CN103421043A - Hydrosis process improvement method for synthesizing glyphosate by alkyl ester process - Google Patents
Hydrosis process improvement method for synthesizing glyphosate by alkyl ester process Download PDFInfo
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- CN103421043A CN103421043A CN2012104260723A CN201210426072A CN103421043A CN 103421043 A CN103421043 A CN 103421043A CN 2012104260723 A CN2012104260723 A CN 2012104260723A CN 201210426072 A CN201210426072 A CN 201210426072A CN 103421043 A CN103421043 A CN 103421043A
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Abstract
The invention relates to a hydrosis process improvement method for synthesizing glyphosate by an alkyl ester process. The method comprises the following steps: at the temperature of 40-50 DEG C, feeding paraformaldehyde, methyl alcohol and triethylamine as materials into a reaction kettle, stirring, adding glycine after the materials are clarified, adding dimethyl phosphite after the mixture is clarified, rising the temperature to be 50-60 DEG C, and keeping the temperature for 50 min; reducing the temperature to be 30 DEG C, and adding hydrochloric acid; slowing rising the temperature after stirring for 30 min to evaporate methyl alcohol; rising the temperature to be 110-125 DEG C; adding water into the reaction kettle, reducing the temperature to be below 70 DEG C, and externally cooling with cold water to reduce the temperature of the reaction kettle to be below 10 DEG C; adding triethylamine, controlling the temperature to be 15-25 DEG C, and reaching the reaction endpoint when the pH value in the reaction kettle is 0.5-1.5; transferring the materials to a crystallization kettle, reducing the temperature to be below 10 DEG C to crystallize the materials for a time; filtering, washing and drying the crystal to obtain glyphosate technical.
Description
Technical field
The present invention relates to the pesticide chemical field, be specifically related to improving one's methods of a kind of alkyl esterification method synthesizing glyphosate hydrolysis process.
Background technology
Glyphosate herbicidal is the kind of output maximum in the World chemical Pesticidal products, accounts for more than 30% of agricultural chemicals ultimate production.Approximately 800,000 tons of the yearly capacities of China's glyphosate, have two kinds of synthetic methods of alkyl esterification method and IDA method, and wherein alkyl esterification method production output accounts for more than 70% of ultimate production.The synthetic production of now widely used alkyl esterification method glyphosate technique is to take paraformaldehyde as starting raw material, methyl alcohol is solvent, triethylamine is catalyzer, make the paraformaldehyde depolymerization, then add glycine to carry out addition reaction, add again dimethylphosphite to carry out condensation reaction, add afterwards hydrochloric acid to carry out acid hydrolytic reaction, slowly heat up and carry out dealcoholysis in hydrolysis reaction, depickling, while being warming up to 110-125 ℃, add water for cooling to 75 ℃ left and right, then add the NaOH regulator solution pH value that massfraction is 30%, the pH value regulation range is that 1-1.5(practice shows: the regulator solution pH value is between 1-1.5, can reduce the solubleness of glyphosate in solution, improve the solid yield of glyphosate).Again, suction filtration standing through crystallisation by cooling, washing, dryly just can produce glyphosate technicals, glyphosate yield approximately 73-75%.
But the weak point of this technique is: in (1) this technique, add NaOH to regulate the pH value of material, to improve the solid recovery rate of glyphosate, can in glyphosate technicals, introduce a large amount of Na+ like this, the higher quality product that can affect glyphosate preparation formulation of Na+ content in glyphosate technicals is especially that preparation high content glyphosate liquid preparation is prone to crystalline polamer in the winter time.And glyphosate technicals products export export trade customer requirement, must carry out strict control to Na+ content in glyphosate technicals.(2) in order to control the content of Na+ in glyphosate technicals, must increase the difficulty of the washing procedure of former medicine, particularly increase the bath water amount, thereby strengthen the glyphosate mother solution wastewater discharge, increase the glyphosate waste water processing cost.
