CN101928299A - Clean process method for preparing high-purity glyphosate from glycine - Google Patents
Clean process method for preparing high-purity glyphosate from glycine Download PDFInfo
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- CN101928299A CN101928299A CN2009101041239A CN200910104123A CN101928299A CN 101928299 A CN101928299 A CN 101928299A CN 2009101041239 A CN2009101041239 A CN 2009101041239A CN 200910104123 A CN200910104123 A CN 200910104123A CN 101928299 A CN101928299 A CN 101928299A
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- glyphosate
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Abstract
The invention relates to an environment-friendly clean process method for synthesizing high-purity glyphosate by a glycine method. The invention is characterized by comprising the following steps of: carrying out synthesis reaction on the excessive glycine which is used as a starting material and depolymerized paraformaldehyde methanol solutions to obtain a methanol solution as an intermediate; making the reaction solution react with dimethylphosphite; dewatering mixture of recovered methanol by desolution and triethylamine and directly using; carrying out acidolysis on precipitates in the presence of hydrochloric acid to obtain a glyphosate reactant system and methyl chloride by-products; carrying out treatment including purification, crystallization, filter, product drying and the like on the glyphosate reactant system to obtain high-purity raw glyphosate powder; and crystallizing by using the mother solution in the purification process for the glyphosate reactant system to obtain products. The mother solution is recycled without emissions so that the environment-friendly clean production is realized.
Description
A kind ofly relating to the clean process method that glycine prepares high-purity glyphosate, is to be the clean process method of the former medicine of raw material production herbicide glyphosate with glycine, Paraformaldehyde 96 and alkyl phosphite, belongs to the clean preparation method of pesticide original medicine.
Glyphosate has another name called the sweet acid of phosphine, and chemical name is N-(phosphonomethyl) glycine, English N-(phosphono methyl) glycine by name, and general glyphosate by name, chemical structure skeleton symbol are (HO)
2POCH
2NHCH
2COOH.
Glyphosate is a kind of steriland herbicide of wide spectrum efficiently, is found and development and use in 1972 by U.S. Monsanto Company, and is because of it has good interior suction conductive performance, very effective to the removing of multiple dark root malignant weed; In recent years, this product has obtained using widely, and along with the popularization of genetically modified crops, its range of application will further enlarge.
The industrial product route of synthesizing glyphosate is more at present, as chloromethyl phosphonic acids method, iminodiethanoic acid (IDA) method, dialkyl phosphite method and phosphorous test etc., but really realize industrializedly mainly containing two, article one, what be that U.S. Monsanto Company adopts is iminodiethanoic acid (IDA) route of starting raw material with prussic acid or diethanolamine, what another was that China generally adopts is the dialkyl phosphite route of starting raw material with the glycine, and these two lines all can obtain purity and be not less than 93.5% the former powder of glyphosate.
Up to the present, numerous research launches around the IDA route, and disclosing respectively with iminodiethanoic acid (IDA) as US5312973, US5023369 is that starting raw material prepares pmida98 and prepared the method for glyphosate by the pmida98 oxidation: ZL93120707, ZL96195765 also disclose respectively by the iminodiacetic acid (salt) acid alkali metal salt and have prepared pmida98 and prepared the method for glyphosate by the pmida98 hydrogen peroxide oxidation.
The main embodiment of dialkyl phosphite route research is as follows, and application number is that to disclose a kind of be the glyphosate preparation technology of raw material with the phosphate dialkyl ester for 85102988 patent of invention; Application number be 00125933 patent of invention disclose a kind of to the improvement of dialkyl phosphite technology, do not adopt multistage formaldehyde but utilize the by product methylal of self to come synthesizing glyphosate; " trimethyl phosphite synthesizing glyphosate technical study " (" PESTICIDES ") 1999,38 (6) in addition, P8 have introduced trimethyl phosphite and the glycine method at the aqueous phase synthesizing glyphosate; 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; Application number provides a kind of method of mother liquor processing for 200410099086.4 patent of invention; Application number is an a kind of step method of condensing that adopts glycine and inorganic salt and Paraformaldehyde 96, methyl alcohol and tertiary amine thereof to feed intake simultaneously of patent proposition of 200510105695.0; Application number is the post-treatment new process that 200510115909.2 patent proposes a kind of preparing glyphosate by glycin method.
Dialkyl phosphite technology obtains tremendous development in China, this route process using Paraformaldehyde 96 the depolymerization of methyl alcohol triethylamine system obtain formal, then with the glycine condensation, again with the dialkyl phosphite condensation, last acidifying, separating methanol, depickling, crystallization, filtration, oven dry obtain the former powder of glyphosate.
