CN100340566C - Treatment method of glyphosate mother liquor - Google Patents
Treatment method of glyphosate mother liquor Download PDFInfo
- Publication number
- CN100340566C CN100340566C CNB2005100532894A CN200510053289A CN100340566C CN 100340566 C CN100340566 C CN 100340566C CN B2005100532894 A CNB2005100532894 A CN B2005100532894A CN 200510053289 A CN200510053289 A CN 200510053289A CN 100340566 C CN100340566 C CN 100340566C
- Authority
- CN
- China
- Prior art keywords
- mother liquor
- glyphosate
- mother
- sodium bicarbonate
- produces
- 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
Links
Images
Landscapes
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The present invention relates to a processing method by synthesizing glyphosate to prepare mother liquor by an alkyl ester method. The present invention has the method that after triethylamine is recovered, alkali mother liquor is concentrated, a large quantity of by-products of sodium chloride are removed, ammonia gas and carbon dioxide are orderly led into the alkali mother liquor to thoroughly react and is filtered, and the filter liquor is processed to prepare glyphosate solution. The method can eliminate the problem of soil alkalization caused by the application of the glyphosate solution containing much sodium chloride, and simultaneously can enhance the drug effect of the glyphosate solution prepared by the technique, reduce the cost and save the energy consumption.
Description
Technical field
The present invention relates to the novel method that alkyl esterification method prepares a kind of glyphosate mother solution processing of glyphosate.
Background technology
Glyphosate is a kind of steriland herbicide, and present domestic preparation glyphosate adopts alkyl esterification method more.This technology produces a large amount of Na that contains when producing glyphosate technicals
+Acid mother liquid, the catalyst of triethylamine of using when containing a large amount of synthesizing in the mother liquor.Domestic glyphosate production producer common employing when handling this kind mother liquor recovery catalyst of triethylamine adds in the liquid caustic soda and technology: be about to 30% sodium hydroxide solution and add in the mother liquor, regulate pH value 10-12, standing demix, upper strata triethylamine recovery is re-used in glyphosate synthesizes, and a small amount of triethylamine is told in lower floor's mother liquor rectifying, and remainder is through concentrating, remove part sodium-chlor, sodium chloride concentration is saturated in the concentrated mother liquor, and glyphosate content is about 2%-2.5%, is used to prepare 10% sodium glyphosate aqua.After having used this kind and containing 10% sodium glyphosate aqua of more sodium-chlor, make that sodium chloride content is too high in the soil, easily cause soil bad dispersibility, soil property viscous, become soda soil, crop is caused damage, finally cause crop failure and downgrade.In addition, the weeding usefulness of 10% sodium glyphosate aqua (quick-acting and thoroughness) is slightly inferior than other glyphosate formulation.
Summary of the invention
Purpose of the present invention just provides and handles the method that mother liquor is recycled in a kind of alkyl esterification method glyphosate production technology.This method not only can be eliminated because of using the problem of the salting of soil that the gyphosate solution that contains more sodium-chlor causes, and also can improve the aqua drug effect with this technology preparation simultaneously, reduces cost energy efficient.
According to the present invention, can be achieved through the following technical solutions the object of the invention:
Solid sodium bicarbonate is added in the acid mother liquid that produces in the preparation glyphosate production process, pH value is 3～7, add 30% sodium hydroxide, the adjusting pH value is 10-12, standing demix, it is synthetic that upper strata triethylamine recovery is re-used in glyphosate, after a small amount of triethylamine is told in lower floor's mother liquor rectifying, the heating of residue alkaline mother liquor is concentrated a large amount of sodium-chlor of removal, get concentrated mother liquor, in concentrated mother liquor, feed ammonia successively, behind the carbon dioxide, fully reaction is removed throw out (sodium bicarbonate), concentrating filter liquor, remove part ammonium chloride, be used to prepare gyphosate solution.
