CN101591352B - Novel process for preparing glyphosate by glycin method - Google Patents
Novel process for preparing glyphosate by glycin method Download PDFInfo
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Abstract
The invention relates to a method for preparing glyphosate, which comprises the following steps: according to certain mixture ratio, putting glycin and paraformaldehyde into a monacid alcohol/tertiary amine system together for depolymerization condensation; then, after the mixture and dialkyl phosphate in mixing amount undergo condensation reaction, directly reclaiming monacid alcohol and tertiary amine; then, controlling temperature for acidolysis; in the acidolysis or after the acidolysis, removing and oxidizing formaldehyde; and deacidifying and neutralizing the reactant to prepare the glyphosate. The method adopts a plurality of methods such as reduction of the mixture ratio of the paraformaldehyde, direct exsolution and application, low-temperature acidolysis after the exsolution and the like to remove the influence of the formaldehyde, reduce consumption and stabilize the yield and the quality of the glyphosate.
Description
Invention field
The present invention relates to a kind of is the method for feedstock production herbicide glyphosate (N-(phosphonomethyl) glycine) with the alkyl phosphite; Specifically, the inventive method comprises the steps: that glycocoll and Paraformaldehyde 96 are dropped into monohydroxy-alcohol/tertiary amine system simultaneously according to certain proportioning separates polycondensation reaction, can select this moment to reclaim volatile components such as alkohol and amine through the mode that normal pressure, decompression or air are resolved; Dialkyl phosphite with proportional quantity carries out condensation reaction again; The mode of resolving through normal pressure, decompression or air afterwards reclaims alkohol and amine, temperature control acidolysis again, and in acidolysis, remove or oxidation of formaldehyde; Glyphosate 62 IPA Salt is prepared in depickling or neutralization then.
Background of invention
Glyphosate 62 IPA Salt has another name called the sweet acid of phosphine, and chemical name is N-(phosphonomethyl) glycocoll, and chemical structural formula is (I):
It is a kind of steriland herbicide of wide spectrum efficiently; Find and development and use in 1972 by U.S. Monsanto Company; Because of it has good interior suction conductive performance, very effective to the control of multiple dark root malignant weed, Absatzvolumen increases rapidly in recent years; Along with the popularization of some genetically modified crops, its range of application will further enlarge.
Year scale at the dialkyl phosphite synthesizing glyphosate of China has reached 200,000 tons/year.It is less then to study report for the dialkyl phosphite route, and application number is that to disclose a kind of be the Glyphosate 62 IPA Salt preparation technology of raw material with the dialkyl phosphite for 85102988 patent of invention; Application number is that 00125933 patent of invention discloses a kind of improvement to dialkyl phosphite technology, does not adopt Paraformaldehyde 96 but utilizes the by product methylal of self to come synthesizing glyphosate; " trimethyl phosphite synthesizing glyphosate technical study " (" PESTICIDES " 1999.Vol.38No.6P8) introduced trimethyl phosphite and the glycocoll method at the aqueous phase synthesizing glyphosate in addition; Application number is that to provide a kind of be the method for starting raw material synthesizing glyphosate with the glycocoll an alkali metal salt to the patent of invention of 03147313.X.
Dialkyl phosphite technology adopts Paraformaldehyde 96 to obtain methylal in pure amine system depolymerization more at present, and then with the glycocoll condensation, with the dialkyl phosphite reaction, last acidolysis, dealcoholysis, depickling, crystallization, filtration, oven dry obtain the former powder of Glyphosate 62 IPA Salt again.
Summary of the invention
The present invention provides the novel process of the preparation Glyphosate 62 IPA Salt (N-(phosphonomethyl) glycine) of a kind of low cost, high yield, energy-conserving and environment-protective.
The present invention is that application number is the improvement invention of 200510105695.0 patented claims.When stating patented claim technology on the implementation, we find, along with the carrying out of acidolysis process; Temperature raises gradually; The content of formaldehyde also increases gradually, directly cause a large amount of Glyphosate 62 IPA Salts in acid system with formaldehyde condensation, cause Glyphosate 62 IPA Salt content to descend and the nitrogen by product increase that methylates.Discover that further the temperature of control acidolysis removes or oxidation of formaldehyde simultaneously, not only can the stable prod yield; And can also reduce the consumption and the consumption of material, and reduce acid, alkali consumption and the three wastes and produce, reduce the methanol rectification process; Promote production capacity greatly, reduce investment.In this invention, can reduce even avoid the generation of methyl chloride during acidolysis dramatically simultaneously, reduce the loss of methyl chloride, further reduce investment pollution, minimizing methyl alcohol and the hydrochloric acid of environment.
Method of the present invention is, the mode through usual manner (normal pressure, decompression also or gas resolve) for example below 20-110 ℃, reclaims monohydroxy-alcohol and tertiary amine at lesser temps with phosphorous acid alkyl dialkyl esterification condensation liquid earlier; After no obvious liquid flows out; Esterification condensation liquid after the concentration adds the mineral acid acidolysis by proportioning, and in acidolysis, removes or oxidation of formaldehyde, until reacting completely; Reduce pressure then depickling (below the P=-0.02Mpa all can) or directly add in the alkali and regulate the pH value; Separate out product, filtration drying obtains the former powder of Glyphosate 62 IPA Salt, and filtrating is used to prepare the liquid Glyphosate 62 IPA Salt.Monohydroxy-alcohol, the tertiary amine that reclaims can be used for washing isolating inorganic salt from esterification condensation liquid, replenishes a little after washing separates and can directly apply mechanically.In the methods of the invention; After finishing, the esterification condensation reaction can select fully to reclaim volatile components such as monohydroxy-alcohol and tertiary amine through the mode that normal pressure, decompression or air are resolved as far as possible; Further get rid of the influence of methylal to subsequent reactions; Only need add proper amount of solvent behind the precipitation and get final product this moment, and in this method, esterifying liquid still reclaims solvent.
In existing technology, contain a large amount of moisture content in the alcoholic solution of recovery, needing after the rectifying could recovery set usefulness, and in addition, the recovery of amine and the method for rectifying add alkali in the mother liquor earlier makes it dissociate out, separates the rectifying tertiary amine then, reaches recovery set usefulness after the request for utilization.In this inventive method; Most alcohol and part tertiary amine just reclaim under anhydrous situation; Therefore can directly apply mechanically, that has saved most of material adds operations such as alkali, drying, neutralization deacidification, rectifying, has practiced thrift starting material and equipment input greatly; Improve usage ratio of equipment accordingly, reduced production cost.Compare with existing technology, under equal conditions this technology acidolysis usage ratio of equipment be existing technology 2-4 doubly, greatly reduce the load of depickling simultaneously.Along with the disengaging reaction system constantly of formaldehyde, under the low temperature acidolysis more complete, the product destructive probability that is decomposed reduces, and reacts more stable.
In concrete embodiment, the inventive method comprises the steps:
1), carries out condensation reaction with the phosphorous acid dialkyl again with glycocoll and Paraformaldehyde 96 drops into monohydroxy-alcohol simultaneously and tertiary amine system is separated polycondensation reaction;
The mode of 2) resolving through normal pressure, decompression or gas reclaims monohydroxy-alcohol and tertiary amine; After no obvious liquid flows out; Temperature control adds the mineral acid acidolysis again, and in acidolysis, removes or oxidation of formaldehyde, up to reacting completely; Glyphosate 62 IPA Salt is prepared in reduce pressure then depickling (below the P=-0.02Mpa all can) and/or directly add in the alkali and regulate pH value and deacidify.
In preferred embodiments, the inventive method comprises the steps:
1) glycocoll and Paraformaldehyde 96 are dropped in monohydroxy-alcohol and the tertiary amine system simultaneously, be stirred to transparent after, be warming up to about 40-50 ℃, add dialkyl phosphite again, 40-70 ℃ of insulation until reacting completely;
The mode of 2) resolving through decompression or gas reclaims monohydroxy-alcohol and tertiary amine, after no obvious liquid flows out, is cooled to naturally about 40 ℃; Temperature control adds hydrochloric acidolysis again; And in acidolysis, resolve through gas and/or the mode of decompression removes formaldehyde, perhaps at the simultaneous oxidation formaldehyde of acidolysis, up to reacting completely; Glyphosate 62 IPA Salt is prepared in reduce pressure then depickling (below the P=-0.02Mpa all can) and/or directly add in the alkali and regulate pH value and deacidify.