The reaction that adds glycine after the Paraformaldehyde 96 depolymerization, reaction system are that two molecule formaldehyde and a part glycine are synthetic; But finally in the acidolysis process, the formaldehyde that must discharge a part again just can become the target product glyphosate.In this process, not only waste raw material, and cause the very big difficulty of wastewater treatment, therefore embody the non-feature of environmental protection of production technique.Because the release of this a part formaldehyde needs comparatively exacting terms in the acidolysis process: higher as temperature requirement, but the effective product of system decomposes serious under comparatively high temps; Therefore the acidolysis transformation efficiency becomes the technical bottleneck that present glycine method is produced glyphosate, transformation efficiency lowly not only has a strong impact on yield, the more important thing is that product purity is not high, the product effective content can only remain on all the time about 95% or more than, be difficult to obtain higher-quality product.
The environment-friendly clean process method that the purpose of this invention is to provide the synthetic high-purity glyphosate of a kind of glycine method, it is characterized in that with the glycine being starting raw material, through under a large amount of excessive situations of glycine, realizing building-up reactions, obtain the synthetic intermediate methanol solution with the Paraformaldehyde 96 methanol solution of depolymerization; This reaction solution reacts with dimethylphosphite again, and precipitation reclaims methyl alcohol and the triethylamine mixed solution is directly applied mechanically by dehydration; Precipitate acidolysis under the hydrochloric acid effect obtains the glyphosate reactant system, obtains the methyl chloride by-product simultaneously; The glyphosate reactant system through purification, crystallization, filtration, product drying etc. handle the former powder of high-purity glyphosate.Mother liquid recycle in glyphosate reactant system cleaning section, crystallization obtains product, Recycling Mother Solution is used does not have discharging, realizes environment-protecting clean production.Technological process provided by the invention mainly divided for three steps carried out:
The first step: the Paraformaldehyde 96 methanol solution of depolymerization obtains the intermediate compound I methanol solution with a large amount of excessive glycine reactants.
CH
2O+NH
2CH
2COOH→HOCH
2NHCH
2COOH
(intermediate compound I)
The Paraformaldehyde 96 methanol solution of depolymerization is having in the presence of the triethylamine, and normal pressure down obtains the intermediate compound I methanol solution with excessive in a large number glycine reactants, and intermediate compound I is that a hydrogen atom on the glycine amino is by formaldehyde group metathetical product; Glycine and formaldehyde mole ratio can be 1200, are preferably 1.2-50 in the system reaction environment, and temperature is 10 ℃-65 ℃, is preferably 25 ℃-45 ℃; Excessive glycine filtration cycle is applied mechanically.
Second step: the intermediate compound I methanol solution that the first step obtains obtains esterification intermediate II methanol solution with the dimethylphosphite reaction.
HOCH
2NHCH
2COOH+(CH
3O)
2POH→(CH
3O)
2POCH
2NHCH
2COOH+H
2O
(intermediate compound I) (intermediate II)
Intermediate compound I methanol solution and dimethylphosphite reaction, temperature of reaction is generally carried out under 40 ℃-75 ℃; Reaction times generally needs 1-5 hour.Esterification later stage negative pressure precipitation reclaims methyl alcohol, reclaims triethylamine simultaneously, reclaims mixing solutions after removing water treatment, recycled.
The 3rd step: the esterification intermediate II behind the precipitation obtains the glyphosate system through the hydrochloric acid soln acidifying; Obtain the by product methyl chloride simultaneously.
(CH
3O)
2POCH
2NHCH
2COOH+HCl→(HO)
2POCH
2NHCH
2COOH+CH
3Cl
(intermediate II) (glyphosate)
Intermediate II is in acidization, and rare formaldehyde, formal discharge, and are convenient to the processing of methyl chloride by-product, can make the process environmental protection that becomes; Temperature of reaction is relatively low, can react completely below 80 ℃, has not only guaranteed transformation efficiency but also prevented the side reaction generation, has not only improved yield greatly, and has guaranteed the high purity of product.
