CN101591352A - 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 present invention relates to a kind of method for preparing glyphosate, this method comprises the steps: that glycine and Paraformaldehyde 96 are dropped into monohydroxy-alcohol/tertiary amine system simultaneously according to certain proportioning separates polycondensation reaction, dialkyl phosphite with proportional quantity carries out directly reclaiming monohydroxy-alcohol and tertiary amine after the condensation reaction again, controlling temperature acidolysis again, and remove or oxidation of formaldehyde in acidolysis or after the acidolysis, glyphosate is prepared in depickling and/or neutralization then.The present invention adopts and reduces Paraformaldehyde 96 proportioning, direct precipitation and apply mechanically, several different methods such as low temperature acidolysis is eliminated formaldehyde behind the precipitation influence, reduce the yield and the quality that consume, stablized 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 glycine and Paraformaldehyde 96 are dropped into monohydroxy-alcohol/tertiary amine system simultaneously according to certain proportioning separates polycondensation reaction; can select to pass through normal pressure this moment; the mode that decompression or air are resolved reclaims volatile components such as alkohol and amine; dialkyl phosphite with proportional quantity carries out condensation reaction again; pass through normal pressure afterwards; the mode that decompression or air are resolved reclaims alkohol and amine; temperature control acidolysis again; and in acidolysis, remove or oxidation of formaldehyde; glyphosate is prepared in depickling or neutralization then.
Background of invention
Glyphosate has another name called the sweet acid of phosphine, and chemical name is N-(phosphonomethyl) glycine, 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, control to multiple dark root malignant weed is very effective, sales volume 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 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 glycine method at the aqueous phase synthesizing glyphosate in addition; Application number is the method for starting raw material synthesizing glyphosate with the glycine an alkali metal salt for the patent of invention of 03147313.X provides a kind of.
Dialkyl phosphite technology adopts Paraformaldehyde 96 to obtain methylal in pure amine system depolymerization more at present, and then with the glycine condensation, with the dialkyl phosphite reaction, last acidolysis, dealcoholysis, depickling, crystallization, filtration, oven dry obtain the former powder of glyphosate again.
Summary of the invention
The invention provides the novel process of the preparation glyphosate (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 patent applications.When stating patent application 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 glyphosates in acid system with formaldehyde condensation, cause glyphosate 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, elder generation is (normal pressure by conventional methods, decompression also or gas resolve) mode with phosphorous acid alkyl dialkyl esterification condensation liquid at lesser temps for example below 20-110 ℃, reclaim monohydroxy-alcohol and tertiary amine, after no obvious liquid flows out, esterification condensation liquid after the concentration adds the mineral acid acidolysis by proportioning, and in acidolysis, remove 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, and filtrate being used to prepares the liquid glyphosate.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 by 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, 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 service requirements.In this inventive method, most alcohol and part tertiary amine just reclaim under anhydrous situation, can directly apply mechanically, therefore that has saved most of material adds operations such as alkali, drying, neutralization deacidification, rectifying, starting material and equipment input have been saved 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 specific embodiment, the inventive method comprises the steps:
1), carries out condensation reaction with the phosphorous acid dialkyl again with glycine and Paraformaldehyde 96 drops into monohydroxy-alcohol simultaneously and tertiary amine system is separated polycondensation reaction;
2) mode of resolving by 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, remove or oxidation of formaldehyde, up to reacting completely, glyphosate 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) glycine 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;
2) mode of resolving by decompression or gas reclaims monohydroxy-alcohol and tertiary amine, after no obvious liquid flows out, naturally be cooled to about 40 ℃, temperature control adds hydrochloric acidolysis again, and in acidolysis, resolve by gas and/or the mode of decompression removes formaldehyde, perhaps at the simultaneous oxidation formaldehyde of acidolysis, up to reacting completely, glyphosate 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, add for example neutralizations such as sodium hydroxide, potassium hydroxide or sodium bicarbonate 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:
Glycine: Paraformaldehyde 96 is 1: 1.2-2, preferred 1: 1.4-1.95.
Glycine: dialkyl phosphite is 1: 0.95-1.3, preferred 1: 0.95-1.19.
Described precipitation (taking off monohydroxy-alcohol and tertiary amine etc.) and acidolysis temperature are 20-110 ℃, are preferably 40-80 ℃.
The described 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 technology to glycine to be reformed, and has proposed to reduce the proportioning of Paraformaldehyde 96 and dialkyl phosphite; Low temperature acidolysis and removing simultaneously or the novel process of oxidation of formaldehyde behind the esterification condensation liquid elder generation precipitation.This technology not only can make most monoalcohol solvents and nearly half tertiary amine reclaim earlier 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 and nearly half the tertiary amine that can reduce most monohydroxy-alcohols add alkali recovery load, 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 automatization of glyphosate technology.New processing method has been optimized former proportioning, has found the key factor that influences yield fluctuation, and the production capacity of glyphosate is significantly improved, simultaneously its yield and quality tends towards stability and slightly improve.Have bigger economy and environmental benefit.
