CN101648972B - Method for recycling glyphosate from glyphosate mother liquid - Google Patents
Method for recycling glyphosate from glyphosate mother liquid Download PDFInfo
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- CN101648972B CN101648972B CN2009101524272A CN200910152427A CN101648972B CN 101648972 B CN101648972 B CN 101648972B CN 2009101524272 A CN2009101524272 A CN 2009101524272A CN 200910152427 A CN200910152427 A CN 200910152427A CN 101648972 B CN101648972 B CN 101648972B
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Abstract
The invention relates to a method for recycling glyphosate from glyphosate mother liquid. The glyphosate mother liquid contains N,N-dimethylglycine, sulfate ion, ferric ion and impurities of arsenic ion, lead ion, mercury ion, and the like. The method comprises the following steps: adopting anion absorbent resin, in particular to anion absorbent resin with alkalescence to carry out absorption and separation including resin separation by means of parallel connection or series connection to separate the glyphosate from the mother liquid, thereby improving the product yield, effectively reducing the cost and reducing pollution.
Description
Technical field
The present invention relates to a kind of method, to containing N, N-N-methylsarcosine, sulfate ion from glyphosate mother solution recovery Glyphosate 62 IPA Salt; The higher glyphosate mother solution of saltiness of iron ion and arsenic, lead, the isoionic impurity of mercury adopts negatively charged ion polymeric adsorbent, particularly weakly-basic anion polymeric adsorbent; Fractionation by adsorption and comprise the resin isolation of carrying out with parallel connection or series system; Thereby the Glyphosate 62 IPA Salt in the mother liquor separates, and improves product yield, effectively reduces cost, and reduces and pollutes.
Background technology
Glyphosate 62 IPA Salt has another name called N-((phosphonomethyl)) glycocoll, is a kind of high-efficiency broad spectrum weedicide.Mainly contain two kinds of production technique of IDA method and glycine method at present.All there is the handling problem of glyphosate mother solution in two kinds of production technique.
CN101190926 and CN1648131 are employed in the glyphosate mother solution method that feeds ammonia and regulate pH value, the ammonium glyphosate after reclaiming triethylamine and obtaining concentrating.
CN1676527 discloses and in glyphosate mother solution, has added bicarbonate of ammonia, reclaims triethylamine, and filtrating is handled the method for back preparation gyphosate solution.
CN1824667 discloses and in glyphosate mother solution, has fed ammonia, carbonic acid gas successively, the reaction after-filtration, and filtrating is used for disposing the technology of gyphosate solution.
CN101195639 discloses glyphosate mother solution; Adopt diffusion dialysis, electrodialysis and diffusion dialysis and electrodialytic combination, reclaim the technology of hydrochloric acid, catalyst of triethylamine and Glyphosate 62 IPA Salt respectively, the diffusion dialysis film that this technology adopted; Cost is higher, limited service life, segregation rate are lower; Be unfavorable for large-scale industrial production, and electrodialytic efficiency is higher, and separating effect is undesirable.
CN1827626 discloses and has adopted membrane technique to put forward the method for Glyphosate 62 IPA Salt in the dense glyphosate mother solution; CN101058586 discloses the method for utilizing Glyphosate 62 IPA Salt in the high saliferous glyphosate mother solution of membrane technique concentrating and separating; CN101434620 discloses technology and the production system of from IDA method glyphosate mother solution, isolating former medicine through multistage membrane-concentrated technology; But the cost of film is higher, and limited service life, for scale operation certain limitation is arranged.
CN1050542 discloses and has made the aqueous solution that contains N-phosphonomethylglycine and impurity (for example N-formyl radical-N-phosphonomethylglycine, phosphorous acid etc.) flow through the ion exchange column that contains weakly basic anion exchange resin; Removing these impurity, thus purifying and concentrated N-phosphonomethylglycine method.
WO2006/055441 has announced and has utilized the patent that reclaims precious metal in the aqueous process streams of ion exchange resin from Glyphosate 62 IPA Salt is synthetic.
To the utilization of resin, present stage is mainly used in the impurity of removing in the Glyphosate 62 IPA Salt or reclaims the noble metal catalyst in the reaction in the Glyphosate 62 IPA Salt industry.The resin that impurity adopted that is used for removing Glyphosate 62 IPA Salt is weakly basic anion exchange resin, and handled system is the mother liquor that contains the Glyphosate 62 IPA Salt of N-formyl radical-N-phosphonomethylglycine and impurity such as N-phosphonomethyliminoacidetic acidetic, phosphorous acid formaldehyde formic acid.