Summary of the invention
In view of this, the purpose of this invention is to provide improving one's methods of a kind of alkyl esterification method synthesizing glyphosate hydrolysis process, to solve the synthetic deficiency of producing glyphosate technique of abovementioned alkyl ester method.Utilize the triethylamine organic bases, not only the adjustable material pH value improves the glyphosate yield, and in the glyphosate technicals obtained without the existence of Na+, thereby reduce glyphosate technicals bath water amount, reduce the glyphosate waste water processing cost.
To achieve these goals, the present invention has adopted improving one's methods of following hydrolysis process, comprises the steps:
Step 1, under 40～50 ℃, by paraformaldehyde, methyl alcohol and triethylamine three, as material, drop in reactor, then stir;
Step 2, stir for some time, and the material in the question response still adds glycine after becoming clarification while stirring in reactor, remembers that the total material in reactor now is the first mixture;
Step 3, stir certain hour, after the first mixture becomes clarification, adds dimethylphosphite while stirring in reactor, then by temperature control equipment, makes reactor be warming up to 50～60 ℃, is incubated 50 minutes;
Step 4, be cooled to 30 ℃ by temperature control equipment by reactor, under agitation in reactor, adds appropriate hydrochloric acid;
Step 5, after stirring 30 minutes, make reactor slowly be warming up to 75～90 ℃ by temperature control equipment, evaporates methyl alcohol;
Step 6, after methyl alcohol all evaporates, make reactor be warming up to 110～125 ℃ by temperature control equipment;
Step 7, and then add water in reactor, reactor is cooled to below 70 ℃, and can makes material be diluted, then, with the outer cooling reactor of cold water, make reactor continue to be cooled to below 10 ℃;
Step 8, add a certain amount of triethylamine while stirring in reactor, and control in this process temperature all the time within 15～25 ℃ of scopes, make the pH value of the total material in reactor between 0.5～1.5 scope, now just reach reaction end, remember that the total material in reactor now is the second mixture;
Step 9, be transferred to the second mixture in crystallization kettle, in low rate mixing, opens the cooling water of crystallization kettle chuck, and the crystallization kettle temperature is down to below 10 ℃, makes the second crystalline mixture;
Step 10, the second crystalline mixture, after for some time, filters the product after crystallization, obtains crystal and filtrate, then crystal is washed, dries, and the filter cake obtained is the glyphosate technicals product;
Wherein, the paraformaldehyde in step 1 is reaction raw materials, and methyl alcohol is reaction solvent, and triethylamine is the catalyzer of reaction;
Filtrate in step 10 is to reclaim triethylamine through the triethylamine retrieving arrangement, and the triethylamine after recovery is applied mechanically aborning as raw material.
Further, hydrolysis process method provided by the invention, its feature can also be: wherein, in step 8, triethylamine needs slowly to drip.
Further, hydrolysis process method provided by the invention, its feature can also be: wherein, in step 10, the crystallization time of the second mixture is greater than 8 hours.
Invention effect and effect
The present invention discloses improving one's methods of a kind of alkyl esterification method synthesizing glyphosate hydrolysis process, adopts the triethylamine organic bases to regulate the pH value of material when the glyphosate synthesis hydrolysis reaction finishes.Utilize the triethylamine organic bases, not only the adjustable material pH value improves the glyphosate yield, and reacts in synthetic glyphosate technicals without the existence of Na+, can reduce like this glyphosate technicals bath water amount, reduces the glyphosate waste water processing cost.Because triethylamine possesses retrieving arrangement as the glyphosate synthesis catalyzer in existing technique, and the technical maturity rate of recovery reaches more than 95%, therefore, the product after the improvement hydrolyzing process adds triethylamine as the organic bases neutralizing hydrolysis is without the equipment investment and the production operating costs that increase the triethylamine retrieving arrangement.
Embodiment
Below in conjunction with specific embodiment, further illustrate the present invention.It should be understood that these embodiment only are not used in and limit the scope of the invention for the present invention is described.
