CN102134261A - Process for preparing glyphosate by glycine method - Google Patents
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- CN102134261A CN102134261A CN2010101009132A CN201010100913A CN102134261A CN 102134261 A CN102134261 A CN 102134261A CN 2010101009132 A CN2010101009132 A CN 2010101009132A CN 201010100913 A CN201010100913 A CN 201010100913A CN 102134261 A CN102134261 A CN 102134261A
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Abstract
The invention relates to a method for preparing glyphosate, which comprises the following steps: adding glycine and paraformaldehyde into a monohydric alcohol/tertiary amine system at one time according to an optimized mixing ratio for a depolymerization and condensation reaction, performing the condensation reaction of the product of the depolymerization and condensation reaction and dialkyl phosphate in an optimized mixing amount under an optimized pH value condition, recovering monohydric alcohol and tertiary amine, controlling temperature for acidified hydrolysis, removing or oxidizing formaldehyde at the same time as acidified hydrolysis, precipitating glyphosate, and recycling the mother liquor as acid directly. When the technique of desolventizing, low-temperature acidification and mother liquor recycling, which is provided by the invention, is used, the consumption of paraformaldehyde, phosphite ester, alcohol, acid and alkali is reduced, energy consumption in distillation and mother liquor concentration processes is reduced, the generation of chloromethane is inhibited effectively, the yield reduction of the glyphosate due to the damage of formaldehyde is avoided to a maximum degree, the mother liquor processing amount and acid and alkali consumption are reduced to a maximum degree, and the yield of raw powder is improved.
Description
Invention field
The present invention relates to a kind of is the novel process of feedstock production glyphosate with the alkyl phosphite, specifically, the inventive method comprises the steps: glycine and Paraformaldehyde 96 are dropped into monohydroxy-alcohol/tertiary amine system simultaneously and separate polycondensation reaction according to optimizing proportioning, carry out condensation reaction with the dialkyl phosphite of optimizing proportional quantity again, pH in the strict control reaction process, after condensation is finished directly under the heat tracing condition with normal pressure, the mode that decompression or air are resolved reclaims alkohol and amine, temperature control acidification hydrolization then, and in acidification hydrolization or acidifying remove or oxidation of formaldehyde when finishing, direct crystallization obtains glyphosate, and its mother liquor is directly applied mechanically as acid.Adopt the technology of the present invention of first precipitation, low temperature acidifying again, mother liquid recycle, not only can significantly reduce the material consumption of Paraformaldehyde 96, phosphorous acid ester, alcohol, acid, alkali, can also reduce the energy consumption in rectifying, the mother liquor concentration process, effectively suppress destruction and the methyl chloride generation of methyl chloride generation and formaldehyde to glyphosate, at utmost avoid formaldehyde the destruction of glyphosate to be caused the reduction of yield, maximum amplitude reduces mother liquor treatment capacity and acid and alkali consumption amount, improves former powder yield.
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.
The operational path of glycine synthesizing glyphosate is the main technique route of China, accounts for about 50% of China's glyphosate aggregated capacity, has certain cost competitive edge.Glycine route patent and report less, it is that raw material is separated polycondensation with glycine, Paraformaldehyde 96, dialkyl phosphite that the patent of invention of application number 85102988 discloses a kind of, again with the direct acidification hydrolization of excessive hydrochloric acid, be warming up to 110 ℃ of dealcoholysis, depickling, the preparation technology of the glyphosate of a large amount of methylals of by-product and methyl chloride; Application number be the patent of 03147313.X only glycine to be used instead the glycine an alkali metal salt be starting raw material, do not optimize other processing condition; Application number provides a kind of first precipitation glyphosate preparation technology of acidolysis again for 200510115909.2 patent of invention, but has the yield instability, and fluctuation is big, is difficult to reach the problem of old process recovery ratio.
