CN101704842A - Process for preparing glyphosate by using glycine - Google Patents
Process for preparing glyphosate by using glycine Download PDFInfo
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- CN101704842A CN101704842A CN200910050070A CN200910050070A CN101704842A CN 101704842 A CN101704842 A CN 101704842A CN 200910050070 A CN200910050070 A CN 200910050070A CN 200910050070 A CN200910050070 A CN 200910050070A CN 101704842 A CN101704842 A CN 101704842A
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Abstract
The invention relates to a process for preparing glyphosate by using glycine, which comprises the following steps: (1) putting paraformaldehyde, methanol and triethylamine in a reaction vessel, maintaining the reaction temperature to be 30-50 DEG C and stirring until the mixture is transparent; (2) adding the glycine to the reaction solution, and reacting to obtain condensation solution; (3) adding diisopropyl phosphate to the condensation solution, and reacting to obtain esterification solution; (4) adding hydrochloric acid to the esterification solution for acidification treatment to obtain hydrolysis solution; and (5) under the condition of normal pressure, controlling the temperature to be 80-130 DEG C for desolvation and deacidification, then under vacuum pressure, controlling the temperature to be 80-130 DEG C for deacidification by adding water two times, and finally adding deionized water and stirring for crystallization and leaching to obtain solid glyphosate. Compared with the prior art, the process has higher yield and convenient operation, saves the cost, and is suitable for industrial production due to production repeatability.
Description
Technical field
The present invention relates to a kind of preparation technology, especially relate to a kind of preparation technology of glyphosate by using glycine.
Background technology
Glyphosate, chemical name are N-(phosphonic acids methyl) glycine, are to inhale conductivity wide spectrum steriland herbicide in a kind of organic phosphates.Researched and developed success first by U.S. Monsanto Company in 1971, because it has the premium properties that many other weedicides do not possess, efficiently, wide spectrum, low toxicity, environmentally safe etc., and other some superior biological natures, be one of agricultural chemicals of present global sales maximum, lasting over more than 30 year.In recent years, along with the popularization of genetically modified crops in the global range, developing more rapidly, is the weedicide kind of present global sales maximum.
Both at home and abroad the synthetic method for the sweet unicorn of grass has a lot of patent reports, is also to be rare in agricultural chemicals more than its synthetic method, and through exploration and the research of three more than ten years, the production technique of careless sweet unicorn also begins day by day ripe and perfect.Glyphosate technology that at present can large-scale industrial production is representative with IDA operational path and glycine-dialkyl phosphite method mainly.
Influence to the glyphosate process recovery ratio in the glyphosate by using glycine process is mainly as follows: the moisture content of (1) careless sweet unicorn synthetic system is to the sweet unicorn yield influence of grass; (2) glycine impurity is to the influence of reaction; (3) polymerization degree of Paraformaldehyde 96 and moisture content are to the influence of reaction; (4) stirring velocity and temperature of reaction wait a series of many-sided factors to the influence of synthetic system.Wherein moisture is direct to the influence of glyphosate synthetic system.Further analyze glyphosate by using glycine operational path principle, we can find in the process of Paraformaldehyde 96 depolymerization, and glycine and methylal or hemiacetal addition contract with process in all can produce less water, this part water can destroy dimethylphosphite.A lot of enterprises are for addressing this problem, add into dimethylphosphite, expectation improves the yield of product, but often cause in the reaction process reactive component complicated in this process, for example the easy hydrolysis of dimethylphosphite meeting generates phosphorous acid and methyl alcohol etc., the final quality that influences product has strengthened proportioning raw materials simultaneously, improves production cost of products.
The glyphosate development of China is started in the eighties in last century, although technological development progress along with glyphosate, represent the IDA method of advanced technologies technological line progressively to be promoted, still domestic glyphosate production producer is more than 80%, and it is main mainly still adopting glycine-dialkyl phosphite method.This mainly by developing history and domestic technology relatively abroad fall behind, the IDA method is former suspects that factor causes to being difficult to obtain etc. in many ways just.Domestic glyphosate by using glycine operational path is also comparatively ripe through years of development, but continuous appearance along with new technology route, how to tackle the challenge of these novel procesies, on existing factory building equipment foundations of having gone into operation, further optimize technology, increasing competitiveness of product, is a very necessary problem.
Summary of the invention
Purpose of the present invention be exactly provide a kind of in order to overcome the defective that above-mentioned prior art exists and improve yield, save cost, the preparation technology of glyphosate by using glycine that amplification effect is good.
