CN101704844A - Method for preparing glyphosate by alkyl phosphite - Google Patents
Method for preparing glyphosate by alkyl phosphite Download PDFInfo
- Publication number
- CN101704844A CN101704844A CN200910050073A CN200910050073A CN101704844A CN 101704844 A CN101704844 A CN 101704844A CN 200910050073 A CN200910050073 A CN 200910050073A CN 200910050073 A CN200910050073 A CN 200910050073A CN 101704844 A CN101704844 A CN 101704844A
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- reaction
- alkyl phosphite
- adds
- glyphosate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
The invention relates to a method for preparing glyphosate by alkyl phosphite. The method comprises the following steps: (1) putting paraformaldehyde, triethylamine, methanol and molecular sieve in a container to obtain transparent depolymerizing reaction solution through depolymerizing reaction; (2) adding glycin in the depolymerizing reaction solution to perform addition reaction; (3) adding triethylamine and alkyl phosphite in the reaction solution to perform condensation reaction, and eliminating molecular sieve through filtration after the reaction; (4) adding hydrochloric acid in the reaction solution without molecular sieve and obtaining hydrolytic reaction solution through acidolysis; and (5) carrying out decompressed dealcoholization and deacidification, natural cooling crystallization, suction filtration and drying of the hydrolytic reaction solution to obtain the raw powder of glyphosate. Compared with the prior art, the method makes use of molecular sieve to eliminate water in a system and adopts a method of adding catalyst triethylamine step by step, thereby quickening reaction speed, reducing material and energy consumption and substantially increasing the yield and quality of glyphosate.
Description
Technical field
The present invention relates to a kind of preparation method of compound, especially relate to a kind of method of preparing glyphosate by alkyl phosphite.
Background technology
Glyphosate is a kind of efficient, low toxicity, wide spectrum steriland herbicide, uses to have exceeded 25 years.In recent years, because the transgenic crop large-scale promotion of resistance glyphosate, the market requirement of glyphosate increases rapidly, constantly substitutes the weedicide of other classes, occupies the first place that world's agricultural chemicals is sold for years.
The glyphosate production method mainly contains two kinds, is the IDA method of starting raw material with iminodiethanoic acid (be called for short IDA) promptly and is the glycine method of raw material with the glycine.Though world's main flow technology is the IDA method, but because " glycine " method technology is simple, the domestic production development of raw material glycine, dimethylphosphite is rapid, constant product quality, buying is relatively easy, add to be subjected to the few restriction of domestic iminodiacetic acid (salt) acid yield, IDA produces the route slower development, and the glyphosate of ultimate production 70% still adopts glycine method.
And aspect technical research, the numerous domestic report is studied about the IDA route, and the reaction mechanism more complicated of glycine route, never what breakthrough, report less, application number are that 00125933 patent of invention discloses the process modification that a kind of by product methylal that utilizes self comes synthesizing glyphosate; Application number is that to disclose a kind of be the glyphosate preparation technology of raw material with glycine and alkyl phosphite for 200510105695 patent of invention; Application number is that 200510012841 patent of invention discloses a kind of novel process for preparing glyphosate.
Summary of the invention
Purpose of the present invention is exactly to provide a kind of speed of response fast for the defective that overcomes above-mentioned prior art existence, and energy consumption and material consumption are low, the method for a kind of preparing glyphosate by alkyl phosphite that the yield of glyphosate and quality are higher.
Purpose of the present invention can be achieved through the following technical solutions:
A kind of method of preparing glyphosate by alkyl phosphite is characterized in that, this method may further comprise the steps:
(1) Paraformaldehyde 96, triethylamine, methyl alcohol, molecular sieve are placed the four-hole boiling flask of taking back stream prolong, thermometer and whipping appts, under 35-50 ℃ condition, stirring reaction 10-60min obtains transparent depolymerization reaction liquid;
(2) add glycine in depolymerization reaction liquid, under 30-38 ℃ condition, stirring reaction 20-50min obtains transparent reaction solution;
(3) in the reaction solution that step (2) obtains, add triethylamine and alkyl phosphite, under 51-54 ℃ condition, condensation reaction 50-70min, reaction removes by filter molecular sieve after finishing, and with 20-40g methanol wash molecular sieve;
(4) adding concentration expressed in percentage by weight in the reaction solution of removing molecular sieve is the hydrochloric acid of 30-35%, carries out acidolysis under 30-60 ℃ condition, obtains hydrolysis reaction liquid;
(5) hydrolysis reaction liquid dealcoholysis depickling under the 0.2-0.5MPa vacuum when temperature reaches 105-110 ℃, stops decompression, adds the 80-100g deionized water, more successively through natural cooling crystallization, and suction filtration and be drying to obtain the former powder of glyphosate.