Ion exchange resin is a kind of ionic exchanger with ion-exchange capacity of synthetic, water-fast polymer acid, polymeric alkali and polysalt.Contain a kind of (or several kinds) chemical active radical in the ion exchange resin; It promptly is an exchange functional group; In the aqueous solution, can dissociate out some positively charged ion (like H+ or Na+) or negatively charged ion (like OH-or Cl-), other positively charged ions or the negatively charged ion that had originally in the adsorbent solution simultaneously.Be that ion and the ion in the solution in the resin intercoursed, thereby the ion isolation in the solution is come out.
The general pretreatment technology that anionite-exchange resin adopted is following:
1, slowly flow through resin with 1NNaOH solution, consumption is about 2-3 times of strongly basic anionic resin volume, and the 3-5 of weakly basic anion resin volume times, per hour 1.5 times of bed volume flow through.
2, water flushing, water outlet PH is about 9, crosses resin with the NaCl solution stream of 3 times of resin volumes 5%, flow velocity is identical with 1.
3, flow through resin with the 1N hydrochloric acid soln, consumption and flow velocity are identical with 1.
4, water wash to water outlet PH be about 5.
5, use 1NNaOH solution, slowly flow through resin, consumption is 3-5 a times of resin volume, and flow velocity is identical with 1.
6, after alkaline stream finished, using deionized water rinsing was about 7 to going out water ph value, got final product near neutral.
For ion exchange resin; Iron ion in the separation system can cause ion exchange resin to be poisoned, and resin anion(R.A) is easy to made the resin blackening by the Organic pollutants in the liquid phase; Separating effect reduces; And the saltiness in the separated liquid phase is with the performance of remarkably influenced ion exchange resin, and saltiness is high more, and the performance of ion exchange resin is poor more.
Polymeric adsorbent is meant the high-crosslinking-degree three-dimensional polymeric molecule bead that does not contain ion-exchange group, and there is the duct of many molecular levels its inside, provides to be spread in the absorption place.Polymeric adsorbent is a kind of polymer absorbant with porous three dimensional structure synthetic, is the Van der Waals force that mainly relies between it and the molecule (adsorbate) that is adsorbed, carries out through its huge specific surface that physical adsorption works.Polymeric adsorbent is a kind of novel non-ionic resin, and its separation principle and ion exchange resin have the difference of essence.
Polymeric adsorbent mainly is physical adsorption for the absorption of adsorbate.Physical adsorption mainly is through Van der Waals force absorption, and its adsorption process depends on the size on temperature, pressure, surface, and little with the microtexture relation on surface.Its adsorption mechanism is because the atom field of force on the solid surface is unsaturated, and surface energy is arranged, thereby can adsorb some molecule to reduce surface energy.Solid adsorbs solute molecule from solution after, the concentration of solution will reduce, and the molecule that is adsorbed will be on solid surface dense gathering.See that from microstructure polymeric adsorbent includes many netted opening structures with microcosmic bead, the particulate total surface area is very big, has certain polar group, makes resin have bigger adsorptive power; On the other hand, there is certain scope in the aperture in these netted holes, makes them have certain selectivity to the compound through the aperture according to the difference of its molecular weight.Organic cpds reaches isolating purpose through certain solvent elution according to the difference of adsorptive power and the size of molecular weight on polymeric adsorbent.
The structure of polymeric adsorbent comprises chemical structure and physical structure.Monomeric polymerization or polymkeric substance through having various function group carry out the functional group reaction, can obtain the polymeric adsorbent of chemical structures.And the physical structure of resin mainly is its pore structure.
Different according to the polarity of resin, that polymeric adsorbent can be divided into is nonpolar, four types of Semi-polarity and low-pole, strong polarity.Nonpolar adsorption resin is to be got by the very little monomer polymerization of dipole moment; Do not contain any functional group; The hydrophobicity of hole table is stronger, can through with small molecules in the effect adsorbent solution of hydrophobic part in organism, be best suited for and from polar solvent (like water), adsorb apolar substance.The Semi-polarity polymeric adsorbent contains ester group, and its surface has concurrently hydrophobic and hydrophilic segment, both can also can from non-polar solvent, adsorb polar material by adsorbing apolar substance in the polar solvent.Polar resin contains carboxamido-group, cyanic acid, phenolic hydroxyl group isopolarity functional group, and they are through electrostatic interaction absorption polar material.And strong polar resin is meant and contains nitrogen oxide, pyridyl volume polymkeric substance, also is through strong electrostatic interaction absorption polar material.