Purpose of the present invention can be achieved through the following technical solutions:
A kind of preparation technology of glyphosate by using glycine is characterized in that, this technology may further comprise the steps:
(1) with Paraformaldehyde 96, methyl alcohol and triethylamine by weight 1: (5-6): (1.2-2) join in the reaction vessel, keep temperature of reaction, stir and obtain transparent reaction soln at 30-50 ℃;
(2) add glycine in above-mentioned reaction soln, maintain the temperature at 30-50 ℃, stirring reaction 1-2h obtains condensation solution, and the add-on of glycine and the weight ratio of Paraformaldehyde 96 are (1-1.5): 1;
(3) add alkyl phosphite in condensation solution, maintain the temperature at 30-70 ℃, stirring reaction 1-4h obtains esterification solution, and the add-on of alkyl phosphite and the weight ratio of Paraformaldehyde 96 are (2-2.5): 1;
(4) add hydrochloric acid in esterification solution and carry out acidification, maintain the temperature at 20-60 ℃, obtain hydrating solution, the add-on of hydrochloric acid and the weight ratio of Paraformaldehyde 96 are (6.3-6.8): 1;
(5) under condition of normal pressure, controlled temperature carries out the precipitation depickling at 80-130 ℃, and again under vacuum pressure, controlled temperature is at 80-130 ℃, adds the water depickling 2 times, adds deionized water at last, promptly gets solid glyphosate behind stirred crystallization, the suction filtration.
Alkyl phosphite in the described step (3) comprises dimethylphosphite.
The concentration expressed in percentage by weight of the hydrochloric acid in the described step (4) is 10-35%.
Vacuum pressure in the described step (5) is 0.2-0.5MPa.
Compared with prior art, the present invention has the following advantages:
(1) under fixed raw materials technology conditions of mixture ratios, the operating method that adopts drip than original process conditions no matter be that the big activation of solid glyphosate yield or total recovery improves 2-3 percentage point;
(2) existing glyphosate by using glycine technology of having gone into operation, industrial scale is bigger, and improved technology has just been carried out small change to original technology, does not increase the improvement cost substantially, implements very convenient, simple possible; Workable;
(3) adopt the glyphosate production of glycine route huge, dog-eat-dog, suitable, reasonable optimizing processing condition can be saved production cost, improve competitiveness of product, and scale is big more, and economy was imitated remarkable more;
(4) through checking repeatedly, repetition stability is good, has carried out amplifying 20 times engineering experiment simultaneously in the lab scale process for the processing condition after the improvement, and experimental result shows that effect is equally remarkable, can suitability for industrialized production.
Embodiment
The present invention is described in detail below in conjunction with specific embodiment.
Embodiment 1
(1) Paraformaldehyde 96 33.6g, methyl alcohol 168g and triethylamine 40.3g are added have reflux exchanger, temperature is taken into account in the there-necked flask of whipping appts, keeps temperature of reaction at 30 ℃, stir and obtain transparent reaction soln;
(2) add glycine 33g in above-mentioned reaction soln, maintain the temperature at 30 ℃, stirring reaction 1h obtains condensation solution;
(3) add dimethylphosphite 68.5g in condensation solution, maintain the temperature at 30 ℃, stirring reaction 1h obtains esterification solution;
(4) adding concentration expressed in percentage by weight in esterification solution is that 10% hydrochloric acid 212g carries out acidification, maintains the temperature at 20 ℃, obtains hydrating solution;
(5) under condition of normal pressure, controlled temperature is at 80 ℃, carry out the precipitation depickling, under the vacuum pressure of 0.2MPa, controlled temperature divides to add the water depickling 2 times at 80 ℃ again, add deionized water at last, promptly get solid glyphosate 68.67g behind stirred crystallization, the suction filtration, the solid glyphosate yield is 73.8%, and total yield is 78.9%.
Embodiment 2
(1) Paraformaldehyde 96 33.6g, methyl alcohol 195g and triethylamine 52.2g are added have reflux exchanger, temperature is taken into account in the there-necked flask of whipping appts, keeps temperature of reaction at 40 ℃, stir and obtain transparent reaction soln;
(2) add glycine 38.3g in above-mentioned reaction soln, maintain the temperature at 40 ℃, stirring reaction 1.5h obtains condensation solution;
(3) add dimethylphosphite 72.1g in condensation solution, maintain the temperature at 40 ℃, stirring reaction 1.5h obtains esterification solution;
(4) adding concentration expressed in percentage by weight in esterification solution is that 30% hydrochloric acid 212g carries out acidification, maintains the temperature at 30 ℃, obtains hydrating solution;
(5) under condition of normal pressure, controlled temperature is at 100 ℃, carry out the precipitation depickling, under the vacuum pressure of 0.3MPa, controlled temperature divides to add the water depickling 2 times at 100 ℃ again, add deionized water at last, promptly get solid glyphosate 69.28g behind stirred crystallization, the suction filtration, the solid glyphosate yield is 76.7%, and total yield is 83%.
Embodiment 3
(1) Paraformaldehyde 96 33.6g, methyl alcohol 201.6g and triethylamine 67.2g are added have reflux exchanger, temperature is taken into account in the there-necked flask of whipping appts, keeps temperature of reaction at 50 ℃, stir and obtain transparent reaction soln;
(2) add glycine 50.4g in above-mentioned reaction soln, maintain the temperature at 45 ℃, stirring reaction 2h obtains condensation solution;
(3) add dimethylphosphite 84g in condensation solution, maintain the temperature at 60 ℃, stirring reaction 1.5h obtains esterification solution;
(4) adding concentration expressed in percentage by weight in esterification solution is that 35% hydrochloric acid 228.5g carries out acidification, maintains the temperature at 40 ℃, obtains hydrating solution;
(5) under condition of normal pressure, controlled temperature is at 100 ℃, carry out the precipitation depickling, under the vacuum pressure of 0.4MPa, controlled temperature divides to add the water depickling 2 times at 110 ℃ again, add deionized water at last, promptly get solid glyphosate 69.9g behind stirred crystallization, the suction filtration, the solid glyphosate yield is 77.28%, and total yield is 82.3%.