The glyphosate production enterprise of glycine route continues to use the operational path of application number 85102988 patents of invention substantially at present.But this operational path adopts a large amount of methyl alcohol to make solvent, glycine: the Paraformaldehyde 96 amount of substance reaches more than 1: 2, glycine: the dimethylphosphite amount of substance reaches more than 1: 1.2, separating polycondensation need carry out in anhydrous system, and the acidolysis process need adds a large amount of hydrochloric acid and is heated to 110 ℃, cause a large amount of methyl alcohol and hydrochloric acid to generate methyl chloride, excessive greatly formaldehyde and methyl alcohol generate methylal, have water and acid in the methyl alcohol that steams in a large number, need rectifying to reclaim methylal and anhydrous methanol, the acid hydrolysis solution after concentrating is owing to excess formaldehyde under the higher temperature causes yield not high.The mother liquor of separating out the former powder of glyphosate adds can only remove part salt and water by concentrating after alkali reclaims triethylamine, can't reach 10% glyphosate content, and the former powder of needs interpolation just can be mixed with 10% aqua.Because residual a large amount of sodium-chlor and other by product in the aqua, country has forbidden producing 10% gyphosate solution after 2009.Therefore, this technology material consumption, energy consumption are big, and single still production capacity is low, face the raising of yield, material consumption, energy consumption reduce methyl chloride, methylal effective recycling, difficult problems such as the recovery of waste liquor and 10% liquid grass are superseded are necessary to save energy and reduce the cost the research of new cleanproduction process.
Summary of the invention
The invention provides a kind of novel process of preparing glyphosate by glycin method.
We find by the former technology of glyphosate deeply being scrutinized the back: react that the content of formaldehyde and phosphorous acid all can influence glyphosate yield and former powder content in the temperature, acid hydrolysis solution of control, the acidolysis process of moisture, the condensation course pH of proportioning, the system of each stage material, and reduce Paraformaldehyde 96 and phosphorous acid ester proportioning as far as possible, control lower acidolysis temperature and be by products such as suppressing to increase sweet phosphine, hydroxymethyl phosphonic acid and improve the key of yield.Have the temperature height in former acidolysis technology, excess formaldehyde and phosphorous acid cause glyphosate destroyed in acidolysis and last handling process, and the system of a large amount of methyl alcohol, formaldehyde and hydrochloric acid causes a large amount of by product methyl chloride, methylal to generate.
Most monoalcohol solvents and nearly half tertiary amine are reclaimed earlier directly to be applied mechanically, can reduce the consumption of 20-50% left and right sides hydrochloric acid and caustic soda and the generation of abraum salt, and can reduce the rectifying once more of most monohydroxy-alcohols and nearly half tertiary amine and add alkali and reclaim the most alcohol of load and part tertiary amine and can reclaim in distillation under anhydrous condition and obtain, water content is very low, making simple process slightly just can directly apply mechanically, therefore saved the alkali that adds of most of material, dry, the neutralization deacidification, operations such as rectifying, starting material and equipment input have been saved greatly, improve usage ratio of equipment accordingly, reduced production cost.Reduce the methanol rectification process, promote production capacity greatly, reduce investment.
We further discover, pH when dripping triethylamine control condensation by gradation is in the 7.0-8.0 scope time, not only reduces the excessive proportioning of Paraformaldehyde 96 and phosphorous acid, and can improve the selectivity of reaction, suppress the generation of hydroxymethyl phosphonic acid ester, thereby reduce the dimethylphosphite consumption.
We also find in the present invention, controlling lower acidolysis temperature or removing simultaneously or oxidation of formaldehyde, can reduce and increase sweet phosphine and hydroxymethyl phosphonic acid generation, stabilize and increase the glyphosate yield, reduce the consumption and the solvent vapo(u)r consumption of reactant, reduce even avoid the generation of methyl chloride and methylal, reduce acid, alkali consumption and the three wastes and produce.When acidolysis temperature was controlled at 20-40 ℃, influence significantly reduced to yield in side reaction, does not generate methyl chloride under this temperature condition substantially.Though the acidolysis time prolongs to some extent, owing to most of triethylamine has been steamed during desolventizing, acidolysis can be carried out under higher concentration and acidity, because acidolysis temperature is low, the alcohol amount is few, therefore reacting charging capacity can increase greatly, and single still charging capacity was compared originally and doubled at least, can remedy the production capacity reduction that low temperature acidolysis time lengthening causes substantially.And the generation of methyl chloride and methylal can be suppressed substantially, can save the recovery purification devices of methyl chloride and methylal fully.