Polymeric adsorbent is that raw material adds a certain amount of pore-creating agent divinylbenzene and is polymerized with vinylbenzene, a-vinyl toluene, TEB 3K, propionitrile etc. mainly; Mostly be spherical particle; Diameter generally between 0.3～1.25mm, stablize diluted acid, diluted alkaline under the room temperature by swellable in solvent.
The pretreatment process with ubiquity that polymeric adsorbent adopted is following:
1, will prepare the new resin that the dress post uses, soak 2 hours with methyl alcohol or other water-soluble solvents (like ethanol, acetone) of 2 times of left and right sides volumes, and stirring frequently, make the abundant swelling of resin.
2, will be fully swollen polymeric adsorbent dress post, with the flow velocity of 3 to 4 times of bed volumes per hour, that 5 to 8 times methyl alcohol or other water miscible solvents (like ethanol, acetone) is through resin layer, constant mixed to the effluent thin up.
3, after the methanol treatment, with the flow velocity of 6 to 8 times of bed volumes per hour with deionized water through resin layer, displacing methyl alcohol can come into operation.
Saltiness in institute's separation system does not have influence for polymeric adsorbent, and iron ion can not cause polymeric adsorbent to be poisoned.
The weakly-basic anion polymeric adsorbent that belongs to that we adopt has essence different with ion exchange resin.
Summary of the invention
The glyphosate mother solution that the present invention is directed to mainly is to produce the glyphosate mother solution that Glyphosate 62 IPA Salt technology produces to glycine method; Wherein mainly contain N; N-N-methylsarcosine, sulfate ion, the higher glyphosate mother solution of saltiness of iron ion and arsenic, lead, the isoionic impurity of mercury.In the glyphosate mother solution owing to also have foreign ion such as iron ion; Can cause ion exchange resin to be poisoned; And the organic substance in the mother liquor can pollute ion exchange resin; And the salt in the mother liquor can cause the separation performance of ion exchange resin significantly to reduce, and therefore can't separate with the separation method of the ion exchange resin described in the patent CN1050542.
Polymeric adsorbent, itself does not receive the influence of foreign ions such as iron ion, and the saltiness in the mother liquor does not have remarkably influenced to polymeric adsorbent.
Contain a kind of (or several kinds) chemical active radical in the ion exchange resin, promptly exchange functional group, some negatively charged ion that in the aqueous solution, can dissociate out (like OH-or Cl-), other negatively charged ion that had originally in the adsorbent solution simultaneously.Be that ion and the ion in the solution in the resin intercoursed, thereby the ion isolation in the solution is come out.Therefore, carry out fractionation by adsorption, receive anion-containing influence in the mother liquor, and the selectivity of absorption is not good through ion exchange resin.And the weakly-basic anion polymeric adsorbent, mainly through Van der Waals force absorption, its adsorption mechanism is because the atom field of force on the solid surface is unsaturated, and surface energy is arranged, thereby can adsorb some molecule to reduce surface energy.See that from microstructure polymeric adsorbent includes many netted opening structures with microcosmic bead, the particulate total surface area is very big, has certain polar group, makes resin have bigger adsorptive power; On the other hand, there is certain scope in the aperture in these netted holes, makes them have certain selectivity to the compound through the aperture according to the difference of its molecular weight.Organic cpds reaches isolating purpose through certain solvent elution according to the difference of adsorptive power and the size of molecular weight on polymeric adsorbent.Therefore the weakly-basic anion polymeric adsorbent has stronger selectivity and adsorptive power.And not influenced by other impurity negatively charged ion in the adsorbate.
Therefore the present invention is directed to this kind glyphosate mother solution; Adopt the Glyphosate 62 IPA Salt in the negatively charged ion polymeric adsorbent absorption mother liquor, the Glyphosate 62 IPA Salt to resin absorption carries out desorb again, thereby the Glyphosate 62 IPA Salt in the mother liquor is separated; Improve product yield, effectively reduce cost, reduce and pollute.