Step 2) temperature control acidolysis reaction temperature is preferably 40-80 ℃ in, and the decompression depickling stops decompression when temperature reaches 110 ℃; In another preferred embodiment; Step 2) mode that adopts decompression or gas to resolve reclaims alkohol and amine; Adopt 40-80 ℃ of insulation acidolysis, the drum air is resolved and to be removed or oxidation of formaldehyde finishes until reaction in the time of acidolysis, adds the for example neutralizations such as sodium hydroxide, Pottasium Hydroxide or sodium hydrogencarbonate of conventional alkali afterwards; Adjust pH is 0.7-3.0, is preferably 1.5-2.5.
Reaction obtains N-dialkyl (phosphonomethyl) glycine in step 1), is referred to as esterification condensation liquid.
In the methods of the invention, material proportion of employing (mol ratio) and condition are:
Glycocoll: Paraformaldehyde 96 is 1: 1.2-2, preferred 1: 1.4-1.95.
Glycocoll: dialkyl phosphite is 1: 0.95-1.3, preferred 1: 0.95-1.19.
Said precipitation (taking off monohydroxy-alcohol and tertiary amine etc.) and acidolysis temperature are 20-110 ℃, are preferably 40-80 ℃.
The said formaldehyde temperature that removes is 20-110 ℃, is preferably 40-80 ℃.
Described oxygenant is H for example
2O
2, NaClO etc.
Described mineral acid is hydrochloric acid, sulfuric acid or nitric acid etc., preferably hydrochloric acid.
The inventive method prepares Glyphosate 62 IPA Salt technology to glycocoll to be reformed, and has proposed to reduce the proportioning of Paraformaldehyde 96 and dialkyl phosphite; The low temperature acidolysis also removes the perhaps novel process of oxidation of formaldehyde simultaneously behind the esterification condensation liquid elder generation precipitation.This technology not only can make most monoalcohol solvents reclaim earlier with nearly half tertiary amine and directly apply mechanically; Can reduce the consumption of 20-50% left and right sides hydrochloric acid and caustic soda and the generation of abraum salt; And the rectifying once more that can reduce most monohydroxy-alcohols adds alkali recovery load with nearly half tertiary amine; Simultaneously can reduce even avoid the generation of methyl chloride largely, reduce it to the pollution of environment, further reduce the loss of methyl alcohol and hydrochloric acid, further reduce investment.This technology has promoted the post-processed ability of device greatly, significantly reduces material consumption, energy consumption, more helps implementing maximization, serialization and the robotization of Glyphosate 62 IPA Salt technology.New process method has been optimized former proportioning, has found the key factor that influences yield fluctuation, and the production capacity of Glyphosate 62 IPA Salt is significantly improved, and its yield is with quality tends towards stability and slightly raising simultaneously.Have bigger economy and environmental benefit.
Embodiment
The present invention's employing hereinafter provides indefiniteness embodiment and is described further.
Control Example 1
Paraformaldehyde 96 16.1g (0.537mol), triethylamine 25.6g (0.253mol), glycocoll 19g (0.25mol) and 120ml methyl alcohol are placed the 500mL four-hole boiling flask of taking back flow condenser, TM and stirring simultaneously; Be stirred to and be warming up to 45 ℃ after transparent; Add dimethylphosphite 30.90g (0.3mol); 45-65 ℃ of insulation reaction, finish until reaction.At 45-70 ℃ of reclaim under reduced pressure methyl alcohol and triethylamine, do not have obvious liquid outflow back and be cooled to naturally about 40 ℃, slowly dripping hydrochloric acid (30%) 76g (0.625mol); 40-70 ℃ of insulation acidolysis is until reacting completely, and the depickling of reducing pressure then is when temperature reaches 110 ℃; Stop decompression, add 40g water, crystallisation by cooling; The suction filtration drying obtains the former powder 34.03g of Glyphosate 62 IPA Salt (content 95.5%), former powder yield 77%, total recovery 81% at last.
Control Example 2
Paraformaldehyde 96 16.1g (0.537mol), triethylamine 25.6g (0.253mol), glycocoll 19g (0.25mol) and 120ml methyl alcohol are placed the 500mL four-hole boiling flask of taking back flow condenser, TM and stirring simultaneously; Be stirred to and be warming up to 45 ℃ after transparent; Add dimethylphosphite 30.90g (0.30mol); 45-65 ℃ of insulation reaction, finish until reaction.100 ℃ of normal pressures reclaim methyl alcohol and triethylamine, do not have to be cooled to naturally about 40 ℃ after obvious liquid flows out, slowly dripping hydrochloric acid (30%) 76g (0.625mol); 40-70 ℃ of insulation acidolysis is until reacting completely, and the depickling of reducing pressure then is when temperature reaches 110 ℃; Stop decompression, add 40g water, crystallisation by cooling; The dry last former powder 34.31g of Glyphosate 62 IPA Salt (content 94.8%), former powder yield 77%, the total recovery 82.5% of getting of suction filtration.