Feed ammonia and carbonic acid gas in the concentrated alkaline mother liquor of sodium chloride-containing, produce sodium bicarbonate precipitation (solubleness of sodium bicarbonate in this system is very little), reaction equation is:
CO
2+NH
3+H
2O+NaCl→NH
4Cl+NaHCO
3↓
During the by product sodium bicarbonate that produces can be reused for and the acid mother liquid that produces in the glyphosate production process, can reduce the consumption of liquid caustic soda thus, produce a large amount of carbonic acid gas in the N-process, can recycle in subsequent reactions;
HCO
3 -+H
+→CO
2↑+H
2O
Adopting the inventive method to recycle glyphosate mother solution has the following advantages:
(1), adopt in the mother liquor after the present invention handles and contain the ammonium chloride that in a large number the gyphosate solution drug effect is had synergism, and sodium chloride-containing or content is not seldom substantially.
(2), adopt 10% gyphosate solution of the mother liquor preparation after the present invention handles owing to contain the ammonium chloride that has synergism in a large number.Therefore, the herbicidal effect of 10% gyphosate solution improves.
(3), adopt the mother liquor preparation after the present invention handles 10% gyphosate solution since substantially not sodium chloride-containing or content seldom, therefore having eliminated a large amount of sodium-chlor is released in the soil problem of environmental pollutions such as the soil salinization phenomenon that causes.
(4), adopt the present invention to handle to feed the sodium bicarbonate precipitation that generates behind ammonia, the carbon dioxide in the mother liquor process successively and can replace other alkaline matter to be back in the glyphosate production process, the carbon dioxide that produces can be back to the treating processes of mother liquor again, be fully used with mother liquor in making, thereby can't consume the exhaust emission that is caused too much with mother liquor in fundamentally having avoided.
(5), adopting the present invention to handle mother liquor, to also have an advantage be that existing apparatus does not need big change.
Description of drawings
Schema of the present invention is seen accompanying drawing 1
Being neutralized to PH with sodium bicarbonate and liquid caustic soda respectively from the acid mother liquid of glyphosate synthesis procedure is 10-12, layering, the upper strata is a triethylamine, lower floor is the mother liquor of sodium chloride-containing, still contains a small amount of triethylamine in this mother liquor, after rectifying steams triethylamine alkaline mother liquor; The alkaline mother liquor heating concentrates removes a large amount of by product sodium-chlor, concentrating the water of condensation that produces discharges after biochemical treatment, in this concentrated mother liquor, feed ammonia again, and upward go on foot with the carbon dioxide that produces in the sodium bicarbonate N-process, restock feeds an amount of carbonic acid gas in addition, and ammonia, carbonic acid gas react in sodium chloride aqueous solution, generating the sodium bicarbonate crystallization separates out, after filtration, sodium bicarbonate returns and is used for the neutralizing acid aqueous mother liquor, and concentrating filter liquor can be prepared gyphosate solution.
Accompanying drawing 2 is traditional glyphosate mother solution treatment process, and acid mother liquid is in liquid caustic soda and after reclaiming triethylamine, and direct concentrating is used to prepare gyphosate solution, by product sodium-chlor.
Embodiment
Embodiment 1
In the preparation glyphosate production process, concentrate and remove sodium-chlor after mother liquor 1000g in feed the ammonia of 25g earlier, feed the carbon dioxide of 65g again, after fully stirring, centrifugation obtains 120g sodium bicarbonate and filtrate.The glyphosphonic acid that adds metering to filtrate is 10% until glyphosate content, obtains finished product 10% gyphosate solution.
Embodiment 2
In the preparation glyphosate production process, concentrate and remove sodium-chlor after mother liquor 1000g in feed the ammonia of 75g earlier, feed the carbon dioxide of 200g again, after fully stirring, centrifugation obtains 350g sodium bicarbonate and filtrate.The glyphosphonic acid that adds metering to filtrate is 10% until glyphosate content, obtains finished product 10% gyphosate solution.
Embodiment 3
Get the 1000g acid mother liquid in the glyphosate production process, add the sodium bicarbonate 105g that produces among the embodiment 1, collect the carbon dioxide 53g that produces, reaction back pH value is 5.4, adds 30%NaOH880g again, and pH value is 11, layering, the upper strata gets triethylamine 206g, and lower floor's mother liquor gets triethylamine 13g through distillation; Concentrate remaining alkaline mother liquor, remove sodium-chlor 41g, concentrated mother liquor 500g, feed the ammonia of 28g in the concentrated mother liquor earlier, feed the carbon dioxide of collecting again, and supplementary carbon dioxide gas 20g, after fully stirring, filtration obtains the 103g sodium bicarbonate.The glyphosphonic acid that adds metering in the concentrated filtrate is 10% until glyphosate content, obtains 10% gyphosate solution.