The present invention adopts the Glyphosate 62 IPA Salt in the negatively charged ion polymeric adsorbent fractionation by adsorption mother liquor; Contain N in the mother liquor; N-N-methylsarcosine, sulfate ion; Iron ion and arsenic, lead, the isoionic impurity of mercury, particularly weakly-basic anion polymeric adsorbent, and comprise the resin isolation of carrying out with parallel connection or series system.At 0～90 ℃, to the acid mother liquor of pH value 0～7 or 7～14 alkali liquor, flow velocity 0.1～20BV/h; Adsorb through resin respectively, separate adsorption desorption with basic soln again, comprise alkali metal hydroxide, alkaline carbonate, ammoniacal liquor, volatile caustic; And Isopropylamine, n n dimetylaniline equimolecular quantity are at 300 aqueous solution with interior organic amine; Particularly the aqueous solution of aqueous sodium hydroxide solution and Isopropylamine, n n dimetylaniline more after treatment, is isolated the method for Glyphosate 62 IPA Salt.
Particularly, the present invention realizes through following technical scheme:
Steps A: glyphosate mother solution is carried out concentration and filtration, obtain clarified mother liquor;
Step B: the resin of in adsorption column, packing into, after conventional pre-treatment, the Glyphosate 62 IPA Salt clarified mother liquor upper prop that steps A is obtained adsorbs; It is 0.1～20BV/h with flow velocity that temperature is controlled at 0～90 ℃; Make solution stream through resin, Glyphosate 62 IPA Salt is adsorbed, and absorption effluent is carried out wastewater treatment;
Step C: configuration 3～8% sodium hydroxide solution., Isopropylamine solution or other basic solns be desorbing agent, temperature is controlled at 0～90 ℃, flow velocity 0.1～20BV/h carries out desorption, the desorption water outlet is recyclable Glyphosate 62 IPA Salt through acidifying or after handling.
Alternatively; The Glyphosate 62 IPA Salt clarified mother liquor that in step B, will obtain through steps A is through placed in-line resin groups; First resin column is used to remove impurity such as increasing sweet phosphine; And the effluent of first resin removed Glyphosate 62 IPA Salt through second resin, and it is 0.1～20BV/h with flow velocity that temperature is controlled at 0～90 ℃, the effluent through second resin column carries out waste water or other processing.
In step C,, can adopt different parsing agent according to the resin that is adopted among the step B.Can adopt and top the same basic soln for the series connection resin, also can adopt 4%～8% hydrochloric acid soln.
Negatively charged ion polymeric adsorbent among the present invention is that those skilled in the art are familiar with; Comprise following commercially available negatively charged ion polymeric adsorbent: Wan Dong chemical plant, Anhui Province WD-XF strong basicity high-exchange-capacity negatively charged ion polymeric adsorbent; The H103 of Anhui Samsung resin Science and Technology Ltd., DM11; Xi'an blue dawn of the resin LX-8 of ltd, XDA-300, LX-26M, LX-100A, XDA-200, the blue dark extraordinary resin Ls Cable Ltd.-100B in Xi'an, LS-103, LS-13, LS-36; LS-18, the WX-5 of Anhui Wan Dong chemical industry ltd.Other negatively charged ion polymeric adsorbents well-known to those skilled in the art also can use.
The basic soln that is used to resolve comprises the aqueous solution of alkali metal hydroxide, like sodium hydroxide etc.; Ammoniacal liquor or volatile caustic, volatile salt etc., and alkali-metal carbonate solution and organic amines such as Isopropylamine, n n dimetylaniline.
The present invention is directed to glyphosate mother solution, particularly contain N, N-N-methylsarcosine, sulfate ion; The glyphosate mother solution of iron ion and arsenic, lead, the isoionic impurity of mercury, wherein the impurity iron ion can cause resin poison, adopts the Glyphosate 62 IPA Salt in the negatively charged ion polymeric adsorbent absorption mother liquor; Glyphosate 62 IPA Salt to resin absorption carries out desorb again; Thereby the Glyphosate 62 IPA Salt in the mother liquor separates, and improves product yield, effectively reduces cost, and reduces and pollutes.Adopt present technique to handle glyphosate mother solution, can reclaim the Glyphosate 62 IPA Salt 97% or more in the mother liquor, not only change is handled mother liquor in the past and need be spent expensively, also reclaims valuable Glyphosate 62 IPA Salt create beneficial result simultaneously.