Embodiment 4
(1) Paraformaldehyde 96 686g, methyl alcohol 3900g and triethylamine 1044g are added have reflux exchanger, temperature is taken into account in the Glass Containers of whipping appts, keeps temperature of reaction at 50 ℃, stir and obtain transparent reaction soln;
(2) add glycine 767.8g in above-mentioned reaction soln, maintain the temperature at 50 ℃, stirring reaction 2h obtains condensation solution;
(3) add dimethylphosphite 1425.8g in condensation solution, maintain the temperature at 70 ℃, stirring reaction 4h obtains esterification solution;
(4) adding concentration expressed in percentage by weight in esterification solution is that 35% hydrochloric acid 4460g carries out acidification, maintains the temperature at 60 ℃, obtains hydrating solution;
(5) under condition of normal pressure, controlled temperature is at 130 ℃, carry out the precipitation depickling, under the vacuum pressure of 0.5MPa, controlled temperature divides to add the water depickling 2 times at 130 ℃ again, add deionized water at last, promptly get solid glyphosate 1380g behind stirred crystallization, the suction filtration, the solid glyphosate yield is 76.06%, and total yield is 82.8%.
Claims (4)
1. the preparation technology of a glyphosate by using glycine is characterized in that, this technology may further comprise the steps:
(1) with Paraformaldehyde 96, methyl alcohol and triethylamine by weight 1: (5-6): (1.2-2) join in the reaction vessel, keep temperature of reaction, stir and obtain transparent reaction soln at 30-50 ℃;
(2) add glycine in above-mentioned reaction soln, maintain the temperature at 30-50 ℃, stirring reaction 1-2h obtains condensation solution, and the add-on of glycine and the weight ratio of Paraformaldehyde 96 are (1-1.5): 1;
(3) add alkyl phosphite in condensation solution, maintain the temperature at 30-70 ℃, stirring reaction 1-4h obtains esterification solution, and the add-on of alkyl phosphite and the weight ratio of Paraformaldehyde 96 are (2-2.5): 1;
(4) add hydrochloric acid in esterification solution and carry out acidification, maintain the temperature at 20-60 ℃, obtain hydrating solution, the add-on of hydrochloric acid and the weight ratio of Paraformaldehyde 96 are (6.3-6.8): 1;
(5) under condition of normal pressure, controlled temperature carries out the precipitation depickling at 80-130 ℃, and again under vacuum pressure, controlled temperature is at 80-130 ℃, adds the water depickling 2 times, adds deionized water at last, promptly gets solid glyphosate behind stirred crystallization, the suction filtration.
2. the preparation technology of a kind of glyphosate by using glycine according to claim 1 is characterized in that, the alkyl phosphite in the described step (3) comprises dimethylphosphite.
3. the preparation technology of a kind of glyphosate by using glycine according to claim 1 is characterized in that, the concentration expressed in percentage by weight of the hydrochloric acid in the described step (4) is 10-35%.
4. the preparation technology of a kind of glyphosate by using glycine according to claim 1 is characterized in that, the vacuum pressure in the described step (5) is 0.2-0.5MPa.
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| CN200910050070A CN101704842A (en) | 2009-04-27 | 2009-04-27 | Process for preparing glyphosate by using glycine |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN107325126A (en) * | 2017-07-13 | 2017-11-07 | 安徽东至广信农化有限公司 | A kind of acidizing process of glyphosate production technique |
| 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 |
| CN113185548A (en) * | 2021-05-10 | 2021-07-30 | 浙江新安化工集团股份有限公司 | Glyphosate synthesis method for improving utilization rate of dimethyl phosphite |
| CN113402549A (en) * | 2021-07-14 | 2021-09-17 | 安徽东至广信农化有限公司 | Preparation method of glyphosate technical |
-
2009
- 2009-04-27 CN CN200910050070A patent/CN101704842A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN107325126A (en) * | 2017-07-13 | 2017-11-07 | 安徽东至广信农化有限公司 | A kind of acidizing process of glyphosate production technique |
| 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 |
| CN113185548A (en) * | 2021-05-10 | 2021-07-30 | 浙江新安化工集团股份有限公司 | Glyphosate synthesis method for improving utilization rate of dimethyl phosphite |
| CN113402549A (en) * | 2021-07-14 | 2021-09-17 | 安徽东至广信农化有限公司 | Preparation method of glyphosate technical |
| CN113402549B (en) * | 2021-07-14 | 2024-05-31 | 安徽东至广信农化有限公司 | Preparation method of glyphosate raw medicine |
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Application publication date: 20100512 |