CN101648972A - Method for recycling glyphosate from glyphosate mother liquid - Google Patents
Method for recycling glyphosate from glyphosate mother liquid Download PDFInfo
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- CN101648972A CN101648972A CN200910152427A CN200910152427A CN101648972A CN 101648972 A CN101648972 A CN 101648972A CN 200910152427 A CN200910152427 A CN 200910152427A CN 200910152427 A CN200910152427 A CN 200910152427A CN 101648972 A CN101648972 A CN 101648972A
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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 andseparation 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 reducingthe cost and reducing pollution.
Description
Technical field
The present invention relates to a kind of method that reclaims glyphosate from glyphosate mother solution, at containing N, N-N-methylsarcosine, sulfate ion, 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 in the mother liquor is separated, improve product yield, effectively reduce cost, reduce and pollute.
Background technology
Glyphosate has another name called N-((phosphonomethyl)) glycine, 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 adopt the method that feeds ammonia in glyphosate mother solution to regulate pH value, reclaim triethylamine and obtain concentrating after ammonium glyphosate.
CN1676527 discloses and added bicarbonate of ammonia in glyphosate mother solution, reclaims triethylamine, and filtrate is handled the method for back preparation gyphosate solution.
CN1824667 discloses and fed ammonia, carbonic acid gas successively in glyphosate mother solution, the reaction after-filtration, and filtrate being used for disposed 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 respectively, the diffusion dialysis film that this technology adopted, cost is higher, the life-span is limited, segregation rate is 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 in the dense glyphosate mother solution, CN101058586 discloses the method for utilizing glyphosate in the high saliferous glyphosate mother solution of membrane technique concentrating and separating, CN101434620 discloses technology and the production system of isolating former medicine by multistage membrane concentration technology from IDA method glyphosate mother solution, but the cost of film is higher, and the life-span is limited, 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 weak base 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 is synthetic.
To the utilization of resin, present stage is mainly used in the impurity of removing in the glyphosate or reclaims noble metal catalyst in the reaction in the glyphosate industry.The resin that impurity adopted that is used for removing glyphosate is weak base anion-exchange resin, and handled system is the mother liquor that contains the glyphosate 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) chemical active radical in the ion exchange resin, it promptly is an exchange functional group, some positively charged ion (as H+ or Na+) or negatively charged ion (as OH-or Cl-), other positively charged ions or the negatively charged ion that had originally in the adsorbent solution simultaneously can dissociate out in the aqueous solution.Be that ion in the resin and the ion in the solution are intercoursed, thereby the ion isolation in the solution is come out.
The general pretreatment technology that anionite-exchange resin adopted is as follows:
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 finishes, be about 7 to going out water ph value, get final product near neutral with deionized water rinsing.
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 by the Organic pollutants in the liquid phase, make the resin blackening, 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, is undertaken by 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 by 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 dense poly-on solid surface.On microstructure, polymeric adsorbent includes many netted opening structures with microcosmic bead, and 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 by the aperture according to the difference of its molecular weight.Organic compound 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.Carry out the functional group reaction by monomeric polymerization or the polymkeric substance that has various function group, can obtain the polymeric adsorbent of different chemical structures.And the physical structure of resin mainly is its pore structure.
According to the polarity difference of resin, that polymeric adsorbent can be divided into is nonpolar, Semi-polarity and low-pole, strong polarity four classes.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 by with small molecules in the effect adsorbent solution of hydrophobic part in organism, be best suited for and from polar solvent (as 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 adsorb polar material from non-polar solvent by adsorbing apolar substance in the polar solvent.Polar resin contains amide group, cyano group, phenolic hydroxyl group isopolarity functional group, and they adsorb polar material by electrostatic interaction.And strong polar resin is meant and contains nitrogen oxide, pyridyl volume polymkeric substance, also is by 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, methyl methacrylate, 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 as follows:
1, will prepare the new resin that the dress post uses, soak 2 hours with methyl alcohol or other water-soluble solvents (as 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 (as ethanol, acetone) is by resin layer, constant mixed to the effluent liquid thin up.
3, after methyl alcohol is handled, with the flow velocity of 6 to 8 times of bed volumes per hour with deionized water by 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 technology produces at 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, 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 is not subjected to the influence of foreign ions such as iron ion, and the saltiness in the mother liquor has no significant effect polymeric adsorbent.
Contain a kind of (or several) chemical active radical in the ion exchange resin, promptly exchange functional group, some negatively charged ion that in the aqueous solution, can dissociate out (as OH-or Cl-), other negatively charged ion that had originally in the adsorbent solution simultaneously.Be that ion in the resin and the ion in the solution are intercoursed, thereby the ion isolation in the solution is come out.Therefore, carry out fractionation by adsorption, be subjected to anion-containing influence in the mother liquor, and the selectivity of absorption is not good by ion exchange resin.And the weakly-basic anion polymeric adsorbent, mainly by 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.On microstructure, polymeric adsorbent includes many netted opening structures with microcosmic bead, and 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 by the aperture according to the difference of its molecular weight.Organic compound 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 in the negatively charged ion polymeric adsorbent absorption mother liquor, the glyphosate to resin absorption carries out desorb again, thereby the glyphosate in the mother liquor is separated, improve product yield, effectively reduce cost, reduce and pollute.
The present invention adopts the glyphosate 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, weakly-basic anion polymeric adsorbent particularly, 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 by resin respectively, separate adsorption desorption with basic solution again, comprise alkali metal hydroxide, alkaline carbonate, ammoniacal liquor, ammonium hydroxide, and Isopropylamine, dimethylamine equimolecular quantity are at 300 aqueous solution with interior organic amine, particularly the aqueous solution of aqueous sodium hydroxide solution and Isopropylamine, dimethylamine more after treatment, is isolated the method for glyphosate.