Embodiment:
Embodiment 1:
Get glyphosate mother solution 500g, Glyphosate 62 IPA Salt concentration is 1.0%, increases sweet phosphine concentration 2.4%; Through handling, regulating its pH value is 1.5, gets LS-36 negatively charged ion polymeric adsorbent 50ml and LS-18 adsorpting anion absorption 35ml resin; Adorn post respectively and resin is carried out pre-treatment, resin column adopts series system to connect, and the glyphosate mother solution upper prop is adsorbed; 5 ℃ of adsorption temps, flow velocity 2BV/h, the recovery 97.0%.Adsorb saturated after, first resin with 4% sodium hydroxide solution at 60 ℃, carry out desorption under the flow velocity 4BV/h condition; Desorbed solution is after concentrating, and increasing sweet phosphine concentration is 11.5%, increases the sweet phosphine recovery 95.8%; Second resin separates drying with 4% hydrochloric acid soln desorption after concentrating; Get Glyphosate 62 IPA Salt crystal 4 .81g, Glyphosate 62 IPA Salt content 98.7%.
Embodiment 2:
Get glyphosate mother solution 1000g, its Glyphosate 62 IPA Salt concentration is 1.3%, through handling; Regulating its pH value is 2.5, gets LX-18 negatively charged ion polymeric adsorbent 50ml dress post and resin is carried out pre-treatment, and the glyphosate mother solution upper prop is adsorbed; 25 ℃ of adsorption temps, flow velocity 10BV/h, the recovery 91.8%.Adsorb saturated back with 8% sodium hydroxide solution at 50 ℃, carry out desorption under the flow velocity 5BV/h condition, obtaining sodium glyphosate concentration is 5.6%, desorption rate is 94.3%.Sodium glyphosate solution is added hydrochloric acid regulate pH value to 1.5～2, sedimentation and filtration, drying gets Glyphosate 62 IPA Salt crystal 11.55g, Glyphosate 62 IPA Salt content 97.4%.
Embodiment 3:
Get Glyphosate 62 IPA Salt alkali liquor 800g, its Glyphosate 62 IPA Salt concentration is 0.8%, through handling; Regulating its pH value is 3.5, gets H-103 negatively charged ion polymeric adsorbent 50ml dress post and resin is carried out pre-treatment, and the glyphosate mother solution upper prop is adsorbed; 15 ℃ of adsorption temps, flow velocity 5BV/h, the recovery 92.3%.Adsorb saturated back with 25% ammoniacal liquor at 40 ℃, carry out desorption under the flow velocity 7.5BV/h condition, obtaining the ammonium glyphosate salt concn is 12.8%, desorption rate is 95.9%.The ammonium glyphosate salts solution is added hydrochloric acid regulate pH value to 1.5～2, sedimentation and filtration, drying gets Glyphosate 62 IPA Salt crystal 5 .9g, Glyphosate 62 IPA Salt content 96.1%.
Embodiment 4:
Get glyphosate mother solution 700g, its Glyphosate 62 IPA Salt concentration is 1%, through handling; Regulating its pH value is 1.5, gets WD-XF polymeric adsorbent 100ml dress post and resin is carried out pre-treatment, and the glyphosate mother solution upper prop is adsorbed; 25 ℃ of adsorption temps, flow velocity 1BV/h, the recovery 88.7%.Adsorb saturated back with Isopropylamine solution at 60 ℃, carry out desorption under the flow velocity 2BV/h condition, obtaining Glyphosate 62 IPA Salt concentration is 5.6%, desorption rate is 90.4%.Sodium glyphosate solution is added hydrochloric acid regulate pH value to 1.5～2, sedimentation and filtration, drying gets Glyphosate 62 IPA Salt crystal 5 .8g, Glyphosate 62 IPA Salt content 96.8%.
Although the preceding text specific embodiments of the invention has given to describe in detail and explanation; But should indicatedly be; We can carry out various equivalences to above-mentioned embodiment according to conception of the present invention and change and modification; When the function that it produced does not exceed spiritual that specification sheets and accompanying drawing contain yet, all should be within protection scope of the present invention.