Reactions steps process of the present invention is: the Paraformaldehyde 96 methanol solution of depolymerization obtains the intermediate compound I methanol solution having in the presence of the triethylamine and a large amount of excessive glycine reactants, and excessive glycine filters and applies mechanically; Intermediate compound I methanol solution and dimethylphosphite esterification obtain the intermediate II methanol solution; Intermediate II methanol solution process carrying out precipitation treatment, recycled after recovery methyl alcohol and triethylamine, the processed; The acidifying in hydrochloric environment of intermediate II behind the precipitation obtains the glyphosate reactant system, obtains byproduct chloromethane simultaneously; The glyphosate reactant system through purification, crystallization, filtration, product drying etc. handle the former powder of high-purity glyphosate.Mother liquor purification process cover is used for the glyphosate reactant system to be purified Crystallization Procedure, realizes the environment-protecting clean production that Recycling Mother Solution is used does not have discharging.
Accompanying drawing is a process flow sheet of the present invention.
From above-mentioned reactions steps and technical process, can find out feature of the present invention:
1, patent of the present invention provide a kind of take glycine as raw material, through with the polyformaldehyde reaction of depolymerization, dimethylphosphite esterification, acidifying obtains the high-purity glyphosate environment-protecting clean manufacturing technique method of glyphosate in the presence of hydrochloric acid again. In the paraformaldehyde building-up process of glycine and depolymerization, adopt a large amount of excessive methods of glycine, synthetic intermediate is that a hydrogen atom on the glycine amino is by the product of formaldehyde group displacement.
2, present technique process program, very effective numerous and diverse operation sequence of having avoided pilot process greatly reduces the operational labour intensity of site technique; Reduce simultaneously equipment investment, reduced energy consumption, saved raw material, also greatly reduce the loss of intermediate material.
3, can accomplish three-waste free discharge fully in the whole technical process, be proper environment-friendly clean process. Solvent in the system etc. can recycled, and mother liquor can be realized recycled, and high polymer and the mechanical admixture of trace can be concentrated burning disposal.
4, the maximum feature of this technology is that acidification reaction is carried out under very gentle condition, has simplified acidizing process; Not only greatly improve reaction conversion ratio, the more important thing is the glyphosate products that can obtain high-load.
5, this technology can obtain highly purified chloromethanes byproduct very easily, makes producing glyphosate by using glycine realize very good economic benefit and social benefit.
Embodiment:
Experimental example 1: 160L methyl alcohol is fed in the 500L reactor with volume pump, drops into 95% Paraformaldehyde 96 31.9k, throw 95% triethylamine 75L again in reactor, stirring reaction under 30 ℃ of temperature, till the dissolving, obtain depolymerization Paraformaldehyde 96 methanol solution fully, standby.In the reactor that has return channel, condenser of another 1000L, drop into 320L methyl alcohol and 98kg98.5% glycine, maintain the temperature at 40 ℃ and stir down; Again with above-mentioned depolymerization Paraformaldehyde 96 methanol solution slowly stream be added in the reactor and react; 80 minutes stream adds and finishes, and it is static to continue to stir 1 hour postcooling down at 45 ℃, filters to isolate glycine, obtains the methanol solution of intermediate compound I.Drop into 98% dimethylphosphite 134.8kg reaction at 45 ℃, slowly be warmed up to about 60 ℃ and reacted 4 hours down; The decompression precipitation reclaims methyl alcohol and reclaims triethylamine simultaneously; When pressure stops precipitation at-0.088MPa, temperature of charge when being elevated to 95 ℃.The methyl alcohol and the Trimethylamine 99 mixing solutions that reclaim, directly cover is used to prepare depolymerization Paraformaldehyde 96 methanol solution after molecular sieve dewaters; Reactant behind the precipitation adds 37% aqueous hydrochloric acid 197.3kg acidolysis, and temperature progressively is elevated to 80 ℃, and keeps 1 hour down at 80 ℃.Acidolysis reaction discharges methyl chloride, collects and obtains the methyl chloride by-product, is used for organosilyl production; Acid hydrolysis solution is through purification, cooling, crystallization, separation, dry product 147.2kg, the content 98.70% of getting; Mother liquor 284.6kg contains glyphosate 3.76kg, mother liquid recycle.A yield 85.93%, total recovery 88.16%.
