keep sedimentary N-((phosphonomethyl)) glycine product to be suspended in the liquid phase, and the upward flow speed in the upper area in the described decantation district on described second slurry outlet is under the settling velocity of N-((phosphonomethyl)) glycine product particle of at least 80% weight in lower region.

6, remove from the initial aqueous solution that comprises N-((phosphonomethyl)) glycine product and anhydrate and make therefrom crystalline method of N-((phosphonomethyl)) glycine product, this method comprises:

Moisture evaporation raw mix is incorporated into evaporating area, and described raw mix comprises the described initial aqueous solution;

In the presence of solid particulate N-((phosphonomethyl)) glycine product, in described evaporating area, water is evaporated from described raw mix, thereby produce the vapor phase that comprises water vapour, from aqueous liquid phase, be settled out N-((phosphonomethyl)) glycine product, and generation comprises N-((phosphonomethyl)) glycine product solid and N-((phosphonomethyl)) glycine product is saturated substantially or the evaporate of oversaturated mother liquor;

Described evaporate is divided into the relative poor mother liquor fraction with N-((phosphonomethyl)) glycine product solid of poor relatively N-((phosphonomethyl)) the glycine product solid fraction of mother liquor; With

The ratio that keeps particle N-((phosphonomethyl)) glycine product solid and mother liquor in described evaporating area is greater than the ratio of the N-that is produced gradually by evaporative effect ((phosphonomethyl)) glycine product solid with the mother liquor that produces gradually thus.

7, be used for catalyzed oxidation N-((phosphonomethyl)) iminodiethanoic acid substrate to generate the continuation method of N-((phosphonomethyl)) glycine product, this method comprises:

The liquid phase feed stream that will comprise the water-containing material stream that contains N-((phosphonomethyl)) iminodiethanoic acid substrate is incorporated into the primary oxidation reactor district, and the primary oxidation reactor district comprises the primary fixed bed that contains oxide catalyst;

Oxygenant is incorporated into the primary oxidation reactor district;

In the primary oxidation reactor district, N-((phosphonomethyl)) iminodiethanoic acid substrate is oxidized to N-((phosphonomethyl)) glycine product continuously, thereby forms the primary reaction mixture that comprises N-((phosphonomethyl)) glycine product and unreacted N-((phosphonomethyl)) iminodiethanoic acid substrate;

Discharge the primary reaction mixture from the primary oxidation reactor district; With

The water-containing material that unit weight sensible heat content difference between described reaction mixture and described water-containing material stream is remained below per unit weight flows the thermopositive reaction heat that produces in reaction zone.

8, be used for catalyzed oxidation N-((phosphonomethyl)) iminodiethanoic acid substrate to generate the method for N-((phosphonomethyl)) glycine product, this method comprises:

The water-containing material stream that will comprise N-((phosphonomethyl)) iminodiethanoic acid substrate is incorporated into first of serial oxidation reaction zone, and each of serial oxidation reaction zone comprises oxide catalyst;

In first oxidation reaction zone,, produce the intermediate oxidation reaction product with the oxidation of N-((phosphonomethyl)) iminodiethanoic acid substrate;

The intermediate oxidation reaction product is incorporated into second oxidation reaction zone that comprises the fixed bed that contains precious metal/C catalyst; With

Oxidized byproduct formaldehyde and/or formic acid in second oxidation reaction zone.

9, be used for catalyzed oxidation N-((phosphonomethyl)) iminodiethanoic acid substrate to generate the continuation method of N-((phosphonomethyl)) glycine product, this method comprises:

The water-containing material stream that will contain N-((phosphonomethyl)) iminodiethanoic acid substrate is incorporated in the oxidation reaction zone that comprises the fixed bed that contains oxide catalyst;

To contain O ₂Gas is incorporated into oxidation reaction zone; With

In oxidation reaction zone, N-((phosphonomethyl)) iminodiethanoic acid substrate is oxidized to N-((phosphonomethyl)) glycine product continuously; thereby produce the oxidation mixtures that comprises N-((phosphonomethyl)) glycine product, the mass flow rate of the liquid phase in the fixed bed is about 20 to about 800 with the mass flow rate of gas phase ratio.