We find also that acid hydrolysis solution needn't concentrate and can directly separate out glyphosate in the present invention, separating out hydrochloric acid remaining in the mother liquor behind the glyphosate need not remove or neutralize, add a certain amount of hydrochloric acid or feed a certain amount of HCl gas instead hydrochloric acid cover and be used for the next batch acidolysis, experiment shows that mother liquor can apply mechanically 3-10 time, apply mechanically and do not influence quality product in the process, can effectively reduce the mother liquor amount, make the glyphosate mother solution amount be reduced to original 20-30%, make the glyphosate yield improve about 4-6%, reduced simultaneously and prepared 10% the employed former powder of aqua, made former powder yield improve greatly.Can save bronsted lowry acids and bases bronsted lowry, reduce triethylamine yield and recovered frequency simultaneously, reduce the steam output of mother liquor, have remarkable social economy and environmental protection effect.
In specific embodiment, the inventive method comprises the steps:
1) in separating polycondensation reaction the amount of substance of each material than glycine: Paraformaldehyde 96: methyl alcohol: triethylamine: dimethylphosphite is 1: 1.2-2.0: 6-15: 0.7-1.2: 0.8-1.3, Paraformaldehyde 96, glycine are dropped into methyl alcohol and the depolymerization of triethylamine amine system, 35-45 ℃ is reacted 20-40min down, drop into the phosphorous acid dialkyl again after the system clarification and carry out condensation reaction in the pH of 7.0-8.0 scope, 45-65 ℃ is reacted 2-4h down.
2) mode of resolving by normal pressure, decompression or gas 30-80 ℃ of condition reclaims alkohol and amine, concentrated solution is being lower than the hydrochloric acid that splashes into 1.5-4 times of glycine amount of substance under 40 ℃ of conditions, controlled temperature 20-70 ℃ of acidolysis again, and the mode by gas parsing or decompression removes or oxidation of formaldehyde in acidolysis, acidolysis finishes the direct decrease temperature crystalline in back and prepares glyphosate, filters and obtains glyphosate.
3) separate out the crystalline mother liquor add 0.2-2 times of glycine amount of substance hydrochloric acid or feed the hydrochloric acid gas of a great deal of after cover be used for the next batch acidolysis, apply mechanically 1-10 time.
In a more preferred embodiment, acidification hydrolization temperature of reaction step 2) is 30-50 ℃; In another preferred embodiment, step 2) acidification hydrolization adopts 30-50 ℃ of insulation acidification hydrolization, and the drum air is resolved and removed or formaldehyde finishes until reaction in the time of acidification hydrolization.
Reaction obtains N-dialkyl (phosphonomethyl) glycine in step 1), is referred to as esterification condensation liquid.
Main innovate point of the present invention and optimal conditions are:
Glycine: Paraformaldehyde 96 is 1: 1.2-2, preferred 1: 1.4-1.7.
Glycine: triethylamine is 1: 0.7-1.2, preferred 1: 0.85-1.0.
Glycine: methyl alcohol is 1: 6-15, preferred 1: 9-12.
Glycine: dialkyl phosphite is 1: 0.8-1.3, preferred 1: 0.95-1.15.
Glycine: hydrochloric acid is 1: 2.5-4.5, preferred 1: 2.5-3.5.
Described condensation reaction control pH scope is 7.0-8.0, is preferably 7.3-7.8.
Described acidification hydrolization temperature is 20-70 ℃, is preferably 30-50 ℃.