Embodiment 4
Get the 2000g acid mother liquid in the glyphosate production process, add the sodium bicarbonate 319g that produces among the embodiment 2, collect the carbon dioxide 151g that produces, reaction back pH value is 5.4, adds 30%NaOH1620g again, and pH value is 11, layering, the upper strata gets triethylamine 411g, and lower floor's mother liquor gets triethylamine 26g through distillation; Concentrate remaining alkaline mother liquor, remove sodium-chlor 79g, concentrated mother liquor 1000g, feed the ammonia of 75g in the concentrated mother liquor earlier, feed the carbon dioxide of collecting again, and supplementary carbon dioxide gas 45g, after fully stirring, filtration obtains the 315g sodium bicarbonate.The glyphosphonic acid that adds metering in the concentrated filtrate is 10% until glyphosate content, obtains 10% gyphosate solution.
Embodiment 5 tests of pesticide effectiveness
The old field that test is selected in night watch tower carries out, and the weeds kind is mainly nutgrass flatsedge, Bermuda grass etc.Adopt Red Star participants in a bridge game pressure pressure atomizer, 5 processing are established in test, triplicate, and district's group is arranged at random, 5 square metres of each sub-district areas.A, b are handled in test, c, d are respectively embodiment 1,2,3,4 gained 10% gyphosate solution 9 grams, and e is former technology gained 10% gyphosate solution 9 grams.
Test in medication on November 2 in 2004, each is handled and converts water 30-40Kg/ mu by institute's dosage, directed even spraying, and blank only sprays clear water.Fine during medication, about temperature 15-20 ℃, rained heavily in the 6th day after the medication, temperature all is about 8-18 ℃.Utilize CD method log, see Table 1.
Annotate: the CD method is meant the product with effect of herbicides relative coverage and drug effect degree, passes judgment on steriland herbicide to mixing the method for living weed community preventive effect.Formulate is: Wc is the preventive effect of steriland herbicide to the living weed community of mud in Wc=C * D formula.C is a drug effect relative coverage value in the medication district, i.e. have in the weeds that are subjected to the medicine symptom and the medication district the relative level of coverage that whole weeds are compared in the medication district, gives the C assignment with the method for range estimation with the number between 1.0 to 10.0.If all weeds all show and are subjected to the medicine symptom in the medication district, no matter the weight of its symptom then, the C value is 10.0; If only have fragmentary weeds tool to be subjected to the medicine symptom in the medication district, its area is no more than 10%, and then the C value is 1.0.D is the drug effect degree of weeds in the medication district, looks weight that weeds poison and same the tax with the numerical value between 1.0 to 10.0, and the relation of its main numerical value and toxicity symptom sees Table 2.
The relation of table 2 D value and weeds toxicity symptom
| The D value | The weeds toxicity symptom |
| 10.0 | Whole strain is withered |
| 8.0 | Blade, young stem or rachis are withered, big slight yellow of stem or chlorosis.Can not continued growth, the plant part is withered |
| 6.0 | Leaf chlorosis or jaundice or partial blade are withered, and stem is near normally, still can slowly grow |
| 4.0 | Minority leaf chlorosis or jaundice, plant strain growth are normal substantially |
| 1.0 | Fragmentary blade tool calomel poisoning symptom |
Table 1
| Date | November 9 | November 12 | November 15 | November 17 | November 21 | |||||||||||||||
| Repeat | 1 | 2 | 3 | On average | 1 | 2 | 3 | On average | 1 | 2 | 3 | On average | 1 | 2 | 3 | On average | 1 | 2 | 3 | On average |
| a | 1.6 | 1.8 | 1.6 | 1.7 | 3.2 | 3.2 | 3.3 | 3.2 | 4.6 | 4.6 | 4.7 | 4.6 | 6.7 | 6.8 | 6.7 | 6.7 | 8.3 | 8.2 | 8.2 | 8.2 |
| b | 2.0 | 1.9 | 1.9 | 2.0 | 3.5 | 3.4 | 3.5 | 3.5 | 5.0 | 4.8 | 4.9 | 4.9 | 6.9 | 7.1 | 7.1 | 7.1 | 8.7 | 8.6 | 8.7 | 8.7 |
| c | 1.6 | 1.8 | 1.7 | 1.7 | 3.2 | 3.2 | 3.1 | 3.2 | 4.6 | 4.6 | 4.5 | 4.6 | 6.7 | 6.8 | 6.9 | 6.8 | 8.3 | 8.3 | 8.4 | 8.3 |
| d | 1.9 | 1.8 | 1.9 | 1.9 | 3.4 | 3.3 | 3.4 | 3.4 | 5.0 | 4.8 | 4.8 | 4.9 | 7.2 | 7.2 | 7.1 | 7.2 | 8.6 | 8.6 | 8.7 | 8.6 |
| e | 1.5 | 1.4 | 1.5 | 1.5 | 2.9 | 3.1 | 2.9 | 2.9 | 4.3 | 4.4 | 4.3 | 4.4 | 6.2 | 6.3 | 6.3 | 6.3 | 8.0 | 7.9 | 8.1 | 8.0 |
As can be seen from Table 1, the gyphosate solution drug effect that is prepared by the inventive method obviously is better than the gyphosate solution of former explained hereafter.