10, be used for catalyzed oxidation N-((phosphonomethyl)) iminodiethanoic acid substrate to generate the continuation method of N-((phosphonomethyl)) glycine product, this method comprises:

The water-containing material stream that will contain N-((phosphonomethyl)) iminodiethanoic acid substrate is incorporated in the oxidation reaction zone that comprises the fixed bed that contains oxide catalyst;

To contain O ₂Gas is incorporated into oxidation reaction zone; With

In oxidation reaction zone, N-((phosphonomethyl)) iminodiethanoic acid substrate is oxidized to N-((phosphonomethyl)) glycine product continuously; thereby obtain to comprise the oxidation mixtures of N-((phosphonomethyl)) glycine product, the liquid phase residual amount in fixed bed is about 0.1 to about 0.5 with the volume ratio of total bed volume.

11, be used for catalyzed oxidation N-((phosphonomethyl)) iminodiethanoic acid substrate to generate the continuation method of N-((phosphonomethyl)) glycine product, this method comprises:

The water-containing material stream that will contain N-((phosphonomethyl)) iminodiethanoic acid substrate is incorporated into the oxidation reaction zone that comprises the fixed bed that contains oxide catalyst;

To contain O ₂Gas is incorporated into oxidation reaction zone; With

In oxidation reaction zone, N-((phosphonomethyl)) iminodiethanoic acid substrate is oxidized to N-((phosphonomethyl)) glycine product continuously; thereby obtain to comprise the oxidation mixtures of N-((phosphonomethyl)) glycine product, be not higher than about 100psia in the oxygen partial pressure of the liquid outlet of fixed bed.

12, be used for catalyzed oxidation N-((phosphonomethyl)) iminodiethanoic acid substrate to generate the continuation method of N-((phosphonomethyl)) glycine product, this method comprises:

The water-containing material stream that will contain N-((phosphonomethyl)) iminodiethanoic acid substrate is incorporated into the oxidation reaction zone that comprises the fixed bed that contains oxide catalyst;

To contain O ₂Gas is incorporated into oxidation reaction zone; With

In oxidation reaction zone, N-((phosphonomethyl)) iminodiethanoic acid substrate is oxidized to N-((phosphonomethyl)) glycine product continuously; thereby obtain to comprise the oxidation mixtures of N-((phosphonomethyl)) glycine product; N-in liquid phase ((phosphonomethyl)) iminodiethanoic acid concentration of substrate is lower than the optional position of the fixed bed of about 0.1ppm, and oxygen partial pressure is not higher than about 50psia.

13, be used for catalyzed oxidation N-((phosphonomethyl)) iminodiethanoic acid substrate to generate the continuation method of N-((phosphonomethyl)) glycine product, this method comprises:

The water-containing material stream that will contain N-((phosphonomethyl)) iminodiethanoic acid substrate is incorporated into the oxidation reaction zone that comprises the fixed bed that contains oxide catalyst, and catalyst surface area is about 100 to about 6000m with the ratio of liquid holdup in the fixed bed ²/ cm ³

Oxygenant is incorporated into oxidation reaction zone; With

In oxidation reaction zone, N-((phosphonomethyl)) iminodiethanoic acid substrate is oxidized to N-((phosphonomethyl)) glycine product continuously, thereby obtains to comprise the oxidation mixtures of N-((phosphonomethyl)) glycine product.