The described formaldehyde temperature that removes is 20-70 ℃, is preferably 30-50 ℃.
The 0.2-2 that it is the glycine amount of substance that described mother liquor is added hydrochloric acid content or the logical hydrogen chloride gas scale of construction doubly, applying mechanically number of times is 1-10 time, is preferably 3-5 time.
The inventive method prepares glyphosate technology to glycine and reforms, found the key factor that influences the yield fluctuation, develop clean environment firendly, and the new cleanproduction process that significantly improves of the production capacity that can make glyphosate, when guaranteeing glyphosate yield and stay in grade, yield slightly improves, and greatly reduces the material consumption energy consumption and the three wastes, has very big application and popularization value.
Embodiment
The present invention's employing hereinafter provides indefiniteness embodiment and is described further.
Comparative examples 1
Paraformaldehyde 96 16.1g (0.500mol), 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 33.90g (0.3mol), 45-65 ℃ of insulation reaction, finish until reaction.Naturally be cooled to about 40 ℃, slowly dripping hydrochloric acid (30%) 76g (0.625mol) was warming up to 110 ℃ in 5 hours, and acidolysis reaction is back decompression depickling fully, when temperature reaches 110 ℃, stop decompression, add 40g water, crystallisation by cooling, the suction filtration drying obtains the former powder 33.28g of glyphosate (content 94.7%) at last, former powder yield 74.6%, total recovery 82.3%, mother liquor 110.35g.
Comparative examples 2
Paraformaldehyde 96 16.1g (0.500mol), 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 31.63g (0.288mol), 45-65 ℃ of insulation reaction, finish until reaction.Naturally be cooled to about 40 ℃, slowly dripping hydrochloric acid (30%) 76g (0.625mol) was warming up to 110 ℃ in 5 hours, and acidolysis reaction is back decompression depickling fully, when temperature reaches 110 ℃, stop decompression, add 40g water, crystallisation by cooling, the suction filtration drying obtains the former powder 31.12g of glyphosate (content 95.3%) at last, former powder yield 70.2%, total recovery 77.3%, mother liquor 118.45g.
Comparative examples 3
Paraformaldehyde 96 16.1g (0.500mol), 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 33.90g (0.30mol), 45-65 ℃ of insulation reaction, finish until reaction.80 ℃ of normal pressures reclaim methyl alcohol and triethylamine, do not have and be cooled to naturally about 40 ℃ after obvious liquid flows out, slow dripping hydrochloric acid (30%) 76g (0.625mol), 40-80 ℃ of insulation acidification hydrolization is until reacting completely, bulging simultaneously air parsing removes formaldehyde and finishes until acidification hydrolization, 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 31.16g of glyphosate (content 96.5%), former powder yield 71.18%, total recovery 77.46%, mother liquor 120.66g.
Embodiment 1
Paraformaldehyde 96 15.63g (0.500mol), 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 50 ℃ after transparent, add dimethylphosphite 33.90g (0.30mol), control pH is 7.3-7.5,45-65 ℃ of insulation reaction, finish until reaction.45-70 ℃ of bulging air resolved or reclaim under reduced pressure 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), 30-50 ℃ of insulation acidification hydrolization 16h, bulging simultaneously air parsing removes formaldehyde and finishes until acidification hydrolization.Reaction solution is added hydrochloric acid (30%) 25g (0.21mol) back and is replaced hydrochloric acid to splash into next batch esterification precipitation liquid carrying out acidification hydrolization, separate out crystal, the glyphosate crystal of separating out is filtered, mother liquor continues to apply mechanically, carry out 4 acidolysis altogether with said ratio and condition, three mother liquid recycles.Obtain the former powder 143.31g of glyphosate (content 94.23%) altogether, amount to every batch of average yield 81.5% of former powder, every batch of average total recovery 87.3%, average every crowd of mother liquor 30.24g.