The mol ratio of the Paraformaldehyde 96 that adds in the described step (1), triethylamine, methyl alcohol is (1.8-2.3): (0.7-0.9): (4.0-8.0).
The molecular sieve that adds in the described step (1) comprises 3A molecular sieve or 4A molecular sieve.
The molecular sieve that adds in the described step (1) is 20-60% with respect to the weight ratio of glycine.
The glycine that adds in the described step (2) and the mol ratio of Paraformaldehyde 96 are 1: (1.8-2.3).
The mol ratio of the triethylamine that adds in triethylamine that adds in the described step (3) and the step (1) is 1: (0.2-0.5).
The alkyl phosphite that described step (3) adds and the mol ratio of Paraformaldehyde 96 are (0.9-1.0): (1.8-2.3).
The alkyl phosphite that described step (3) adds comprises dimethylphosphite.
The hydrochloric acid that described step (4) adds and the mol ratio of Paraformaldehyde 96 are (3.0-3.7): (1.8-2.3).
Compared with prior art, the present invention utilizes the water in the molecular sieve removal system, adopt substep to add the method for catalyst of triethylamine, help fast reaction speed, reduce material consumption and energy consumption, compared to the prior art, glyphosate yield of the present invention and quality significantly improve, yield is brought up to 84-86% (in glycine) from 78-81%, and glyphosate content is brought up to 95-98% from 93-95%, and the mother liquor amount of generation also reduces to some extent.This method also has cleaning, environmental protection, characteristics of high efficiency.
Embodiment
Hereinafter provide indefiniteness embodiment, be intended to illustrate the present invention but not limit content of the present invention by any way.
Comparative example 1
(1) Paraformaldehyde 96 0.90mol, triethylamine 0.40mol, methyl alcohol 3.48mol are placed the four-hole boiling flask of taking back stream prolong, thermometer and whipping appts, under 30 ℃ condition, stirring reaction 10min obtains transparent depolymerization reaction liquid;
(2) add glycine 0.4mol in depolymerization reaction liquid, under 30 ℃ condition, stirring reaction 20min obtains transparent reaction solution;
(3) in the reaction solution that step (2) obtains, add triethylamine 0.30mol and dimethylphosphite 0.45mol, under 51 ℃ condition, condensation reaction 50min;
(4) filtrate and washing lotion are merged, in the reaction solution of removing molecular sieve, add concentration expressed in percentage by weight again and be 30% hydrochloric acid 1.50mol, under 30 ℃ condition, carry out acidolysis, obtain hydrolysis reaction liquid;
(5) hydrolysis reaction liquid dealcoholysis depickling under the 0.2MPa vacuum when temperature reaches 105 ℃, stops decompression, add the 85g deionized water, more successively through natural cooling crystallization, suction filtration and be drying to obtain the former powder 65.8g of glyphosate (content 92.1%), former powder yield 77%, total recovery 80%.
Comparative example 2
(1) Paraformaldehyde 96 0.95mol, triethylamine 0.11mol, methyl alcohol 3.50mol are placed the four-hole boiling flask of taking back stream prolong, thermometer and whipping appts, under 35 ℃ condition, stirring reaction 60min obtains transparent depolymerization reaction liquid;
(2) add glycine 0.5mol in depolymerization reaction liquid, under 38 ℃ condition, stirring reaction 50min obtains transparent reaction solution;
(3) in the reaction solution that step (2) obtains, add triethylamine 0.29mol and dimethylphosphite 0.48mol, under 54 ℃ condition, condensation reaction 70min;
(4) filtrate and washing lotion are merged, in the reaction solution of removing molecular sieve, add concentration expressed in percentage by weight again and be 35% hydrochloric acid 1.60mol, under 60 ℃ condition, carry out acidolysis, obtain hydrolysis reaction liquid;
(5) hydrolysis reaction liquid dealcoholysis depickling under the 0.5MPa vacuum when temperature reaches 110 ℃, stops decompression, add the 90g deionized water, more successively through natural cooling crystallization, suction filtration and be drying to obtain the former powder 69.2g of glyphosate (content 94.9%), former powder yield 78%, total recovery 82%.