Experimental example 2: 160L methyl alcohol is fed in the 500L reactor with volume pump, drops into 95% Paraformaldehyde 96 31.9k, throw 95% triethylamine 75L again in reactor, stirring reaction under 30 ℃ of temperature, till the dissolving, obtain depolymerization Paraformaldehyde 96 methanol solution fully, standby.In the reactor that has return channel, condenser of another 1000L, drop into 320L methyl alcohol and 128kg98.5% glycine, maintain the temperature at 40 ℃ and stir down; Again with above-mentioned depolymerization Paraformaldehyde 96 methanol solution slowly stream be added in the reactor and react; 90 minutes stream adds and finishes, and it is static to continue to stir 1 hour postcooling down at 45 ℃, filters to isolate glycine, obtains the methanol solution of intermediate compound I.Drop into 98% dimethylphosphite 134.8kg reaction at 42 ℃, slowly be warmed up to 60 ℃ and reacted 4 hours down; The decompression precipitation reclaims methyl alcohol and reclaims triethylamine simultaneously; When pressure stops precipitation at-0.088MPa, temperature of charge when being elevated to 95 ℃.The methyl alcohol and the Trimethylamine 99 mixing solutions that reclaim, directly cover is used to prepare depolymerization Paraformaldehyde 96 methanol solution after molecular sieve dewaters; Reactant behind the precipitation adds 37% aqueous hydrochloric acid 197.3kg acidolysis, and temperature progressively is elevated to 80 ℃, and keeps 1 hour down at 80 ℃.Acidolysis reaction discharges methyl chloride, collects and obtains the methyl chloride by-product, is used for organosilyl production; Acid hydrolysis solution is through purification, cooling, crystallization, separation, dry product 148.1kg, the content 98.72% of getting; Mother liquor 278.2kg contains glyphosate 3.65kg, mother liquid recycle.A yield 86.48%, total recovery 88.63%.
Claims (3)
1. one kind relates to the clean process method that glycine prepares high-purity glyphosate, and the Paraformaldehyde 96 methanol solution that it is characterized in that depolymerization obtains the intermediate compound I methanol solution having in the presence of the triethylamine and a large amount of excessive glycine reactants; Intermediate compound I methanol solution and dimethylphosphite esterification obtain the intermediate II methanol solution; The intermediate II methanol solution reclaims methyl alcohol and triethylamine recycled after processed through carrying out precipitation treatment; The acidifying in hydrochloric environment of intermediate II behind the precipitation obtains the glyphosate reactant system, obtains byproduct chloromethane simultaneously; The glyphosate reactant system through purification, crystallization, filtration, product drying etc. handle the former powder of high-purity glyphosate; Mother liquor purification process cover is used for the glyphosate reactant system and purifies Crystallization Procedure, realizes the environment-protecting clean production that Recycling Mother Solution is used does not have discharging.
2. the clean process method for preparing high-purity glyphosate according to the described glycine of claim 1, the polyformaldehyde reaction of wherein said glycine a large amount of excessive and depolymerization, obtain the intermediate compound I methanol solution, it is characterized in that: intermediate compound I is that a hydrogen atom on the glycine amino is by formaldehyde group metathetical product; Glycine and formaldehyde mole ratio can be 1-200 in the system reaction environment, are preferably 1.2-50; Temperature is 10 ℃-60 ℃, is preferably 25 ℃-45 ℃; Excessive glycine filtration cycle is applied mechanically.
3. the clean process method for preparing high-purity glyphosate according to the described glycine of claim 1, the acidifying in hydrochloric environment of intermediate II behind the wherein said precipitation obtains the glyphosate reactant system, it is characterized in that: intermediate II is in acidization, rare formaldehyde, formal discharge, be convenient to the processing of methyl chloride by-product, can make the process environmental protection that becomes; Temperature of reaction is relatively low, can react completely below 80 ℃, has not only guaranteed transformation efficiency but also prevented the side reaction generation, has not only improved yield greatly, and has guaranteed the high purity of product.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| CN105254665A (en) * | 2015-11-13 | 2016-01-20 | 安徽省益农化工有限公司 | Preparation technology of glyphosate |
| 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 |
| 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 |
| 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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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85102988A (en) * | 1985-04-01 | 1986-09-10 | 贵州省化工研究所 | The manufacture method of N-phosphono-methyl-glycine |
| CN1165540C (en) * | 2000-08-31 | 2004-09-08 | 浙江新安化工集团股份有限公司 | Process for preparing glyphosate |
| CN100443490C (en) * | 2005-09-23 | 2008-12-17 | 四川省乐山市福华通达农药科技有限公司 | Process for preparing glyphosate |
| 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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2009
- 2009-06-18 CN CN200910104123.9A patent/CN101928299B/en active Active
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102850395A (en) * | 2012-10-11 | 2013-01-02 | 常州储能材料与器件研究院 | Method for synthesizing glyphosate |
| 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 |
| 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 |
| CN105254665A (en) * | 2015-11-13 | 2016-01-20 | 安徽省益农化工有限公司 | Preparation technology of glyphosate |
| 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 |
| 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 |
| 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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