CN102241703B - Improved method for preparing glyphosate from N-phosphonomethyl aminodiacetic acid - Google Patents
Improved method for preparing glyphosate from N-phosphonomethyl aminodiacetic acid Download PDFInfo
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- CN102241703B CN102241703B CN201110116866.5A CN201110116866A CN102241703B CN 102241703 B CN102241703 B CN 102241703B CN 201110116866 A CN201110116866 A CN 201110116866A CN 102241703 B CN102241703 B CN 102241703B
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Abstract
The invention provides an improved method for preparing glyphosate from N-phosphonomethyl aminodiacetic acid. The method comprises the following steps of: adding the N-phosphonomethyl aminodiacetic acid, active carbon and water into a high pressure reactor in a certain ratio; introducing air for oxidation reaction; and when the N-phosphonomethyl aminodiacetic acid content is reduced to a certain range, adding a cooperating catalyst for continuous reaction to obtain the glyphosate. The cooperating catalyst is introduced before the glyphosate is subjected to deep oxidation, a byproduct of formaldehyde generated in the reaction process is effectively removed, the reaction yield is improved, and the quality stability of the glyphosate and salt thereof is effectively improved; moreover, because the byproduct of formaldehyde is removed well, the mother solution can be directly applied mechanically or used for preparing an aqueous solution, wastewater is effectively controlled, and the cost is saved.
Description
Technical field
The invention belongs to the preparation field of glyphosate, be specifically related to a kind of method of improved preparing glyphosate from N-phosphonomethyl aminodiacetic acid.
Background technology
Glyphosate (glyphosate; N-((phosphonomethyl)) glycine) be a kind of low toxicity organophosphorus herbicide of efficiently full systemic action mode; can remove 1 year and perennial weeds and sea tangle kind; due to its remarkable herbicidal performance; agriculture, woods, herd, the application of the aspect such as gardening is very extensive; now become the weedicide kind of global sales maximum, within its year, sales volume occupies first of agricultural chemicals always, has worldwide produced huge economic implications.
In prior art, utilize pmida98 oxidation to produce the technology of glyphosate a lot, mainly contain air oxidation process, transiting metal oxidation method, electrolytic oxidation, hydrogen peroxide oxidation process etc., but all there is certain defect, cannot be applicable to large requirement of producing.
US3969398 discloses take gac as catalyzer, adopts molecular oxygen precursor oxidation preparing glyphosate from N-phosphonomethyl aminodiacetic acid.Although can obtain higher yield, in producing, there is a large amount of by product formaldehyde to exist, can react with glyphosate and generate methyl glyphosate, cause product stability poor.
CN1609111A discloses pmida98 under the Pd/carbon catalyst containing Mn, Fe, Co, Cu or Ni exists, and with oxygen reaction, generates glyphosate.The method has also obtained good yield, but has equally a large amount of by-product formaldehyde in producing, and affects quality product.
CN101337978A discloses the method for utilizing oxygen rich gas catalyzed oxidation high density pmida98 to produce glyphosate.The method be take high density pmida98 as raw material, and gac is catalyzer, and pmida98, gac and water are added in autoclave, passes into oxygen rich gas and carries out oxidizing reaction and make glyphosate.The glyphosate yield that the method obtains is higher, but cannot solve equally a large amount of by-product formaldehyde that produce in production, affects quality product.
Although some can obtain good yield above method, all produce in process of production a large amount of formaldehyde, both affected the quality product of glyphosate, in also making to produce, produced a large amount of formaldehyde-containing wastewaters, make difficult treatment, cost increases.
Summary of the invention
The object of this invention is to provide a kind of improved pmida98 and produce the method for glyphosate, to solve the defect existing in prior art.
The technical solution used in the present invention is as follows:
A kind of improved pmida98 is produced the method for glyphosate, the method be take pmida98 as raw material, gac is catalyzer, load the molecular sieve of precious metal and transition metal be synergistic catalyst, it is characterized in that pmida98, gac and water wiring solution-forming, add in autoclave, pass into air and carry out oxidizing reaction, control 45 ~ 70 ° of C of temperature of reaction, maintain system pressure at 0.4 ~ 0.6MPa simultaneously, when pmida98 content is reduced to certain limit, add synergistic catalyst to continue reaction to finishing, generate glyphosate.
Described gac, pmida98 weight ratio are 1:(4-10), pmida98 aqueous solution mass percent concentration is 20 ~ 50%, synergistic catalyst, pmida98 weight ratio are 1:20-60.