Find that in research process water content is too much in the reaction system, can influence level of response and time during depolymerization reaction, can influence direction and speed during addition reaction, consume alkyl phosphites more, finally influence the yield and the quality of glyphosate, and inorganic salt such as sodium sulfate are removed the moisture weak effect.So the present invention adds molecular sieve in reaction system,, after condensation reaction finishes, remove molecular sieve again with the moisture in the system of removing.
Embodiment 1
(1) Paraformaldehyde 96 0.95mol, triethylamine 0.40mol, methyl alcohol 3.51mol, molecular sieve 7.6g are placed the four-hole boiling flask of taking back stream prolong, thermometer and whipping appts, under 35 ℃ condition, stirring reaction 10min obtains transparent depolymerization reaction liquid;
(2) add glycine 0.5mol in depolymerization reaction liquid, under 30 ℃ condition, stirring reaction 20min obtains transparent reaction solution;
(3) in the reaction solution that step (2) obtains, add triethylamine 0.29mol and dimethylphosphite 0.48mol, under 51 ℃ condition, condensation reaction 50min, reaction removes by filter molecular sieve after finishing, and with 20g methanol wash molecular sieve;
(4) filtrate and washing lotion are merged, in the reaction solution of removing molecular sieve, add concentration expressed in percentage by weight again and be 30% hydrochloric acid 1.60mol, under 30 ℃ condition, carry out acidolysis, obtain hydrolysis reaction liquid;
(5) hydrolysis reaction liquid dealcoholysis depickling under the 0.2MPa vacuum when temperature reaches 105 ℃, stops decompression, add the 80g deionized water, more successively through natural cooling crystallization, suction filtration and be drying to obtain the former powder 70.9g of glyphosate (content 96.1%), former powder yield 81%, total recovery 84%.
Embodiment 2
(1) Paraformaldehyde 96 1.05mol, triethylamine 0.09mol, methyl alcohol 2.50mol, molecular sieve 9.5g are placed the four-hole boiling flask of taking back stream prolong, thermometer and whipping appts, under 40 ℃ condition, stirring reaction 30min obtains transparent depolymerization reaction liquid;
(2) add glycine 0.5mol in depolymerization reaction liquid, under 35 ℃ condition, stirring reaction 40min obtains transparent reaction solution;
(3) in the reaction solution that step (2) obtains, add triethylamine 0.31mol and dimethylphosphite 0.49mol, under 53 ℃ condition, condensation reaction 60min, reaction removes by filter molecular sieve after finishing, and with 40g methanol wash molecular sieve;
(4) filtrate and washing lotion are merged, in the reaction solution of removing molecular sieve, add concentration expressed in percentage by weight again and be 35% hydrochloric acid 1.80mol, under 35 ℃ condition, carry out acidolysis, obtain hydrolysis reaction liquid;
(5) hydrolysis reaction liquid dealcoholysis depickling under the 0.4MPa vacuum when temperature reaches 108 ℃, stops decompression, add the 90g deionized water, more successively through natural cooling crystallization, suction filtration and be drying to obtain the former powder 70.6g of glyphosate (content 97.3%), former powder yield 81%, total recovery 85%.