Paraformaldehyde 96 15.63g (0.5mol), triethylamine 25.6g (0.253mol), glycocoll 19g (0.25mol) and 120ml methyl alcohol are placed the 500mL four-hole boiling flask of taking back flow condenser, TM and stirring simultaneously; Be stirred to and be warming up to 45 ℃ after transparent; Add dimethylphosphite 30.90g (0.30mol); 45-65 ℃ of insulation reaction, finish until reaction.45-70 ℃ of bulging air resolved and reclaimed methyl alcohol and triethylamine, do not have to be cooled to naturally about 40 ℃ after obvious liquid flows out, and slow dripping hydrochloric acid (30%) 38.00g (0.313mol), 50-75 ℃ of insulation acidolysis is until reacting completely; Bulging simultaneously air parsing removes formaldehyde and finishes until acidolysis, and the depickling of reducing pressure then is when temperature reaches 110 ℃; Stop decompression, add 40.00g water, crystallisation by cooling; The suction filtration drying obtains the former powder 34.78g of Glyphosate 62 IPA Salt (content 97%), former powder yield 82.3%, total recovery 85.7%.
Paraformaldehyde 96 11.72g (0.375mol), triethylamine 25.6g (0.253mol), glycocoll 19g (0.25mol) and 120ml methyl alcohol are placed the 500mL four-hole boiling flask of taking back flow condenser, TM and stirring simultaneously; Be stirred to and be warming up to 45 ℃ after transparent; Add dimethylphosphite 29.66g (0.288mol); 45-65 ℃ of insulation reaction, finish until reaction.90-110 ℃ of air distillation Separation and Recovery methyl alcohol and triethylamine do not have obvious liquid and flow out the back and be cooled to about 40 ℃ slow dripping hydrochloric acid (30%) 38.00g (0.313mol) naturally; 50-75 ℃ of insulation acidolysis is until reacting completely; Bulging simultaneously air parsing removes formaldehyde and finishes until acidolysis, and the depickling of under temperature of reaction, reducing pressure adds 20.00g water; Use NaOH (30%) to transfer about pH to 1.5 then; The suction filtration drying obtains the former powder 30.34g of Glyphosate 62 IPA Salt (content 96.5%), former powder yield 71.18%, total recovery 72.46%.
Paraformaldehyde 96 14.47g (0.463mol), triethylamine 25.6g (0.253mol), glycocoll 19g (0.25mol) and 120ml methyl alcohol are placed the 500mL four-hole boiling flask of taking back flow condenser, TM and stirring simultaneously; Be stirred to and be warming up to 45 ℃ after transparent; Add dimethylphosphite 25.75g (0.25mol); 45-65 ℃ of insulation reaction, finish until reaction.Methyl alcohol and triethylamine are reclaimed in 40-70 ℃ of underpressure distillation; Have obvious liquid and flow out the back and be not cooled to naturally about 40 ℃, slow dripping hydrochloric acid (30%) 51.71g (0.425mol), 50-75 ℃ of decompression (P=-0.01 extremely-0.03MPa) acidolysis until reacting completely; Use NaOH (30%) to transfer about pH to 1.5 then; The suction filtration drying obtains the former powder 34.02g of Glyphosate 62 IPA Salt (content 97%), former powder yield 80.5%, total recovery 85.5%.
With Paraformaldehyde 96 11.72g (0.375mol), triethylamine 25.6g (0.253mol), glycocoll/Na
2SO
420.00g (0.25mol) and 120ml methyl alcohol place the 500mL four-hole boiling flask of taking back flow condenser, TM and stirring simultaneously; Be stirred to and be warming up to 45 ℃ after organism dissolves entirely; Add dimethylphosphite 25.75g (0.25mol),, finish until reaction 45-65 ℃ of insulation reaction.Filter and with an amount of methanol wash filter residue, 45-70 ℃ of underpressure distillation Separation and Recovery methyl alcohol and triethylamine behind the merging filtrate do not have obvious liquid and flow out and then be cooled to naturally about 40 ℃; Slow dripping hydrochloric acid (30%) 51.71g (0.425mol), 50-75 ℃ of insulation acidolysis is until reacting completely, and bulging simultaneously air parsing removes formaldehyde and finishes until acidolysis; The decompression depickling when temperature reaches 110 ℃, stops decompression; Add 40g water, crystallisation by cooling, the suction filtration drying obtains the former powder 34.56g of Glyphosate 62 IPA Salt (content 97%); Former powder yield 81.8%, total recovery 86.3%.