Claims (5)
1. method that from glyphosate mother solution, reclaims Glyphosate 62 IPA Salt may further comprise the steps:
Steps A: glyphosate mother solution is carried out concentration and filtration, obtain clarified mother liquor;
Step B: the negatively charged ion polymeric adsorbent of in adsorption column, packing into, after conventional pre-treatment, the Glyphosate 62 IPA Salt clarified mother liquor upper prop that steps A is obtained adsorbs; It is 0.1～20BV/h with flow velocity that temperature is controlled at 0～90 ℃; Make solution stream through resin, Glyphosate 62 IPA Salt is adsorbed, and absorption effluent is carried out wastewater treatment; Said negatively charged ion polymeric adsorbent is Wan Dong chemical plant, Anhui Province WD-XF strong basicity high-exchange-capacity negatively charged ion polymeric adsorbent or the H103 of Anhui Samsung resin Science and Technology Ltd., DM11 or Xi'an blue dawn of the resin LX-8 of ltd; The blue dark extraordinary resin Ls Cable Ltd.-100B in XDA-300, LX-26M, LX-100A, XDA-200 or Xi'an, LS-103, LS-13, LS-36, LS-18 or the WX-5 of Anhui Wan Dong chemical industry ltd;
Step C: the aqueous solution, ammoniacal liquor, volatile caustic, volatile salt, alkali-metal carbonate solution or the organic amine of the alkali metal hydroxide of configuration 3～8% are desorbing agent; Temperature is controlled at 0～90 ℃; Flow velocity 0.1～20BV/h carries out desorption, and the desorption water outlet is recyclable Glyphosate 62 IPA Salt after acidifying.
2. according to the method for claim 1; The Glyphosate 62 IPA Salt clarified mother liquor that wherein in step B, will obtain through steps A is through placed in-line negatively charged ion polymeric adsorbent group; First resin column is used to remove impurity such as increasing sweet phosphine; And the effluent of first resin removed Glyphosate 62 IPA Salt through second resin; It is 0.1～20BV/h with flow velocity that temperature is controlled at 0～90 ℃, and the effluent through second resin column carries out waste water or other are handled, and the desorbing agent of series connection resin is the basic soln the same with claim 1 or adopts 4%～8% hydrochloric acid soln.
3. according to the method for claim 1 or 2, wherein the negatively charged ion polymeric adsorbent is the weakly-basic anion polymeric adsorbent.
4. according to the method for claim 1 or 2 or 3, wherein glyphosate mother solution is to contain N, N-N-methylsarcosine, sulfate ion, the glyphosate mother solution that the saltiness of the impurity of iron ion and arsenic, lead, mercury ion is higher.
5. according to the method for claim 1 or 3, wherein the basic soln of desorption is sodium hydroxide, Isopropylamine or n n dimetylaniline.
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| CN102100978B (en) * | 2010-12-14 | 2013-03-13 | 南京化学试剂有限公司 | Method for removing trace anions from alcohol organic solvent by resin method |
| CN102153584B (en) * | 2011-02-10 | 2013-05-08 | 江苏优士化学有限公司 | Comprehensive treatment technique for recycling glyphosate mother liquor |
| CN104016534A (en) * | 2014-02-25 | 2014-09-03 | 江苏海普功能材料有限公司 | Method for recovering glyphosate production wastewater by resin adsorption |
| CN109621958B (en) * | 2018-12-29 | 2020-09-04 | 中国科学院深圳先进技术研究院 | Method for degrading glyphosate wastewater by virtue of low-temperature plasma concerted catalysis |
| CN114166968A (en) * | 2021-11-29 | 2022-03-11 | 湖北省兴发磷化工研究院有限公司 | Method for rapidly determining content of glyphosine in glyphosate by liquid chromatography |
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| CN1050542A (en) * | 1989-08-17 | 1991-04-10 | 孟山都公司 | The method of purifying N-phosphonomethylglycine |
| CN1827626A (en) * | 2006-04-07 | 2006-09-06 | 浙江龙游绿得农药化工有限公司 | Process for separation and purification of glyphosate from glyphosate solution by membrane technology |
| CN101120009A (en) * | 2004-11-12 | 2008-02-06 | 孟山都技术公司 | Recovery of noble metals from aqueous process streams in the synthesis of glyphosate using adsorption media such as ion exchange resins |
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| CN1050542A (en) * | 1989-08-17 | 1991-04-10 | 孟山都公司 | The method of purifying N-phosphonomethylglycine |
| CN101120009A (en) * | 2004-11-12 | 2008-02-06 | 孟山都技术公司 | Recovery of noble metals from aqueous process streams in the synthesis of glyphosate using adsorption media such as ion exchange resins |
| CN1827626A (en) * | 2006-04-07 | 2006-09-06 | 浙江龙游绿得农药化工有限公司 | Process for separation and purification of glyphosate from glyphosate solution by membrane technology |
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