Claims (3)
1, a kind of treatment process of glyphosate mother solution, comprise and add liquid caustic soda, in and alkyl esterification method prepare a large amount of acid mother liquids that produce in the glyphosate production process, regulate the pH value to 10-12, reclaim catalyst of triethylamine, concentrate remaining alkaline mother liquor, remove a large amount of sodium chloride crystals, it is characterized in that: in the alkaline concentrated mother liquor of removing behind the sodium chloride crystal, feed ammonia successively, carbon dioxide, fully reaction, filter, filtrate is treated to be used to prepare the ammonium glyphosate aqua, in being reused for after the by product sodium bicarbonate reclaims and the acid mother liquid that produces in the glyphosate production process.
2, the treatment process of glyphosate mother solution as claimed in claim 1 is characterized in that: the great amount of carbon dioxide that produces in being reused for after the by product sodium bicarbonate reclaims and during the glyphosphonic acid aqueous mother liquor, reclaim the processing that is used for alkaline mother liquor.
3, the treatment process of glyphosate mother solution as claimed in claim 1, it is characterized in that: in being reused for after the by product sodium bicarbonate reclaims and during the acid mother liquid that produces in the glyphosate production process, elder generation's neutralizing acid aqueous mother liquor to pH value is 3-7, add a certain amount of liquid caustic soda solution again, regulate pH value 10-12.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100532894A CN100340566C (en) | 2005-02-25 | 2005-02-25 | Treatment method of glyphosate mother liquor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100532894A CN100340566C (en) | 2005-02-25 | 2005-02-25 | Treatment method of glyphosate mother liquor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1824668A CN1824668A (en) | 2006-08-30 |
| CN100340566C true CN100340566C (en) | 2007-10-03 |
Family
ID=36935527
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100532894A Active CN100340566C (en) | 2005-02-25 | 2005-02-25 | Treatment method of glyphosate mother liquor |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100340566C (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101402654B (en) * | 2008-11-25 | 2011-09-14 | 江苏大学 | Method for recycling sodium glyphosate with air-float solvent floatation |
| CN101402653B (en) * | 2008-11-25 | 2011-07-06 | 江苏大学 | Method for abstracting and recycling sodium glyphosate with assistance of microwave |
| CN101757761B (en) * | 2008-12-25 | 2011-06-15 | 浙江新安化工集团股份有限公司 | Method for treating glyphosate mother liquor by oxidation method |
| CN101570324B (en) * | 2009-06-16 | 2013-05-08 | 吴伦飞 | Method for recovering phosphite from glyphosate mother liquor |
| CN101974030B (en) * | 2010-09-06 | 2012-05-30 | 山东潍坊润丰化工有限公司 | Preparation method of ammonium glyphosate technical product |
| CN107324973A (en) * | 2017-07-05 | 2017-11-07 | 巨化集团技术中心 | A kind of preparation method of perfluoroalkyl ethanol |
| CN108503393B (en) * | 2018-03-12 | 2021-08-20 | 浙江金帆达生化股份有限公司 | Comprehensive utilization method of nitrogen resources in glyphosate mother liquor |
| CN108948075B (en) * | 2018-08-22 | 2020-08-11 | 江西金龙化工有限公司 | Comprehensive utilization method of glyphosate byproduct ammonia water and alkali |
| CN112479812A (en) * | 2020-12-16 | 2021-03-12 | 南京延长反应技术研究院有限公司 | Micro-interface reaction system and method for preparing ethylene glycol by chloroethanol method |