Embodiment
The present invention's employing hereinafter provides indefiniteness embodiment and is described further.
Comparative examples 1
Paraformaldehyde 96 16.1g (0.537mol), triethylamine 25.6g (0.253mol), glycine 19g (0.25mol) and 120ml methyl alcohol are placed the 500mL four-hole boiling flask of taking back flow condenser, thermometer 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 ℃, slow dripping hydrochloric acid (30%) 76g (0.625mol), 40-70 ℃ of insulation acidolysis is until reacting completely, the depickling of reducing pressure then, when temperature reaches 110 ℃, stop decompression, add 40g water, crystallisation by cooling, the suction filtration drying obtains the former powder 34.03g of glyphosate (content 95.5%), former powder yield 77%, total recovery 81% at last.
Comparative examples 2
Paraformaldehyde 96 16.1g (0.537mol), triethylamine 25.6g (0.253mol), glycine 19g (0.25mol) and 120ml methyl alcohol are placed the 500mL four-hole boiling flask of taking back flow condenser, thermometer 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 obvious liquid outflow back and be cooled to naturally about 40 ℃, slow dripping hydrochloric acid (30%) 76g (0.625mol), 40-70 ℃ of insulation acidolysis is until reacting completely, the depickling of reducing pressure then, when temperature reaches 110 ℃, stop decompression, add 40g water, crystallisation by cooling, the dry last former powder 34.31g of glyphosate (content 94.8%), former powder yield 77%, the total recovery 82.5% of getting of suction filtration.
Embodiment 1
Paraformaldehyde 96 15.63g (0.5mol), triethylamine 25.6g (0.253mol), glycine 19g (0.25mol) and 120ml methyl alcohol are placed the 500mL four-hole boiling flask of taking back flow condenser, thermometer 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, slowly 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 (content 97%), former powder yield 82.3%, total recovery 85.7%.
Embodiment 2
Paraformaldehyde 96 11.72g (0.375mol), triethylamine 25.6g (0.253mol), glycine 19g (0.25mol) and 120ml methyl alcohol are placed the 500mL four-hole boiling flask of taking back flow condenser, thermometer 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 and be cooled to naturally about 40 ℃ after obvious liquid flows out, 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, the depickling of under temperature of reaction, reducing pressure, add 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 (content 96.5%), former powder yield 71.18%, total recovery 72.46%.
Embodiment 3
Paraformaldehyde 96 14.47g (0.463mol), triethylamine 25.6g (0.253mol), glycine 19g (0.25mol) and 120ml methyl alcohol are placed the 500mL four-hole boiling flask of taking back flow condenser, thermometer 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, do not have and be cooled to naturally about 40 ℃ after obvious liquid flows out, slow dripping hydrochloric acid (30%) 51.71g (0.425mol), 50-75 ℃ of decompression (P=-0.01 to-0.03MPa) acidolysis is 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 (content 97%), former powder yield 80.5%, total recovery 85.5%.
Embodiment 4
With Paraformaldehyde 96 11.72g (0.375mol), triethylamine 25.6g (0.253mol), glycine/Na
2SO
420.00g (0.25mol) and 120ml methyl alcohol place the 500mL four-hole boiling flask of taking back flow condenser, thermometer and stirring simultaneously, be stirred to that organism is complete to be warming up to 45 ℃ after molten, 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 and be cooled to naturally about 40 ℃ after obvious liquid flows out, slow dripping hydrochloric acid (30%) 51.71g (0.425mol), 50-75 ℃ of insulation acidolysis is until reacting completely, bulging simultaneously air parsing removes formaldehyde and finishes until acidolysis, the decompression depickling, when temperature reaches 110 ℃, stop decompression, add 40g water, crystallisation by cooling, the suction filtration drying obtains the former powder 34.56g of glyphosate (content 97%), former powder yield 81.8%, total recovery 86.3%.
Embodiment 5
Paraformaldehyde 96 14.47g (0.463mol), triethylamine 25.6g (0.253mol), glycine 19g (0.25mol) and 120ml methyl alcohol are placed the 500mL four-hole boiling flask of taking back flow condenser, thermometer 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 have and stop decompression after obvious liquid flows out and add 60ml methyl alcohol, 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, do not have and be cooled to naturally about 40 ℃ after obvious liquid flows out, slow dripping hydrochloric acid (30%) 51.71g (0.425mol), 50-75 ℃ of decompression (P=-0.01 to-0.03MPa) acidolysis is 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 (content 96%), former powder yield 74.6%, total recovery 80.7%.