Described precious metal is preferably platinum, the preferred titanium of transition metal and iron, and selected molecular sieve is a kind of in y-type zeolite, T-shaped zeolite, mordenite, silica zeolite, type ZSM 5 molecular sieve.Described oxidizing reaction is reduced to 5 ~ 15% at the content of pmida98, adds synergistic catalyst.After oxidizing reaction finishes, crystallization, filters, and the filter cake of collection is put in glyphosate saturated solution, and rising temperature for dissolving is filtered, and reclaims the gac in filtrate, and filtrate crystallisation by cooling filters, and filter cake is dried, and obtains glyphosate crystal.
Further, the present invention specifically can comprise the following steps: by gac, pmida98 and water by a certain percentage wiring solution-forming add in autoclave, gac wherein, pmida98 weight ratio 1:(4-10), pmida98, pmida98 aqueous solution weight ratio is 20 ~ 50%, stir and heat up, pass into air, control temperature of reaction and carry out oxidizing reaction at 45 ~ 70 ° of C, maintain system pressure at 0.4 ~ 0.6MPa simultaneously, react to the content of pmida98 and be reduced to 5 ~ 15%, add synergistic catalyst, synergistic catalyst, pmida98 weight ratio is 1:20-60, continue to be oxidizing to reaction complete.Feed liquid is squeezed in crystallization kettle, and glyphosate sufficient crystallising is separated out, and then filtration, separation, obtain mother liquor.The blending filter cake that contains glyphosate and gac of collecting is put in glyphosate saturated solution, add in reactor, rising temperature for dissolving is filtered, reclaim the catalyzer in filtrate, filtrate is squeezed into crystallisation by cooling in crystallization kettle, filtering separation, crystallization filtrate is glyphosate saturated solution, reclaim so that recycled is collected filter cake and is dried, obtain glyphosate crystal.
Wherein, the mother liquor filtering, separation obtains is applied mechanically, the gac that filtering separation is obtained is with applying mechanically after a small amount of washing.
Preparation method of the present invention is that to take pmida98 (PMIDA) be raw material, gac is catalyzer, the zeolite of carried noble metal and transition metal is as synergistic catalyst, air is oxygenant, by gac: pmida98=1:4-10, add and in autoclave, carry out oxidizing reaction to the content of pmida98 and be reduced to 5 ~ 15%, by synergistic catalyst: pmida98=1:20-60.Add synergistic catalyst, continue reaction and make glyphosate (PMG).
In the feed liquid of glyphosate reaction at present, mainly contain a small amount of pmida98, formaldehyde, formic acid and methyl glyphosate etc., wherein formaldehyde is to cause the topmost reason of glyphosate generation by-product.
Principal reaction equation is
Advantage of the present invention is: utilization of the present invention is in the catalytic oxidation process of pmida98, introduce synergistic catalyst, utilize the distinctive duct of zeolite, effectively avoid on the one hand glyphosate contact precious metal to cause inactivation, can effectively remove on the other hand the formaldehyde and the formic acid by-product that in reaction process, generate, effectively improve the yield of glyphosate, increase the stability of glyphosate or its salt quality.
Embodiment
Example one
First the pmida98 of 300g (mass percentage content is 98%), 30g gac and 300g deionized water are dropped in stainless steel autoclave, stir, be warming up to 45 ° of C, pass into air, carry out oxidizing reaction, maintain system pressure 0.6MPa, react to the content of pmida98 and be reduced to 5%, add 5g synergistic catalyst to continue reaction complete to being oxidized.Feed liquid is moved in crystallization kettle, treat that glyphosate sufficient crystallising separates out, filter, separation, obtaining mother liquor formaldehyde content is 0.09%, and this mother liquor reclaims, and carries out recycled.
The blending filter cake that contains glyphosate and gac of collecting is put in 3000mlPMG saturated solution, rising temperature for dissolving is filtered, and reclaims the catalyzer in filtrate, with stand-by after a small amount of washing, filtrate is squeezed into crystallisation by cooling in crystallization kettle, filtering separation, crystallization filtrate is glyphosate saturated solution, reclaims so that recycled, collecting filter cake is dried, obtain glyphosate crystal 217.9g, content is 98.9%, and yield is 96.5%.
Example two
First the pmida98 of 350g (mass percentage content is 98%), 40g gac and 400g deionized water are dropped in stainless steel autoclave, stir, be warming up to 50 ° of C, pass into air, carry out oxidizing reaction, maintain system pressure 0.6MPa, react to the content of pmida98 and be reduced to 10%, add 8g synergistic catalyst to continue reaction complete to being oxidized.Feed liquid is moved in crystallization kettle, treat that glyphosate sufficient crystallising separates out, filter, separation, obtaining mother liquor formaldehyde content is 0.12%, and this mother liquor reclaims, and carries out recycled.