| CN114287443A (en) * | 2021-12-10 | 2022-04-08 | 湖北泰盛化工有限公司 | Method for producing glyphosate potassium salt water agent by using glyphosate low-quality material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1340507A (en) * | 2000-08-31 | 2002-03-20 | 浙江新安化工集团股份有限公司 | Process for preparing glyphosate |
| CN1422275A (en) * | 2000-04-14 | 2003-06-04 | 美国陶氏益农公司 | Removal of chloride from phosphonomethyliminodiacetic acid process |
| CN1676527A (en) * | 2005-03-07 | 2005-10-05 | 浙江新安化工集团股份有限公司 | Glyphosate mother liquid treating method |
-
2005
- 2005-02-25 CN CNB2005100532894A patent/CN100340566C/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1422275A (en) * | 2000-04-14 | 2003-06-04 | 美国陶氏益农公司 | Removal of chloride from phosphonomethyliminodiacetic acid process |
| CN1340507A (en) * | 2000-08-31 | 2002-03-20 | 浙江新安化工集团股份有限公司 | Process for preparing glyphosate |
| CN1676527A (en) * | 2005-03-07 | 2005-10-05 | 浙江新安化工集团股份有限公司 | Glyphosate mother liquid treating method |
Non-Patent Citations (4)
| Title |
|---|
| 烷基酯法草甘膦生产工艺中的三乙胺连续化回收 任不凡等，农药，第43卷第6期 2004 * |
| 烷基酯生产草甘膦的技术进展 陈晓祥等，现代化工，第2卷 1998 * |
| 草甘膦生产中三乙胺的连续回收工艺 陈锡华，现代化工，第24卷第3期 2004 * |
| 草甘膦结晶母液处理新工艺 薛光才等，湖北化工，第增刊卷 1998 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1824668A (en) | 2006-08-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100340566C (en) | Treatment method of glyphosate mother liquor | |
| US7811352B2 (en) | Fertilizer compositions and methods of using | |
| CN1304402C (en) | Process for treating cglyphosate mother liquor | |
| CN100515945C (en) | Low sodium salt of botanic origin | |
| CN107916108A (en) | A kind of soil conditioner, its preparation method and application | |
| CN1676527A (en) | Glyphosate mother liquid treating method | |
| CN101044091A (en) | Method for crystallizing soluble salts of divalent anions from brine | |
| CN109651433A (en) | A kind of separation method of L-glufosinate-ammonium and gluconic acid | |
| CN100340565C (en) | New method for treating glyphosate mother liquor | |
| CN101704841A (en) | Method for recovering glyphosate mother liquor | |
| CN1123266A (en) | Liquid plant-foliage fertilizer and preparation method thereof | |
| CN1277835C (en) | Process for treating glyphosate mother liquid | |
| CN113929532A (en) | Brown algae oligosaccharide water-soluble fertilizer and preparation method thereof | |
| CA3203347A1 (en) | Efficient methods and compositions for recovery of products from organic acid pretreatment of plant materials | |
| CN110526500A (en) | A kind of reutilization system and method for high COD soybean waste liquid with high salt | |
| US20230406735A1 (en) | Process to separate an aqueous feed | |
| EP2586519A1 (en) | Processing of contaminated waste water from the production of plant protection agents | |
| CN1412107A (en) | Production method of potassium dihydrogen phosphate | |
| CN1803774A (en) | Dichloro quinolinic acid, its preparation method and solid preparation thereof | |
| CN1789117A (en) | Method for producing potassium dihydrogen phosphate and gypsum using hydrochloric acid method | |
| CN100519489C (en) | Method for manufacturing multi-element high-efficiency foliar fertilizer enriched in organic matter | |
| CN106631350A (en) | Preparation method of straw organic liquid specially used for crops | |
| CN116159413A (en) | Desulfurization system, desulfurization method and application of desulfurization byproducts | |
| CN1919799A (en) | Natural biological solubility calcium product, preparation method and use | |
| CN1653904A (en) | Sterilant herbicide and its production process |
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 |