CN101591353B - Novel process for recycling mother solution of glyphosate prepared by glycin method - Google Patents
Novel process for recycling mother solution of glyphosate prepared by glycin method Download PDFInfo
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- CN101591353B CN101591353B CN2008102113969A CN200810211396A CN101591353B CN 101591353 B CN101591353 B CN 101591353B CN 2008102113969 A CN2008102113969 A CN 2008102113969A CN 200810211396 A CN200810211396 A CN 200810211396A CN 101591353 B CN101591353 B CN 101591353B
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Abstract
The invention relates to a novel process for recycling waste liquid produced by preparation of weedicide glyphosate (N-phosphono-methyl glycine) by taking alkyl phosphate as a raw material. The process overcomes the disadvantages of mass energy consumption of desalting by hot condensation, large equipment investment, low content of the glyphosate after being heated, low content of the glyphosate in a condensate, large product loss and the like, can well reclaim byproduct salt and can farthest obtain the solid glyphosate. The novel process for recycling mother solution recycles the waste liquid, meets the clean production requirement of energy conservation and emission-reduction and has good economic and social benefits.
Description
Invention field
The present invention relates to a kind of is the novel method of the effluent resource that produced of feedstock production herbicide glyphosate (N-(phosphonomethyl) glycine) with the alkyl phosphite; specifically; mother liquor absorbing hydrogen chloride gas after the inventive method comprises the steps: to isolate glyphosate and reclaim triethylamine with the glycine method synthetic crystallization; the acid out desalination; acid out desalination mother liquor replaces hydrochloric acid to apply mechanically to hydrolysis procedure, and the recirculation desalination is applied mechanically.Drawbacks such as this technology has overcome that hot concentrated desalination consumes energy in a large number, facility investment is big, glyphosate is subjected to that thermal content reduces, glyphosate content is low in the enriched material, product loss is big, not only by-product salt can well be reclaimed, and solid glyphosate can be obtained to greatest extent.This is a waste liquid recycle, meets the cleaner production requirement of energy-saving and emission-reduction, and the novel process for recycling mother solution of good economic and social benefit is arranged.
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.
Summary of the invention
The invention provides the novel process of the preparation glyphosate (N-(phosphonomethyl) glycine) of a kind of low cost, high yield, energy-conserving and environment-protective.
The present invention is the improvement of traditional glycine synthesizing glyphosate route.Existing synthetic route exist in supplies consumption height, the acidolysis produce formaldehyde in a large number, when concentrating formaldehyde (6-10%) easily under the high-temperature acidic condition with glyphosate generation condensation reaction, cause that yield reduces, quality descends the mother liquor composition complexity.Existing treatment process is that multiple-effect evaporation concentrates desalination, and equipment corrosion is serious, the energy consumption height.The solid grass of 1 ton of every production just has the glyphosate about 200kg to become to have no 10% liquid grass of economic worth approximately.There is the surface that film work-ing life is short, regeneration is difficult, large amount of organic and suspended substance are adsorbed on film in the new membrane processing method that proposes, greatly reduces the service efficiency of film.
We find under study for action: former processing method formaldehyde is excessive, can reduce the consumption of Paraformaldehyde 96 by process optimization, improve and stable prod yield and quality, significantly reduce the content of impurity in the mother liquor, optimization by acidolysis process can further reduce the glyphosate yield losses, reaches the target of only producing former powder.
In existing technology, contain a large amount of moisture content in the alcoholic solution of recovery, need could to use by recovery set after the rectifying.In addition, the recovery of amine and the method for rectifying add alkali in the mother liquor earlier makes it dissociate out, separates the rectifying tertiary amine then, reaches recovery set usefulness after the service requirements.In this inventive method, most alcohol and part tertiary amine just reclaim under anhydrous situation, can directly apply mechanically, therefore that has saved most of material adds operations such as alkali, drying, neutralization deacidification, rectifying, starting material and equipment input have been saved greatly, improve usage ratio of equipment accordingly, reduced production cost.Compare with existing technology, under equal conditions this technology acidolysis usage ratio of equipment be existing technology 2-4 doubly, greatly reduce the load of depickling simultaneously.Along with the disengaging reaction system constantly of formaldehyde, under the low temperature acidolysis more complete, the product destructive probability that is decomposed reduces, and reacts more stable.
The present invention relates to a kind of method for treating waste liquid of glycine method synthesizing glyphosate, it comprises the steps:
1) waste liquid after the glycine method synthetic crystallization is isolated glyphosate and reclaimed triethylamine feeds hydrogen chloride gas, makes that the sodium-chlor in the system is separated out by common-ion effcet, and glyphosate remains in the solution.
2) substitute the hydrochloric acidolysis carboxylate with acid out desalination mother liquor, apply mechanically to the hydrolysis procedure of glycine method synthesis technique, the recirculation desalination is applied mechanically.
Hydrogen chloride gas can derive from dimethylphosphite synthesizing section or other approach, and the acid amount of closing of mother liquor is the best with the week acid amount of just in time mating the esterifying liquid acidolysis.
The inventive method is to the innovation that glycine prepares recycling mother solution of glyphosate technology, proposed with hydrogen chloride gas acid out desalination and reclaims glyphosate simultaneously and the hydrochloric acid cover is used for the hydrolysis procedure cycling and reutilization.This method not only reduced facility investment, greatly reduce energy consumption, significantly improved the yield of solid glyphosate, can accomplish only to produce the no discharging of waste liquid of solid grass substantially, and the salts contg height of separating out simultaneously is easier to utilization.This technology can make the production capacity of glyphosate significantly improve, and its yield and quality tend towards stability simultaneously.Have remarkable economical, environmental benefit.