Paraformaldehyde 96 14.47g (0.463mol), triethylamine 25.6g (0.253mol), glycocoll 19g (0.25mol) and 120ml methyl alcohol are placed the 500mL four-hole boiling flask of taking back flow condenser, TM and stirring simultaneously; Be stirred to transparent after; Volatile substances such as methyl alcohol and triethylamine are reclaimed in 40 ℃ of underpressure distillation; Do not stop decompression and add 60ml methyl alcohol after having obvious liquid outflow, be warming up to 45 ℃ then, add dimethylphosphite 25.75g (0.25mol); 45-65 ℃ of insulation reaction, finish until reaction.40-70 ℃ of gas is resolved and is reclaimed methyl alcohol and triethylamine; Have obvious liquid and flow out the back and be not cooled to naturally about 40 ℃, slow dripping hydrochloric acid (30%) 51.71g (0.425mol), 50-75 ℃ of decompression (P=-0.01 extremely-0.03MPa) acidolysis until reacting completely; Use NaOH (30%) to transfer about pH to 1.5 then; The suction filtration drying obtains the former powder 31.56g of Glyphosate 62 IPA Salt (content 96%), former powder yield 74.6%, total recovery 80.7%.
With Paraformaldehyde 96 11.72g (0.375mol), triethylamine 25.6g (0.253mol), glycocoll/Na
2SO
420.00g (0.25mol) and 120ml methyl alcohol place the 500mL four-hole boiling flask of taking back flow condenser, TM and stirring simultaneously; Be stirred to and be warming up to 45 ℃ after organism dissolves entirely; Add dimethylphosphite 25.75g (0.25mol),, finish until reaction 45-65 ℃ of insulation reaction.Filter and with an amount of methanol wash filter residue, 45-70 ℃ of underpressure distillation Separation and Recovery methyl alcohol and triethylamine behind the merging filtrate do not have obvious liquid and flow out the back and be cooled to about 40 ℃ slow dripping hydrochloric acid (30%) 51.71g (0.425mol) and (10%) 30gH naturally
2O
2, 50-75 ℃ of insulation acidolysis is until reacting completely, and the decompression depickling when temperature reaches 110 ℃, stops decompression, adds 40g water, crystallisation by cooling, the suction filtration drying obtains the former powder 32.56g of Glyphosate 62 IPA Salt (content 95.6%), former powder yield 77.06%, total recovery 82.39%.
With Paraformaldehyde 96 11.72g (0.375mol), triethylamine 25.6g (0.253mol), glycocoll/Na
2SO
420.00g (0.25mol) and 120ml methyl alcohol place the 500mL four-hole boiling flask of taking back flow condenser, TM and stirring simultaneously; Be stirred to and be warming up to 45 ℃ after organism dissolves entirely; Add dimethylphosphite 25.75g (0.25mol),, finish until reaction 45-65 ℃ of insulation reaction.Filter and with an amount of methanol wash filter residue; 45-70 ℃ of underpressure distillation Separation and Recovery methyl alcohol and triethylamine behind the merging filtrate; After not having obvious liquid outflow, directly apply mechanically to the depolymerization condensation step after methyl alcohol that reclaim this moment and triethylamine are added triethylamine, subsequent operations is with embodiment 4.Fig. 1 is the recycled experimental result, and legend ■ curve is represented total recovery, legend ◆ the solid careless yield of curve representative.
Claims (8)
1. method for preparing Glyphosate 62 IPA Salt, it comprises the steps:
1), carries out condensation reaction with the phosphorous acid dialkyl again with glycocoll and Paraformaldehyde 96 drops into monohydroxy-alcohol simultaneously and tertiary amine system is separated polycondensation reaction;
The mode of 2) resolving through normal pressure, decompression or gas reclaims monohydroxy-alcohol and tertiary amine; After no obvious liquid flows out; Temperature control adds the mineral acid acidolysis again, and in acidolysis, removes or oxidation of formaldehyde, up to reacting completely; Glyphosate 62 IPA Salt is prepared in reduce pressure then depickling and/or directly add in the alkali and regulate pH value and deacidify.