Embodiment 2
Embodiment 1 other condition is constant, dimethylphosphite changes 31.63g (0.288mol) into, obtains the former powder 137.90g of glyphosate (content 95.05%) altogether, amounts to every batch of average yield 79.3% of former powder, every batch of average total recovery 84.4%, average every crowd of mother liquor 27.94g.
Embodiment 3
Embodiment 1 other condition is constant, and dimethylphosphite changes 29.95g (0.275mol) into, obtains the former powder 135.12g of glyphosate (content 94.57%), amounts to every batch of former powder yield 76.5%, total recovery 82.1%, average every crowd of mother liquor 29.29g.
Embodiment 4
Embodiment 1 other condition is constant, dimethylphosphite changes 25.75g (0.25mol) into, obtains the former powder 136.97g of glyphosate (content 95.2%) altogether, amounts to every batch of former powder yield 76.37% of glyphosate, every batch of average total recovery 80.71%, average every crowd of mother liquor 28.46g.
Embodiment 5
Embodiment 1 other condition is constant, and Paraformaldehyde 96 changes 11.72g (0.375mol) into, obtains the former powder 140.67g of glyphosate (content 95.7%) altogether, amounts to every batch of former powder yield 79.26% of glyphosate, every batch of average total recovery 85.71%, average every crowd of mother liquor 27.37g.
Embodiment 6
Embodiment 5 other conditions are constant, dimethylphosphite changes 29.95g (0.275mol) into, obtains the former powder 135.65g of glyphosate (content 95.7%) altogether, amounts to every batch of former powder yield 76.36% of glyphosate, every batch of average total recovery 82.41%, average every crowd of mother liquor 29.57g.
Claims (12)
1. method for preparing glyphosate, it comprises the steps:
1) with glycine and Paraformaldehyde 96 drops into monohydroxy-alcohol simultaneously according to certain proportioning and tertiary amine system is separated polycondensation reaction, the dialkyl phosphite with proportional quantity carries out condensation reaction again;
2) reclaim alkohol and amine, add the acidolysis of hydrochloric acid temperature control again, and remove in acidolysis or oxidation of formaldehyde, direct crystallization is prepared glyphosate;
3) cover was used for the next batch acidolysis after mother liquor was added a certain amount of hydrochloric acid or fed quantitative hydrochloric acid gas.
2. method for preparing glyphosate, it comprises the steps:
1) glycine and Paraformaldehyde 96 are dropped in monohydroxy-alcohol and the tertiary amine system according to certain proportioning, be stirred to transparent after, be warming up to about 35-45 ℃, add the dialkyl phosphite of proportional quantity again, control pH is 7.0-8.0,40-65 ℃ of insulation until reacting completely;
2) mode by normal pressure or decompression or gas parsing reclaims alkohol and amine, after not having obvious liquid outflow, the temperature control acidolysis, and in acidolysis, resolve and/or the mode piptonychia aldehyde of decompression or the mode oxidation of formaldehyde of interpolation oxygenant by gas, acidolysis finishes the back direct crystallization and prepares glyphosate;
3) cover was used for the next batch hydrolysis after mother liquor was added a certain amount of hydrochloric acid or fed quantitative hydrochloric acid gas.
3. method according to claim 1 and 2, wherein in the step 1), glycine: Paraformaldehyde 96 is 1: 1.2-2.
4. according to the arbitrary described method of claim 1-3, wherein in the step 1), glycine: dimethylphosphite is 1: 0.8-1.3.
5. according to the arbitrary described method of claim 1-4, wherein in the step 1), adopting and dripping triethylamine hierarchy of control pH scope in batches is 7.0-8.0.
6. according to the arbitrary described method of claim 1-5, wherein step 2) in, reclaiming monohydroxy-alcohol and tertiary amine and take the mode of normal pressure, decompression or gas parsing to reclaim, controlled temperature is not higher than 80 ℃ is advisable, and most of hydramine is steamed as far as possible.
7. according to the arbitrary described method of claim 1-6, wherein step 2) in, monohydroxy-alcohol and tertiary amine recycled reclaimed.