Embodiment mono-
Take paraformaldehyde 24.2g, methyl alcohol 136.2g, triethylamine 40.8g, add in four-hole boiling flask and stir 30 minutes under temperature 40-45 ℃ condition; After in the question response still, material becomes clarification, add glycine 30g, keep uniform temp to stir 40 minutes, after material in flask becomes clarification, then add dimethylphosphite 54g, be warming up to 50-60 ℃; Being incubated after 50 minutes, being cooled to 30 ℃, under stirring, is 30% hydrochloric acid 135ml toward adding massfraction in reactor; Stir after 30 minutes, make flask slowly be warming up to 75-90 ℃, steam methyl alcohol; Treat the methyl alcohol evaporation fully, then make flask be warming up to 115-125 ℃ by temperature control equipment; Then add 20g water that flask is cooled to below 70 ℃, outer cooling with cold water, make in flask to continue to be cooled to below 10 ℃; Slowly drip triethylamine 15g, temperature is controlled at 15-25 ℃; The pH value that obtains all substances in flask with the PH instrumentation is 0.7; Then with cold water, make flask continue to be cooled to below 10 ℃, and to make crystallization time be 9 hours, the gained crystallisate is carried out to suction filtration, washing, take out filter cake, dry and obtain glyphosate technicals, the glyphosate technicals quality obtained is 53.6g.
In the check glyphosate technicals, glyphosate content is 95.6%, by calculating the glyphosate yield, is 77.3%.In glyphosate technicals, Na+ does not detect, and utilizes the triethylamine retrieving arrangement to be reclaimed the triethylamine in filtrate, for the water yield of washing glyphosate technicals, compares with technique and reduces more than 30%.
The effect of embodiment mono-and effect
The present invention discloses improving one's methods of a kind of alkyl esterification method synthesizing glyphosate hydrolysis process, in embodiments of the invention one, adopts the triethylamine organic bases to regulate the pH value of material when the glyphosate synthesis hydrolysis reaction finishes.Utilize the triethylamine organic bases, not only regulate the material pH value and improved the glyphosate yield, and react in synthetic glyphosate technicals the existence without Na+, the bath water amount reduces more than 30%, reduce the glyphosate production wastewater discharge, reduce cost for wastewater treatment, compare the glyphosate yield with former technique and also improve more than 2%.
Embodiment bis-
Take paraformaldehyde 24.2g, methyl alcohol 136.2g, triethylamine 40.8g, add in four-hole boiling flask and stir 30 minutes under temperature 40-45 ℃ condition; After in the question response still, material becomes clarification, add glycine 30g, keep uniform temp to stir 40 minutes, after material in flask becomes clarification, then add dimethylphosphite 54g, be warming up to 50-60 ℃; Being incubated after 50 minutes, being cooled to 30 ℃, under stirring, is 30% hydrochloric acid 135ml toward adding massfraction in reactor; Stir after 30 minutes, make flask slowly be warming up to 75-90 ℃, steam methyl alcohol; Treat the methyl alcohol evaporation fully, then make flask be warming up to 115-125 ℃ by temperature control equipment; Then add 20g water that flask is cooled to below 70 ℃, outer cooling with cold water, make in flask to continue to be cooled to below 10 ℃; Slowly drip triethylamine 23g, temperature is controlled at 15-25 ℃, and the pH value that obtains all substances in flask with the PH instrumentation is 1.0; Then with cold water, make flask continue to be cooled to below 10 ℃, and to make crystallization time be 12 hours, the gained crystallisate is carried out to suction filtration, washing, take out filter cake, dry and obtain glyphosate technicals, the glyphosate technicals quality obtained is 54.4g.
In the check glyphosate technicals, the content of glyphosate is 95.4%, by calculating the glyphosate yield, is more than 78.4%.In glyphosate technicals, Na+ does not detect, and utilizes the triethylamine retrieving arrangement to be reclaimed the triethylamine in filtrate, for the water yield of washing glyphosate technicals, compares with technique and reduces more than 30%.
The effect of embodiment bis-and effect
The present invention discloses improving one's methods of a kind of alkyl esterification method synthesizing glyphosate hydrolysis process, in embodiments of the invention two, adopts the triethylamine organic bases to regulate the pH value of material when the glyphosate synthesis hydrolysis reaction finishes.Utilize the triethylamine organic bases, not only regulate the material pH value and improved the glyphosate yield, and react in synthetic glyphosate technicals the existence without Na+, the bath water amount reduces more than 30%, reduce the glyphosate production wastewater discharge, reduce cost for wastewater treatment, compare the glyphosate yield with former technique and also improve more than 2%.