2. according to the method for claim 1, it comprises the steps:
1) glycocoll and Paraformaldehyde 96 are dropped in monohydroxy-alcohol and the tertiary amine system simultaneously, be stirred to transparent after, be warming up to 40-50 ℃, add dialkyl phosphite again, 40-70 ℃ of insulation until reacting completely;
The mode of 2) resolving through decompression or gas reclaims monohydroxy-alcohol and tertiary amine, after no obvious liquid flows out, is cooled to naturally about 40 ℃; Temperature control adds hydrochloric acidolysis again; And in acidolysis, resolve through gas and/or the mode of decompression removes formaldehyde, perhaps at the simultaneous oxidation formaldehyde of acidolysis, up to reacting completely; Be decompressed to the following depickling of P=-0.02MPa then and/or directly add in the alkali and the deacidification of adjusting pH value, prepare Glyphosate 62 IPA Salt.
3. according to the method for claim 1 or 2, wherein,
Step 2) 20-110 ℃ of the recovery monohydroxy-alcohol and the precipitation temperature of tertiary amine; Step 2) temperature control acidolysis reaction temperature is 20-110 ℃ in, and the decompression depickling stops decompression when temperature reaches 110 ℃.
4. according to the method for claim 3, wherein,
Step 2) precipitation temperature is 40-80 ℃; Step 2) mode that adopts decompression or gas to resolve reclaims monohydroxy-alcohol and tertiary amine, adopts 40-80 ℃ of insulation acidolysis, in the time of acidolysis the drum air resolve remove or oxidation of formaldehyde until the reaction end.
5. according to the method for claim 1 or 2, wherein, the material proportion of employing is glycocoll: the mol ratio of Paraformaldehyde 96 is 1: 1.2-2; Glycocoll: the mol ratio of dialkyl phosphite is 1: 0.95-1.3.
6. according to the method for claim 5, wherein, glycocoll: the mol ratio of Paraformaldehyde 96 is 1: 1.4-1.95; Glycocoll: the mol ratio of dialkyl phosphite is 1: 0.95-1.19.
7. according to the method for claim 1 or 2, wherein, oxidation of formaldehyde adopts oxygenant H
2O
2Or NaClO.
8. according to the method for claim 1 or 2, wherein, step 2) in, depickling adopts conventional alkali to be neutralized to pH=0.7-3.0, perhaps adopts the mode depickling of underpressure distillation, and said conventional alkali is sodium hydroxide, Pottasium Hydroxide or sodium hydrogencarbonate.
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| CN102134261A (en) * | 2010-01-25 | 2011-07-27 | 北京紫光英力化工技术有限公司 | Process for preparing glyphosate by glycine method |
| CN102766160B (en) * | 2012-07-16 | 2015-09-02 | 江苏索普（集团）有限公司 | The novel process of preparing glyphosate by glycin method |
| CN102786547B (en) * | 2012-08-29 | 2015-05-20 | 常州储能材料与器件研究院 | Process for synthesizing glyphosine |
| CN102850395B (en) * | 2012-10-11 | 2015-08-05 | 常州储能材料与器件研究院 | A kind of method of synthesizing glyphosate |
| CN102977137A (en) * | 2012-11-29 | 2013-03-20 | 湖北泰盛化工有限公司 | Condensate recovery method for glyphosate synthesis solution |
| CN106518920B (en) * | 2016-10-30 | 2018-09-18 | 山东润博生物科技有限公司 | A kind of synthetic method of glyphosate |
| CN106543222B (en) * | 2016-10-30 | 2018-09-18 | 山东润博生物科技有限公司 | A kind of production method of glyphosate |
| CN110407870B (en) * | 2019-08-13 | 2024-03-29 | 南通江山农药化工股份有限公司 | Preparation method of glyphosate and microchannel reactor thereof |
| CN110452265A (en) * | 2019-08-30 | 2019-11-15 | 湖北泰盛化工有限公司 | A kind of glyphosate technicals cleaning method |
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| CN1939926A (en) * | 2005-09-30 | 2007-04-04 | 北京清华紫光英力化工技术有限责任公司 | Production of glyphosate by glycine method |
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