Embodiment 3
(1) Paraformaldehyde 96 1.20mol, triethylamine 0.11mol, methyl alcohol 2.80mol, molecular sieve 10.6g are placed the four-hole boiling flask of taking back stream prolong, thermometer and whipping appts, under 50 ℃ condition, stirring reaction 60min obtains transparent depolymerization reaction liquid;
(2) add glycine 0.6mol in depolymerization reaction liquid, under 38 ℃ condition, stirring reaction 50min obtains transparent reaction solution;
(3) in the reaction solution that step (2) obtains, add triethylamine 0.35mol and dimethylphosphite 0.53mol, under 54 ℃ condition, condensation reaction 70min, reaction removes by filter molecular sieve after finishing, and with 40g methanol wash molecular sieve;
(4) filtrate and washing lotion are merged, in the reaction solution of removing molecular sieve, add concentration expressed in percentage by weight again and be 35% hydrochloric acid 1.90mol, under 60 ℃ condition, carry out acidolysis, obtain hydrolysis reaction liquid;
(5) hydrolysis reaction liquid dealcoholysis depickling under the 0.5MPa vacuum when temperature reaches 110 ℃, stops decompression, add the 100g deionized water, more successively through natural cooling crystallization, suction filtration and be drying to obtain the former powder 73.6g of glyphosate (content 97.5%), former powder yield 82%, total recovery 86%.
Claims (9)
1. the method for a preparing glyphosate by alkyl phosphite is characterized in that, this method may further comprise the steps:
(1) Paraformaldehyde 96, triethylamine, methyl alcohol, molecular sieve are placed the four-hole boiling flask of taking back stream prolong, thermometer and whipping appts, under 35-50 ℃ condition, stirring reaction 10-60min obtains transparent depolymerization reaction liquid;
(2) add glycine in depolymerization reaction liquid, under 30-38 ℃ condition, stirring reaction 20-50min obtains transparent reaction solution;
(3) in the reaction solution that step (2) obtains, add triethylamine and alkyl phosphite, under 51-54 ℃ condition, condensation reaction 50-70min, reaction removes by filter molecular sieve after finishing, and with 20-40g methanol wash molecular sieve;
(4) adding concentration expressed in percentage by weight in the reaction solution of removing molecular sieve is the hydrochloric acid of 30-35%, carries out acidolysis under 30-60 ℃ condition, obtains hydrolysis reaction liquid;
(5) hydrolysis reaction liquid dealcoholysis depickling under the 0.2-0.5MPa vacuum when temperature reaches 105-110 ℃, stops decompression, adds the 80-100g deionized water, more successively through natural cooling crystallization, and suction filtration and be drying to obtain the former powder of glyphosate.
2. the method for a kind of preparing glyphosate by alkyl phosphite according to claim 1 is characterized in that, the mol ratio of the Paraformaldehyde 96 that adds in the described step (1), triethylamine, methyl alcohol is (1.8-2.3): (0.7-0.9): (4.0-8.0).
3. the method for a kind of preparing glyphosate by alkyl phosphite according to claim 1 is characterized in that, the molecular sieve that adds in the described step (1) comprises 3A molecular sieve or 4A molecular sieve.
4. the method for a kind of preparing glyphosate by alkyl phosphite according to claim 1 is characterized in that, the molecular sieve that adds in the described step (1) is 20-60% with respect to the weight ratio of glycine.
5. the method for a kind of preparing glyphosate by alkyl phosphite according to claim 1 is characterized in that, the glycine that adds in the described step (2) and the mol ratio of Paraformaldehyde 96 are 1: (1.8-2.3).
6. the method for a kind of preparing glyphosate by alkyl phosphite according to claim 1 is characterized in that, the mol ratio of the triethylamine that adds in triethylamine that adds in the described step (3) and the step (1) is 1: (0.2-0.5).
7. the method for a kind of preparing glyphosate by alkyl phosphite according to claim 1 is characterized in that, the alkyl phosphite that described step (3) adds and the mol ratio of Paraformaldehyde 96 are (0.9-1.0): (1.8-2.3).
8. the method for a kind of preparing glyphosate by alkyl phosphite according to claim 1 is characterized in that, the alkyl phosphite that described step (3) adds comprises dimethylphosphite.