Claims (3)
1. improving one's methods of an alkyl fat method synthesizing glyphosate hydrolysis process, is characterized in that, comprises the following steps:
Step 1, under 40～50 ℃, by paraformaldehyde, methyl alcohol and triethylamine three, as material, drop in reactor, then stir;
Step 2, stir for some time, after the described material in described reactor becomes clarification, adds glycine while stirring in described reactor, remembers that the total material in reactor now is the first mixture;
Step 3, stir certain hour, after described the first mixture becomes clarification, adds dimethylphosphite while stirring in described reactor, then by temperature control equipment, makes described reactor be warming up to 50～60 ℃, is incubated 50 minutes;
Step 4, be cooled to 30 ℃ by temperature control equipment by described reactor, under agitation in described reactor, adds appropriate hydrochloric acid;
Step 5, after stirring 30 minutes, make described reactor slowly be warming up to 75～90 ℃ by described temperature control equipment, evaporates methyl alcohol;
Step 6, after described methyl alcohol all evaporates, make described reactor be warming up to 110～125 ℃ by described temperature control equipment;
Step 7, and then add water in described reactor, described reactor is cooled to below 70 ℃, then, with the outer cooling described reactor of cold water, makes described reactor continue to be cooled to below 10 ℃;
Step 8, add a certain amount of triethylamine while stirring in described reactor, and control in this process temperature all the time within 15～25 ℃ of scopes, make the pH value of the total material in described reactor between 0.5～1.5 scope, now just reach reaction end, the note now total material in described reactor is the second mixture;
Step 9, be transferred to described the second mixture in crystallization kettle, in low rate mixing, opens the cooling water of described crystallization kettle chuck, by described temperature control equipment, described crystallization kettle temperature is down to below 10 ℃, makes described the second crystalline mixture;
Step 10, after described total material crystallization for some time, filter the product after crystallization, obtains crystal and filtrate, then described crystal washed, dries, and the filter cake obtained is the glyphosate technicals product.
2. improving one's methods of hydrolysis process according to claim 1 is characterized in that: wherein, the described triethylamine in described step 8 needs slowly to drip.
3. improving one's methods of hydrolysis process according to claim 1, it is characterized in that: wherein, the described crystallization time of described the second mixture in described step 10 is greater than 8 hours.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| CN114053976A (en) * | 2020-08-04 | 2022-02-18 | 欧佩德伺服电机节能系统有限公司 | Working steps of reaction kettle for preparing glyphosate |
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| CN1648131A (en) * | 2004-12-23 | 2005-08-03 | 浙江新安化工集团股份有限公司 | Process for treating glyphosate mother liquid |
| CN101125862A (en) * | 2007-08-27 | 2008-02-20 | 山东潍坊润丰化工有限公司 | Circulation recovery method for glyphosate mother liquid |
| CN101190926A (en) * | 2006-11-29 | 2008-06-04 | 浙江新安化工集团股份有限公司 | Method for treating glyphosate mother liquid |
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- 2012-10-31 CN CN2012104260723A patent/CN103421043A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1648131A (en) * | 2004-12-23 | 2005-08-03 | 浙江新安化工集团股份有限公司 | Process for treating glyphosate mother liquid |
| CN101190926A (en) * | 2006-11-29 | 2008-06-04 | 浙江新安化工集团股份有限公司 | Method for treating glyphosate mother liquid |
| CN101125862A (en) * | 2007-08-27 | 2008-02-20 | 山东潍坊润丰化工有限公司 | Circulation recovery method for glyphosate mother liquid |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114053976A (en) * | 2020-08-04 | 2022-02-18 | 欧佩德伺服电机节能系统有限公司 | Working steps of reaction kettle for preparing glyphosate |
| 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 |
| 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 |
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Application publication date: 20131204 |