8. according to the arbitrary described method of claim 1-7, wherein step 2) in, the hydrochloric acid of employing 30-37%, glycine: hydrochloric acid is 1: 1.5-4.5.
9. according to the arbitrary described method of claim 1-8, wherein step 2) in, acidolysis condition is a 20-70 ℃ of temperature.
10. the arbitrary described method of claim 1-9, wherein step 2) in, eliminate the mode that formaldehyde takes the gas of underpressure distillation and/or heating drum air to resolve, perhaps adopt and add H
2O
2, oxygenant oxidation such as NaClO mode.
11. according to the arbitrary described method of claim 1-10, wherein step 2) in, decompression acidifying vacuum tightness is P=-0.01MPa to-0.03MPa.
12. according to the arbitrary described method of claim 1-11, wherein in the step 3), glyphosate mother solution add hydrochloric acid content be triethylamine 0.2-2 doubly, applying mechanically number of times is 1-10 time.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103288606A (en) * | 2013-06-09 | 2013-09-11 | 湖北泰盛化工有限公司 | Method for recycling methylal in glyphosate wastewater |
| CN104151355A (en) * | 2014-08-06 | 2014-11-19 | 四川省乐山市福华通达农药科技有限公司 | Treatment technology of dirty powder of glyphosate prepared by glycine method |
| CN106279273A (en) * | 2016-08-13 | 2017-01-04 | 安徽东至广信农化有限公司 | A kind of production technology of glyphosate technicals |
| CN106472489A (en) * | 2016-08-30 | 2017-03-08 | 枣阳市先飞高科农药有限公司 | A kind of herbicide with fast onset pharmacodynamic feature |
| 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 |
| CN107383092A (en) * | 2017-07-13 | 2017-11-24 | 安徽东至广信农化有限公司 | A kind of hydrolyzing process of glyphosate production technique |
| CN108689392A (en) * | 2018-07-09 | 2018-10-23 | 江西金龙化工有限公司 | A kind of glyphosate three wastes integrated conduct method |
| CN114920773A (en) * | 2022-04-29 | 2022-08-19 | 镇江江南化工有限公司 | Method for synthesizing glyphosate by alkyl ester method and production device |
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| CN101591353A (en) * | 2008-05-28 | 2009-12-02 | 北京紫光英力化工技术有限公司 | Novel process for recycling mother solution of glyphosate prepared by glycin method |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103288606A (en) * | 2013-06-09 | 2013-09-11 | 湖北泰盛化工有限公司 | Method for recycling methylal in glyphosate wastewater |
| CN103288606B (en) * | 2013-06-09 | 2015-08-05 | 湖北泰盛化工有限公司 | A kind of method of the methylal reclaimed in glyphosate waste water |
| CN104151355A (en) * | 2014-08-06 | 2014-11-19 | 四川省乐山市福华通达农药科技有限公司 | Treatment technology of dirty powder of glyphosate prepared by glycine method |
| CN106279273A (en) * | 2016-08-13 | 2017-01-04 | 安徽东至广信农化有限公司 | A kind of production technology of glyphosate technicals |
| CN106472489A (en) * | 2016-08-30 | 2017-03-08 | 枣阳市先飞高科农药有限公司 | A kind of herbicide with fast onset pharmacodynamic feature |
| 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 |
| CN107383092A (en) * | 2017-07-13 | 2017-11-24 | 安徽东至广信农化有限公司 | A kind of hydrolyzing process of glyphosate production technique |
| CN108689392A (en) * | 2018-07-09 | 2018-10-23 | 江西金龙化工有限公司 | A kind of glyphosate three wastes integrated conduct method |
| CN108689392B (en) * | 2018-07-09 | 2019-10-25 | 江西金龙化工有限公司 | A kind of glyphosate three wastes integrated conduct method |
| CN114920773A (en) * | 2022-04-29 | 2022-08-19 | 镇江江南化工有限公司 | Method for synthesizing glyphosate by alkyl ester method and production device |
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Application publication date: 20110727 |