Embodiment 6
With Paraformaldehyde 96 11.72g (0.375mol), triethylamine 25.6g (0.253mol), glycine/Na
2SO
420.00g (0.25mol) and 120ml methyl alcohol place the 500mL four-hole boiling flask of taking back flow condenser, thermometer and stirring simultaneously, be stirred to that organism is complete to be warming up to 45 ℃ after molten, 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 (content 95.6%), former powder yield 77.06%, total recovery 82.39%.
Embodiment 7
With Paraformaldehyde 96 11.72g (0.375mol), triethylamine 25.6g (0.253mol), glycine/Na
2SO
420.00g (0.25mol) and 120ml methyl alcohol place the 500mL four-hole boiling flask of taking back flow condenser, thermometer and stirring simultaneously, be stirred to that organism is complete to be warming up to 45 ℃ after molten, 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, a kind of method for preparing glyphosate, it comprises the steps:
1), carries out condensation reaction with the phosphorous acid dialkyl again with glycine and Paraformaldehyde 96 drops into monohydroxy-alcohol simultaneously and tertiary amine system is separated polycondensation reaction;
2) mode of resolving by 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, remove or oxidation of formaldehyde, up to reacting completely, glyphosate 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) glycine 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;
2) mode of resolving by decompression or gas reclaims monohydroxy-alcohol and tertiary amine, after no obvious liquid flows out, naturally be cooled to about 40 ℃, temperature control adds hydrochloric acidolysis again, and in acidolysis, resolve by 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.
3, according to the method for claim 1 or 2, wherein,
20-110 ℃ of the recovery monohydroxy-alcohol of step 1) 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 2 or 3, wherein,
The precipitation temperature of step 1 is 40-80 ℃; Step 2) mode that adopts decompression or gas to resolve reclaims alkohol and 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 arbitrary method of claim 1-4, wherein, the material proportion of employing and condition are glycine: the mol ratio of Paraformaldehyde 96 is 1: 1.2-2; Glycine: the mol ratio of dialkyl phosphite is 1: 0.95-1.3.
6, according to the method for claim 5, wherein, glycine: the mol ratio of Paraformaldehyde 96 is 1: 1.4-1.95; Glycine: the mol ratio of dialkyl phosphite is 1: 0.95-1.19.
7, according to arbitrary method of claim 1-6, wherein, oxidation of formaldehyde adopts oxygenant H
2O
2Or NaClO.
8, according to the arbitrary described method of claim 1-7, 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.
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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 |
| CN102766160A (en) * | 2012-07-16 | 2012-11-07 | 江苏索普（集团）有限公司 | Novel process for preparing glyphosate by utilizing glycine method |
| CN102786547A (en) * | 2012-08-29 | 2012-11-21 | 常州储能材料与器件研究院 | Process for synthesizing glyphosine |
| CN102850395A (en) * | 2012-10-11 | 2013-01-02 | 常州储能材料与器件研究院 | Method for 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 |
| CN106518920A (en) * | 2016-10-30 | 2017-03-22 | 山东润博生物科技有限公司 | Synthetic method of glyphosate |
| CN106543222A (en) * | 2016-10-30 | 2017-03-29 | 山东润博生物科技有限公司 | A kind of production method of glyphosate |
| CN110407870A (en) * | 2019-08-13 | 2019-11-05 | 南通江山农药化工股份有限公司 | The preparation method and its micro passage reaction of glyphosate |
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| CN100513410C (en) * | 2005-09-30 | 2009-07-15 | 重庆三峡英力化工有限公司 | Production of glyphosate by glycine method |
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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 |
| CN102766160A (en) * | 2012-07-16 | 2012-11-07 | 江苏索普（集团）有限公司 | Novel process for preparing glyphosate by utilizing 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 |
| CN102786547A (en) * | 2012-08-29 | 2012-11-21 | 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 |
| CN102850395A (en) * | 2012-10-11 | 2013-01-02 | 常州储能材料与器件研究院 | Method for 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 |
| CN106518920A (en) * | 2016-10-30 | 2017-03-22 | 山东润博生物科技有限公司 | Synthetic method of glyphosate |
| CN106543222A (en) * | 2016-10-30 | 2017-03-29 | 山东润博生物科技有限公司 | A kind of production method of glyphosate |
| CN110407870A (en) * | 2019-08-13 | 2019-11-05 | 南通江山农药化工股份有限公司 | The preparation method and its micro passage reaction 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 |
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