9. the method for a kind of preparing glyphosate by alkyl phosphite according to claim 1 is characterized in that, the hydrochloric acid that described step (4) adds and the mol ratio of Paraformaldehyde 96 are (3.0-3.7): (1.8-2.3).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910050073A CN101704844A (en) | 2009-04-27 | 2009-04-27 | Method for preparing glyphosate by alkyl phosphite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910050073A CN101704844A (en) | 2009-04-27 | 2009-04-27 | Method for preparing glyphosate by alkyl phosphite |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101704844A true CN101704844A (en) | 2010-05-12 |
Family
ID=42375103
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200910050073A Pending CN101704844A (en) | 2009-04-27 | 2009-04-27 | Method for preparing glyphosate by alkyl phosphite |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101704844A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102775441A (en) * | 2012-07-30 | 2012-11-14 | 浙江金帆达生化股份有限公司 | Continuous production method of glyphosate synthetic liquid |
| CN107522738A (en) * | 2017-07-13 | 2017-12-29 | 安徽东至广信农化有限公司 | A kind of synthesis technique of glyphosate |
| CN114031637A (en) * | 2021-11-05 | 2022-02-11 | 安徽东至广信农化有限公司 | Continuous hydrolysis method of glyphosate |
| CN114031637B (en) * | 2021-11-05 | 2024-06-11 | 安徽东至广信农化有限公司 | Method for continuously hydrolyzing glyphosate |
-
2009
- 2009-04-27 CN CN200910050073A patent/CN101704844A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102775441A (en) * | 2012-07-30 | 2012-11-14 | 浙江金帆达生化股份有限公司 | Continuous production method of glyphosate synthetic liquid |
| CN102775441B (en) * | 2012-07-30 | 2015-07-22 | 浙江金帆达生化股份有限公司 | Continuous production method of glyphosate synthetic liquid |
| CN107522738A (en) * | 2017-07-13 | 2017-12-29 | 安徽东至广信农化有限公司 | A kind of synthesis technique of glyphosate |
| CN114031637A (en) * | 2021-11-05 | 2022-02-11 | 安徽东至广信农化有限公司 | Continuous hydrolysis method of glyphosate |
| CN114031637B (en) * | 2021-11-05 | 2024-06-11 | 安徽东至广信农化有限公司 | Method for continuously hydrolyzing glyphosate |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1935816A (en) | Process for preparing glyphosate | |
| CN100526276C (en) | Process of preparing dipentaerythritol and/or tripentaerythritol | |
| CN101265320A (en) | Method for preparing low content of organic chlorine epoxy resin | |
| CN105130765A (en) | Production method for 90-level dipentaerythritol | |
| CN106278863B (en) | A kind of preparation method of 2,4 dichlorophenoxyacetic acid | |
| CN101704844A (en) | Method for preparing glyphosate by alkyl phosphite | |
| CN103073408A (en) | Preparation method of dichlorodiphenylene ether ketone | |
| CN103265443A (en) | Industrial production method of high-purity iminodiacetic acid | |
| CN101704843B (en) | Glyphosate continuous desolventizing production process | |
| CN111807877A (en) | DL-p-hydroxyphenylhydantoin and production process of urea sulfate/ammonium sulfate thereof | |
| CN105541929B (en) | A kind of method that microwave radiation technology organic acid prepares xylo-oligosaccharide | |
| CN105061486B (en) | A kind of preparation method of acidic crosslinking agent | |
| CN101875671A (en) | Synthesis method of glyphosate | |
| CN111393331A (en) | Preparation method of glycocyamine | |
| CN101508678B (en) | Process for preparing 2-methyl-4-amino-5-acetyl aminomethyl pyrimidine | |
| CN1308336C (en) | Process for treating production mother liquor of glyphosate | |
| CN101671363B (en) | Hydrolyzation post-processing technique during preparation of glyphosate through glycin method | |
| CN110862413A (en) | Glyphosate synthesis process and device | |
| CN112778094B (en) | Preparation process of high-purity tetrabromobisphenol A | |
| CN105001086A (en) | Synthetic method of methylclhlorofonmate | |
| CN103012475B (en) | A kind of preparation method of glyphosate | |
| CN111977683A (en) | Preparation method of zinc sulfate monohydrate | |
| CN112645815A (en) | Preparation method for catalytically synthesizing methyl cinnamate based on eutectic solvent | |
| CN101648969B (en) | Preparation method of N-phosphonomethyliminodiacetic acid | |
| CN210765082U (en) | Glyphosate technical cleaning equipment |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20100512 |