14, be used for catalyzed oxidation N-((phosphonomethyl)) iminodiethanoic acid substrate to generate the continuation method of N-((phosphonomethyl)) glycine product, this method comprises:

The water-containing material stream that will contain N-((phosphonomethyl)) iminodiethanoic acid substrate is incorporated into the oxidation reaction zone that comprises the fixed bed that contains oxide catalyst;

To contain O ₂Gas is incorporated into oxidation reaction zone; With

In oxidation reaction zone, N-((phosphonomethyl)) iminodiethanoic acid substrate is oxidized to N-((phosphonomethyl)) glycine product continuously; thereby obtain to comprise the oxidation mixtures of N-((phosphonomethyl)) glycine product; integral mean oxygen partial pressure along liquid flow path in fixed bed is at least about 50psia, and the integral mean temperature of the liquid phase in fixed bed is about 80 ℃ to about 130 ℃.

15, be used for catalyzed oxidation N-((phosphonomethyl)) iminodiethanoic acid substrate to generate the continuation method of N-((phosphonomethyl)) glycine product, this method comprises:

The water-containing material stream that will contain N-((phosphonomethyl)) iminodiethanoic acid substrate is incorporated into oxidation reaction zone, and this oxidation reaction zone comprises the fixed bed that contains the oxide catalyst body and be used to promote other measure of gas/liquid mass transfer;

To contain O ₂Gas is incorporated into oxidation reaction zone; With

In oxidation reaction zone, N-((phosphonomethyl)) iminodiethanoic acid substrate is oxidized to N-((phosphonomethyl)) glycine product continuously, thereby obtains to comprise the oxidation mixtures of N-((phosphonomethyl)) glycine product.

16, be used for catalyzed oxidation N-((phosphonomethyl)) iminodiethanoic acid substrate to generate the continuation method of N-((phosphonomethyl)) glycine product, this method comprises:

The liquid phase feed stream that will comprise the water-containing material mixture that contains N-((phosphonomethyl)) iminodiethanoic acid substrate is incorporated into the primary oxidation reactor district, and this primary oxidation reactor district comprises the fixed bed that contains oxide catalyst;

Oxygenant is incorporated into the primary oxidation reactor district;

In the primary oxidation reactor district, N-((phosphonomethyl)) iminodiethanoic acid substrate is oxidized to N-((phosphonomethyl)) glycine product continuously, thereby produce the liquid phase outlet logistics that comprises the primary reaction mixture, described primary reaction mixture contains N-((phosphonomethyl)) glycine product and unreacted N-((phosphonomethyl)) iminodiethanoic acid substrate; With

Discharge liquid phase outlet logistics from the primary oxidation reactor district; The described liquid phase feed stream introducing speed and the described liquid phase outlet logistics velocity of discharge should make that the liquid phase space-time speed based on total bed volume is about 0.5hr in the described fixed bed ^-1To about 20hr ^-1

17, be used for catalyzed oxidation N-((phosphonomethyl)) iminodiethanoic acid substrate to generate the continuation method of N-((phosphonomethyl)) glycine product, this method comprises:

The first component raw material stream that will comprise N-((phosphonomethyl)) iminodiethanoic acid substrate is incorporated into first of serial continuous reaction zone, and each of described serial reaction district contains oxide catalyst;

Oxygenant is incorporated into first of this serial reaction district;

The described substrate of catalyzed oxidation in described first reaction zone generates the intermediate reaction mixture stream passes that comprises N-((phosphonomethyl)) glycine product;

To transfer to second of this serial reaction district from the intermediate reaction mixture that described first reaction zone is discharged;

Described substrate of catalyzed oxidation in each of described serial reaction district;

Discharge the intermediate reaction mixture from each described reaction zone;

To be incorporated in each follow-up reaction zone at the intermediate reaction mixture that last reaction zone produces;

Other component raw material stream is incorporated in each of one or more described reaction zones after in described series first reaction zone, each described other feedstream comprises N-((phosphonomethyl)) iminodiethanoic acid substrate;

Oxygenant is incorporated in one or more reaction zones after in described series first reaction zone; With

From last of described serial reaction district, discharge final reacting product.

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