Embodiment
The present invention's employing hereinafter provides indefiniteness embodiment and is described further.
Comparative examples 1
Paraformaldehyde 96 16.1g (0.537mol), 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 30.90g (0.3mol), 45-65 ℃ of insulation reaction, finish until reaction.At 45-70 ℃ of reclaim under reduced pressure methyl alcohol and triethylamine, when reaching 40-70%, total weightlessness is cooled to naturally about 40 ℃, slow dripping hydrochloric acid (30%) 76g (0.625mol), and 40-70 ℃ of insulation acidolysis is until reacting completely, the depickling of reducing pressure then, when temperature reaches 110 ℃, stop decompression, add 40g water, crystallisation by cooling, the suction filtration drying obtains the former powder 34.03g of glyphosate, former powder yield 77%, total recovery 81% at last.
Embodiment 1
Adopt the method for comparative examples 1 to prepare glyphosate crystalline mother solution 75.5g, this mother liquor gets pending mother liquor (the pending mother liquor of hereinafter referred) after adding alkali recovery triethylamine, in this pending mother liquor, feed hydrogen chloride gas then, get solidliquid mixture 143.9g at last, obtain sodium-chlor crude product 50.6g behind the suction filtration, acid out desalination mother liquor 83.3g.Through dividing analysis, content of hydrochloric acid is 26.69% in the acid out desalination mother liquor, and cl content 58.50% in the solid sodium chloride, and acid out desalination sodium-chlor clearance is 92.28%, this acid out desalination mother liquor gives over to down batch replacement hydrochloric acid, and according to comparative examples 1 acidification hydrolization part recycled.
Embodiment 2
Adopt the method for embodiment 1 to handle the glyphosate crystalline mother solution, feed hydrogen chloride gas in the pending mother liquor, get solidliquid mixture 144.3g at last, obtain sodium-chlor crude product 51.5g behind the suction filtration, acid out desalination mother liquor 85.2g.Through dividing analysis, content of hydrochloric acid is 27.23% in the acid out desalination mother liquor, and cl content 58.69% in the solid sodium chloride, and acid out desalination sodium-chlor clearance is 92.34%, this acid out desalination mother liquor gives over to down batch replacement hydrochloric acid, and according to comparative examples 1 acidification hydrolization part recycled.
Embodiment 3
Adopt the method for comparative examples 1 to prepare glyphosate, acid out desalination mother liquor with embodiment 1 gained during acidifying replaces hcl acidifying to handle carboxylate, depickling, add water, get the former powder 42.92g of glyphosate (content 95.5%) behind the crystallisation by cooling, former powder yield 78%, total recovery 81.3%, get glyphosate mother solution 78.6g, this mother liquor gets pending mother liquor (the pending mother liquor of hereinafter referred) after adding alkali recovery triethylamine, in this pending mother liquor, feed hydrogen chloride gas then, get solidliquid mixture 147.1g at last, obtain sodium-chlor crude product 54.23g behind the suction filtration, acid out desalination mother liquor 86.8g.Through dividing analysis, content of hydrochloric acid is 25.78% in the acid out desalination mother liquor, and cl content 57.50% in the solid sodium chloride, and acid out desalination sodium-chlor clearance is 92.57%, this acid out desalination mother liquor gives over to down batch replacement hydrochloric acid, and according to comparative examples 1 acidification hydrolization part recycled.
Embodiment 4
Adopt the method for embodiment 3 to handle glyphosate mother solution, and apply mechanically acid out desalination mother liquor repeatedly.Apply mechanically acid out desalination mother liquor experimental result and see Table 1.
Table 1, acid out desalination Recycling Mother Solution are applied mechanically experiment
Claims (2)
1. the method for treating waste liquid of a glycine method synthesizing glyphosate, it comprises the steps:
1) waste liquid after the glycine method synthetic crystallization is isolated glyphosate and reclaimed triethylamine feeds hydrogen chloride gas, makes that the sodium-chlor in the system is separated out by common-ion effcet, and glyphosate remains in the solution;
2) substitute the hydrochloric acidolysis carboxylate with acid out desalination mother liquor, apply mechanically to the hydrolysis procedure of glycine method synthesis technique, the recirculation desalination is applied mechanically.
2. according to the process of claim 1 wherein, hydrogen chloride gas derives from dimethylphosphite synthesizing section or other approach, and the acid content of mother liquor is just in time to mate being as the criterion with the acid amount of esterifying liquid acidolysis.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2008102113969A CN101591353B (en) | 2008-05-28 | 2008-09-25 | Novel process for recycling mother solution of glyphosate prepared by glycin method |
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| CN200810113108 | 2008-05-28 | ||
| CN2008102113969A CN101591353B (en) | 2008-05-28 | 2008-09-25 | Novel process for recycling mother solution of glyphosate prepared by glycin method |
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| CN102134261A (en) * | 2010-01-25 | 2011-07-27 | 北京紫光英力化工技术有限公司 | Process for preparing glyphosate by glycine method |
| CN105524107B (en) * | 2014-09-30 | 2017-12-29 | 北京紫光英力化工技术有限公司 | A kind of PMIDA clean manufacturing and accessory substance novel process for recycling |
| CN110812877B (en) * | 2019-10-12 | 2021-03-23 | 西安交通大学 | Glyphosate mother liquor treatment method and device |
Citations (2)
| 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 |
| CN1962672A (en) * | 2005-11-11 | 2007-05-16 | 重庆三峡英力化工有限公司 | Process of glycine method for preparing glyphosate |
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| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
| CN1962672A (en) * | 2005-11-11 | 2007-05-16 | 重庆三峡英力化工有限公司 | Process of glycine method for preparing glyphosate |
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