The blending filter cake that contains glyphosate and gac of collecting is put in 3500mlPMG saturated solution, rising temperature for dissolving is filtered, and reclaims the catalyzer in filtrate, with stand-by after a small amount of washing, filtrate is squeezed into crystallisation by cooling in crystallization kettle, filtering separation, crystallization filtrate is glyphosate saturated solution, reclaims so that recycled, collecting filter cake is dried, obtain glyphosate crystal 258.5g, content is 98.3%, and yield is 97.5%.
Example three
First the pmida98 of 350g (mass percentage content is 98%), 50g gac and 500g deionized water are dropped in stainless steel autoclave, stir, be warming up to 50 ° of C, pass into air, carry out oxidizing reaction, maintain system pressure 0.5MPa, react to the content of pmida98 and be reduced to 8%, add 10g synergistic catalyst to continue reaction complete to being oxidized.Feed liquid is moved in crystallization kettle, treat that glyphosate sufficient crystallising separates out, filter, separation, obtaining mother liquor formaldehyde content is 0.08%, and this mother liquor reclaims, and carries out recycled.
The blending filter cake that contains glyphosate and gac of collecting is put in 4000mlPMG saturated solution, rising temperature for dissolving is filtered, and reclaims the catalyzer in filtrate, with stand-by after a small amount of washing, filtrate is squeezed into crystallisation by cooling in crystallization kettle, filtering separation, crystallization filtrate is glyphosate saturated solution, reclaims so that recycled, collecting filter cake is dried, obtain glyphosate crystal 258.9g, content is 97.9%, and yield is 97.3%.
Example four
First the pmida98 of 400g (mass percentage content is 98%), 40g gac and 600g deionized water are dropped in stainless steel autoclave, stir, be warming up to 45 ° of C, pass into air, carry out oxidizing reaction, maintain system pressure 0.5MPa, react to the content of pmida98 and be reduced to 15%, add 15g synergistic catalyst to continue reaction complete to being oxidized.Feed liquid is moved in crystallization kettle, treat that glyphosate sufficient crystallising separates out, filter, separation, obtaining mother liquor formaldehyde content is 0.11%, and this mother liquor reclaims, and carries out recycled.
The blending filter cake that contains glyphosate and gac of collecting is put in 4000mlPMG saturated solution, rising temperature for dissolving is filtered, and reclaims the catalyzer in filtrate, with stand-by after a small amount of washing, filtrate is squeezed into crystallisation by cooling in crystallization kettle, filtering separation, crystallization filtrate is glyphosate saturated solution, reclaims so that recycled, collecting filter cake is dried, obtain glyphosate crystal 294.5g, content is 98.9%, and yield is 97.8%.
Claims (3)
1. the method for an improved preparing glyphosate from N-phosphonomethyl aminodiacetic acid, the method be take pmida98 as raw material, gac is catalyzer, load the molecular sieve of precious metal and transition metal be synergistic catalyst, it is characterized in that: by pmida98, gac and water wiring solution-forming, add in autoclave, pass into air and carry out oxidizing reaction, control 45 ~ 70 ℃ of temperature of reaction, maintain system pressure at 0.4 ~ 0.6MPa simultaneously, when pmida98 content is reduced to 5 ~ 15%, add synergistic catalyst to continue reaction to finishing, generate glyphosate; Described precious metal is rubidium, rhodium, palladium, platinum; Described transition metal is iron, tin, copper, titanium; Described molecular sieve is a kind of in Y type zeolite, T type zeolite, mordenite, silica zeolite, ZSM-5 type molecular sieve.
2. according to the method for the improved preparing glyphosate from N-phosphonomethyl aminodiacetic acid described in claim 1, it is characterized in that: described gac, pmida98 weight ratio are 1: (4-10); Described synergistic catalyst, pmida98 weight ratio are 1: (20-60).
3. according to the method for the improved preparing glyphosate from N-phosphonomethyl aminodiacetic acid described in claim 1, it is characterized in that: described pmida98 aqueous solution mass percent concentration is 20 ~ 50%.
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| CN201110116866.5A CN102241703B (en) | 2011-05-07 | 2011-05-07 | Improved method for preparing glyphosate from N-phosphonomethyl aminodiacetic acid |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US3969398A (en) * | 1974-05-01 | 1976-07-13 | Monsanto Company | Process for producing N-phosphonomethyl glycine |
| CN100372857C (en) * | 2004-05-12 | 2008-03-05 | 江苏好收成韦恩农药化工有限公司 | Production process of N-phosphono methyl glycine |
| CN101337978B (en) * | 2008-05-13 | 2011-06-29 | 浙江新安化工集团股份有限公司 | Method for preparing glyphosate by catalytic oxidation of N-(phosphonomethyl) iminodiacetic acid through oxygen-rich gas |
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