Particularly, the present invention is achieved through the following technical solutions:
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 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 is adsorbed, and absorption effluent is carried out wastewater treatment;
Step C: configuration 3～8% sodium hydroxide solution., Isopropylamine solution or other basic solutions 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 through acidifying or after handling.
Alternatively, the glyphosate clarified mother liquor that will obtain by steps A in step B is by placed in-line resin groups, first resin column is used to remove impurity such as increasing sweet phosphine, and the effluent liquid of first resin removed glyphosate by second resin, it is 0.1～20BV/h that temperature is controlled at 0～90 ℃ and flow velocity, and the effluent liquid by 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 solution 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 company limited, 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 company limited.Other negatively charged ion polymeric adsorbents well-known to those skilled in the art also can use.
The basic solution that is used to resolve comprises the aqueous solution of alkali metal hydroxide, as sodium hydroxide etc.; Ammoniacal liquor or ammonium hydroxide, volatile salt etc., and alkali-metal carbonate solution and organic amines such as Isopropylamine, dimethylamine.
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 in the negatively charged ion polymeric adsorbent absorption mother liquor, glyphosate to resin absorption carries out desorb again, thereby the glyphosate in the mother liquor is separated, improve product yield, effectively reduce cost, reduce and pollute.Adopt present technique to handle glyphosate mother solution, can reclaim the glyphosate 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 create beneficial result simultaneously.
Embodiment:
Embodiment 1:
Get glyphosate mother solution 500g, glyphosate concentration is 1.0%, increases sweet phosphine concentration 2.4%, through handling, regulating its pH value is 1.5, get 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, the glyphosate mother solution upper prop is adsorbed, 5 ℃ of adsorption temps, flow velocity 2BV/h, the rate of 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%, increase the sweet phosphine rate of recovery 95.8%, second resin separates drying with 4% hydrochloric acid soln desorption after concentrating, get glyphosate crystal 4 .81g, glyphosate content 98.7%.
Embodiment 2:
Get glyphosate mother solution 1000g, its glyphosate 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 rate of 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 crystal 11.55g, glyphosate content 97.4%.
Embodiment 3:
Get glyphosate alkali liquor 800g, its glyphosate 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 rate of 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 crystal 5 .9g, glyphosate content 96.1%.
Embodiment 4:
Get glyphosate mother solution 700g, its glyphosate 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 rate of recovery 88.7%.Adsorb saturated back and use Isopropylamine solution at 60 ℃, carry out desorption under the flow velocity 2BV/h condition, obtaining glyphosate concentration is 5.6%, and 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 crystal 5 .8g, glyphosate content 96.8%.
Although above the specific embodiment of the present invention has been 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 (6)
1, a kind of method that reclaims glyphosate from glyphosate mother solution 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 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 is adsorbed, and absorption effluent is carried out wastewater treatment;
Step C: the aqueous solution of configuration 3～8% alkali metal hydroxide, ammoniacal liquor, ammonium hydroxide or, volatile salt, alkali-metal carbonate solution or organic amine be 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 through acidifying or after handling.
2, according to the method for claim 1, wherein the glyphosate clarified mother liquor that will obtain by steps A in step B is by 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 liquid of first resin removed glyphosate by second resin, it is 0.1～20BV/h with flow velocity that temperature is controlled at 0～90 ℃, effluent liquid by second resin column carries out waste water or other processing, and the desorbing agent of series connection resin is the basic solution 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 2, wherein the negatively charged ion polymeric adsorbent is WD-XF strong basicity high-exchange-capacity negatively charged ion polymeric adsorbent, H103, DM11, LX-8, XDA-300, LX-26M, LX-100A, XDA-200, LS-100B, LS-103, LS-13, LS-36, LS-18 or WX-5.
6, according to the method for claim 1 or 3, wherein the basic solution of desorption is sodium hydroxide, Isopropylamine or dimethylamine.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102100978A (en) * | 2010-12-14 | 2011-06-22 | 南京化学试剂有限公司 | Method for removing trace anions from alcohol organic solvent by resin method |
| CN102153584A (en) * | 2011-02-10 | 2011-08-17 | 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 |
| CN109621958A (en) * | 2018-12-29 | 2019-04-16 | 中国科学院深圳先进技术研究院 | A kind of method of low-temperature plasma synergistic catalytic degradation glyphosate waste water |
| 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 |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES2022053T3 (en) * | 1989-08-17 | 1995-04-16 | Monsanto Co | N-PHOSPHONOMETHYLGLYCIN PURIFICATION PROCEDURE. |
| AR054096A1 (en) * | 2004-11-12 | 2007-06-06 | Monsanto Technology Llc | RECOVERY OF NOBLE METALS OF WATER PROCESS CURRENTS AND PREPARATION PROCESS OF N- (PHOSPHONOMETIL) -GLYCINE |
| CN100371338C (en) * | 2006-04-07 | 2008-02-27 | 捷马化工股份有限公司 | Process for separation and purification of glyphosate from glyphosate solution by membrane technology |
-
2009
- 2009-09-08 CN CN2009101524272A patent/CN101648972B/en active Active
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102100978A (en) * | 2010-12-14 | 2011-06-22 | 南京化学试剂有限公司 | Method for removing trace anions from alcohol organic solvent by resin method |
| 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 |
| CN102153584A (en) * | 2011-02-10 | 2011-08-17 | 江苏优士化学有限公司 | Comprehensive treatment technique for recycling glyphosate mother liquor |
| 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 |
| CN109621958A (en) * | 2018-12-29 | 2019-04-16 | 中国科学院深圳先进技术研究院 | A kind of method of low-temperature plasma synergistic catalytic degradation glyphosate waste water |
| 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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| CN101648972B (en) | 2012-11-21 |
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