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 PDF

Info

Publication number
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
Authority
CN
China
Prior art keywords
glyphosate
mother liquor
waste liquid
novel process
acid
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.)
Active
Application number
CN2008102113969A
Other languages
Chinese (zh)
Other versions
CN101591353A (en
Inventor
查正炯
尹应武
易飞
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
TH-UNIS INSIGHT Co Ltd
Original Assignee
TH-UNIS INSIGHT Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by TH-UNIS INSIGHT Co Ltd filed Critical TH-UNIS INSIGHT Co Ltd
Priority to CN2008102113969A priority Critical patent/CN101591353B/en
Publication of CN101591353A publication Critical patent/CN101591353A/en
Application granted granted Critical
Publication of CN101591353B publication Critical patent/CN101591353B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Landscapes

  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

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

Recycling mother solution of glyphosate prepared by glycin method technology
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):
Figure G2008102113969D00011
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.
Figure G2008102113969D00051
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.
CN2008102113969A 2008-05-28 2008-09-25 Novel process for recycling mother solution of glyphosate prepared by glycin method Active CN101591353B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN2008102113969A CN101591353B (en) 2008-05-28 2008-09-25 Novel process for recycling mother solution of glyphosate prepared by glycin method

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
CN200810113108.6 2008-05-28
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

Publications (2)

Publication Number Publication Date
CN101591353A CN101591353A (en) 2009-12-02
CN101591353B true CN101591353B (en) 2011-09-07

Family

ID=41406250

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2008102113969A Active CN101591353B (en) 2008-05-28 2008-09-25 Novel process for recycling mother solution of glyphosate prepared by glycin method

Country Status (1)

Country Link
CN (1) CN101591353B (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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)

* Cited by examiner, † Cited by third party
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

Patent Citations (2)

* Cited by examiner, † Cited by third party
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

Also Published As

Publication number Publication date
CN101591353A (en) 2009-12-02

Similar Documents

Publication Publication Date Title
WO2015158157A1 (en) Method for cyclically preparing taurine from hydroxyethyl sulfonic acid alkali metal salt and vinyl sulfonic acid alkali metal salt
CN101591352B (en) Novel process for preparing glyphosate by glycin method
CN102134261A (en) Process for preparing glyphosate by glycine method
CN101709064A (en) Process for synthesizing glyphosate
CN101591353B (en) Novel process for recycling mother solution of glyphosate prepared by glycin method
CN105820186A (en) Glyphosate-production continuous-hydrolysis steam-condensate recycling method
CN102211995A (en) Preparation method of 2,6-dihydroxybenzoic acid
CN103333203A (en) Preparation method of TPO-L photoinitiator
CN1939926A (en) Production of glyphosate by glycine method
US4647689A (en) Preparation of alkyl trifluoroacetoacetate
CN103265443B (en) Industrial production method of high-purity iminodiacetic acid
CN102040522A (en) Method for recycling triethylamine from production of propargite
JP4685766B2 (en) Method for producing lactate ester
CN113248446B (en) 4, 6-dichloropyrimidine purification and phosphorus recycling treatment process
CN110862413A (en) Glyphosate synthesis process and device
CN103539745A (en) Preparation method of secnidazole
CN105315176B (en) Green preparation process of N- (4-ethoxycarbonylphenyl) -N '-methyl-N' -phenylformamidine
CN111646879B (en) Preparation method of 2-methyl-4-chloro
CN102766160A (en) Novel process for preparing glyphosate by utilizing glycine method
CN101671363B (en) Hydrolyzation post-processing technique during preparation of glyphosate through glycin method
CN110563556A (en) method for recovering 2, 4-di-tert-butylphenol from double-helix phosphite antioxidant 626 mother liquor
CN113292597B (en) Method for preparing triethyl phosphate compound by recovering sodium diethylphosphate and ethyl chloride
CN104098602A (en) Energy-saving and clean production method of PMIDA
US2892840A (en) Preparation of cytosine and intermediates
CN104262164A (en) Preparation method of dinitolmide intermediate 3,5-dinitro-ortho-methyl benzoic acid

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant