CN1648131A - Process for treating glyphosate mother liquid - Google Patents
Process for treating glyphosate mother liquid Download PDFInfo
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- CN1648131A CN1648131A CN 200410099086 CN200410099086A CN1648131A CN 1648131 A CN1648131 A CN 1648131A CN 200410099086 CN200410099086 CN 200410099086 CN 200410099086 A CN200410099086 A CN 200410099086A CN 1648131 A CN1648131 A CN 1648131A
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- glyphosate
- mother liquor
- mother solution
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Abstract
The present invention relates to the process of treating glyphosate mother liquor from glycine synthesis process. The treating process includes the following successive steps: 1) introducing ammonia into glyphosate mother liquor to regulate pH to 7-10, letting stand and recovering triethylamine from the upper layer; and 2) decompression distilling lower layer of the mother liquor, cooling, filtering to eliminate ammonium chloride crystal and to obtain concentrated ammonium glyphosate liquid. The said treating process has low production cost, low power consumption and environment friendship, and can obtain concentrated liquid with raised effect. Furthermore, glyphosate may be separated from the mother liquor to raise total glyphosate yield.
Description
(1) technical field
The present invention relates to the mother liquid obtained treatment process of a kind of glyphosate, relate in particular to the mother liquid obtained treatment process of a kind of glycine method synthesizing glyphosate.
(2) background technology
Glyphosate is as the organic phosphine post-emergence herbicide of a kind of efficient, wide spectrum, low toxicity, safety, and is very effective to the control of perennial dark root malignant weed, farming, woods, herd, aspect application such as gardening is very extensive.
The preparation method of glyphosate is a lot, generally makes by glycine method or pmida98 oxidation style.Domestic common employing preparing glyphosate by glycin method.This method has low, the former powder yield of raw materials cost height, product purity advantages of higher, but prior art exists a lot of problems, higher such as energy consumption, to the equipment requirements height, and, can produce a large amount of Cl-acid mother liquids that contain during by preparing glyphosate by glycin method, contain a large amount of catalyst of triethylamine of using when synthetic in the mother liquor.Domestic at present normally with in the 30% sodium hydroxide solution adding 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.This technology exists handles back mother liquor total amount increase (add 30% sodium hydroxide solution and contain a large amount of water), increased the energy consumption when concentrated, and 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.
(3) summary of the invention
The object of the invention is to provide that a kind of production cost is low, energy efficient, protection environment and can improve the glyphosate mother solution treatment process of gained aqua drug effect simultaneously.
Glyphosate mother solution of the present invention is to be equipped with in the technological process of glyphosate with the dialkyl phosphite legal system, finish in the acid hydrolysis of glyphosate, the glyphosate technicals crystal is separated out the remaining mother liquor part in back in system, described treatment process comprises following sequential steps:
(1) feed ammonia in glyphosate mother solution, regulate pH value to 7～10, standing demix reclaims the upper strata triethylamine;
(2) lower floor's mother liquor is through underpressure distillation, and cooling obtains spissated ammonium glyphosate behind the filtration removal ammonia chloride crystal.
Lower floor's mother liquor also preferably distills earlier before underpressure distillation and collects cut below 110 ℃ in the described step (2); Gained cut standing demix reclaims cut upper strata triethylamine, and cut lower floor carries out step (2) and handles.
Glycine method synthesizing glyphosate technology was divided into for four steps usually: synthetic, hydrolysis precipitation, depickling and crystallization; As not depickling behind the hydrolysis precipitation, directly add a certain amount of alkali and regulate pH value and make the solubleness minimum of glyphosate, separating out from reaction solution of maximum then can improve the yield of glyphosate technicals, improves plant factor simultaneously and reduced energy consumption.Particularly, can add a certain amount of alkali at 0～140 ℃ after the acid hydrolysis of glyphosate finishes, the regulation system pH value is 0.7～1.5, and the glyphosate technicals crystal is separated out in system, and the glyphosate mother solution that obtains is done logical ammonia treatment again.
The temperature that feeds ammonia in glyphosate mother solution is generally 60 ℃～110 ℃.
The ammonium glyphosate of gained of the present invention can be used for preparing 10% ammonium glyphosate aqua, and well-known, the weeding usefulness of 10% ammonium glyphosate aqua (quick-acting and thoroughness) is more even better than 10% sodium glyphosate aqua.10% ammonium glyphosate aqua contains more ammonium chloride in addition, and ammonium chloride is called for short " oronain ", claims salmiak again, is a kind of quick-acting nitrogen chemical fertilizer, and nitrogen content is 24%～25%, belongs to physiological acidic fertilizer.It is applicable to crops such as wheat, paddy rice, corn, rape, especially linen-cotton class crop is had fortifying fibre toughness and pulling force and improves the effect of quality.
The treatment process production cost of glyphosate mother solution of the present invention is low, energy efficient, protection environment and can improve the drug effect of gained aqua simultaneously.As not depickling behind the hydrolysis precipitation, directly add a certain amount of alkali and regulate pH value and make the solubleness minimum of glyphosate, separating out from reaction solution of maximum then can improve the yield of glyphosate technicals, improved plant factor simultaneously and reduced energy consumption.
(4) embodiment
Below by embodiment the present invention is further specified, but protection scope of the present invention is not limited to this.
Embodiment 1
Get the 300g glyphosate mother solution, feed the 30.8g ammonia while cooling off, transferring to PH is 7.Standing demix gets upper strata triethylamine 34.4g, and cut below 110 ℃ is collected in lower floor's mother liquor distillation, and cut is standing demix once more, gets upper strata triethylamine 34.6g; The underpressure distillation of residue mother liquor is cooled to normal temperature, filters, and obtains ammonia chloride crystal 35.0g (content 78.6%), and concentrated mother liquor content is 2.8%.
Embodiment 2
Get the 300g glyphosate mother solution, feed the 31.4g ammonia while cooling off, transferring to PH is 7.5.Standing demix gets upper strata triethylamine 38.1g, and cut below 110 ℃ is collected in lower floor's mother liquor distillation, and cut is standing demix once more, gets upper strata triethylamine 33.1g; The underpressure distillation of residue mother liquor is cooled to normal temperature, filters, and obtains ammonia chloride crystal 42.2g (content 82.0%), and concentrated mother liquor content is 3.1%.
Embodiment 3
Get the 300g glyphosate mother solution, feed the 43.2g ammonia while cooling off, transferring to PH is 8.Standing demix gets upper strata triethylamine 50.0g, and cut below 110 ℃ is collected in lower floor's mother liquor distillation, and cut is standing demix once more, gets upper strata triethylamine 20.7g; The underpressure distillation of residue mother liquor is cooled to normal temperature, filters, and obtains ammonia chloride crystal 41.5g (content 82.2%), and concentrated mother liquor content is 3.0%.
Embodiment 4
Get the 300g glyphosate mother solution, feed the 58.5g ammonia while cooling off, transferring to PH is 9.0.Standing demix gets upper strata triethylamine 62.5g, and cut below 110 ℃ is collected in lower floor's mother liquor distillation, and cut is standing demix once more, gets upper strata triethylamine 6.3g; The underpressure distillation of residue mother liquor is cooled to normal temperature, filters, and obtains ammonia chloride crystal 44.3g (content 83.8%), and concentrated mother liquor content is 3.2%.
Embodiment 5
Get the 300g glyphosate mother solution, feed the 64.7g ammonia while cooling off, transferring to PH is 10.Standing demix gets upper strata triethylamine 65.8g, and cut below 110 ℃ is collected in lower floor's mother liquor distillation, and cut is standing demix once more, gets upper strata triethylamine 5.1g; The underpressure distillation of residue mother liquor is cooled to normal temperature, filters, and obtains ammonia chloride crystal 40.6g (content 86.0%), and concentrated mother liquor content is 3.5%.
Embodiment 6
300 gram methyl alcohol, 60 gram triethylamines, 40 gram Paraformaldehyde 96s are added in the four-hole boiling flask, stir, insulation is 60 minutes about 40 ℃.Add glycine 45 grams, 50 ℃ are incubated 60 minutes.Add dimethylphosphite 80 grams then, 65 ℃ are incubated 95 minutes.Be cooled to 30 ℃, add 30% hydrochloric acid 200 gram, intensification precipitation to 120 ℃ is cooled to 95 ℃ and adds 25 gram water, and Dropwise 35 restrains 30% sodium hydroxide solution, and regulating PH is 0.9.Crystallisation by cooling, filtering drying get glyphosate technicals 79.2 grams, content 95.2%, and yield 76.3%, filtrate is described glyphosate mother solution.
Get the above-mentioned glyphosate mother solution 300g that obtains, feed the 43.2g ammonia while cooling off, transferring to PH is 8.Standing demix gets upper strata triethylamine 50.0g, and cut below 110 ℃ is collected in lower floor's mother liquor distillation, and cut is standing demix once more, gets upper strata triethylamine 20.7g; The underpressure distillation of residue mother liquor is cooled to normal temperature, filters, and obtains ammonia chloride crystal 41.5g (content 82.2%), and concentrated mother liquor content is 3.0%.
Embodiment 7
Restrain methyl alcohol, 60 with 300 and restrain in triethylamines, the 40 gram Paraformaldehyde 96s adding four-hole boiling flasks, stir, 30 ℃ are incubated 60 minutes.Add glycine 45 grams, 50 ℃ are incubated 50 minutes.Add dimethylphosphite 80 grams then, 50 ℃ are incubated 80 minutes.Be cooled to 30 ℃, add 30% hydrochloric acid 200 gram, intensification precipitation to 120 ℃ is cooled to 95 ℃ and adds 25 gram water, Dropwise 58 grams 30% potassium hydroxide solution, and regulating PH is 1.2.Crystallisation by cooling, filtering drying get glyphosate technicals 79.2 grams, content 95.2%, and yield 76.3%, filtrate is described glyphosate mother solution.
Get the above-mentioned glyphosate mother solution 300g that obtains, feed the 58.5g ammonia while cooling off, transferring to PH is 9.0.Standing demix gets upper strata triethylamine 62.5g, and cut below 110 ℃ is collected in lower floor's mother liquor distillation, and cut is standing demix once more, gets upper strata triethylamine 6.3g; The underpressure distillation of residue mother liquor is cooled to normal temperature, filters, and obtains ammonia chloride crystal 44.3g (content 83.8%), and concentrated mother liquor content is 3.2%.
Claims (5)
1, a kind of treatment process of glyphosate mother solution, described glyphosate mother solution is to be equipped with in the technological process of glyphosate with the dialkyl phosphite legal system, finish in the acid hydrolysis of glyphosate, the glyphosate technicals crystal is separated out the remaining mother liquor part in back in system, it is characterized in that being to comprise following sequential steps:
(1) feed ammonia in glyphosate mother solution, regulate pH value to 7～10, standing demix reclaims the upper strata triethylamine;
(2) lower floor's mother liquor is through underpressure distillation, and cooling obtains spissated ammonium glyphosate behind the filtration removal ammonia chloride crystal.
2, the treatment process of glyphosate mother solution as claimed in claim 1 is characterized in that: lower floor's mother liquor distills earlier before underpressure distillation and collects cut below 110 ℃ in the described step (2); Gained cut standing demix reclaims cut upper strata triethylamine, and cut lower floor carries out step (2) and handles.
3, the treatment process of glyphosate mother solution as claimed in claim 1 or 2 is characterized in that adding a certain amount of alkali at 0～140 ℃ after the acid hydrolysis of glyphosate finishes, and the regulation system pH value is 0.7～1.5, and the glyphosate technicals crystal is separated out in system.
4, the treatment process of glyphosate mother solution as claimed in claim 3 is characterized in that the temperature of feeding ammonia in glyphosate mother solution is 60 ℃～110 ℃.
5, the treatment process of glyphosate mother solution as claimed in claim 4 is characterized in that described ammonium glyphosate is mixed with 10% ammonium glyphosate aqua again.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN 200410099086 CN1277835C (en) | 2004-12-23 | 2004-12-23 | Process for treating glyphosate mother liquid |
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| CN 200410099086 CN1277835C (en) | 2004-12-23 | 2004-12-23 | Process for treating glyphosate mother liquid |
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| CN1648131A true CN1648131A (en) | 2005-08-03 |
| CN1277835C CN1277835C (en) | 2006-10-04 |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100371338C (en) * | 2006-04-07 | 2008-02-27 | 捷马化工股份有限公司 | Process for separation and purification of glyphosate from glyphosate solution by membrane technology |
| CN100427184C (en) * | 2006-03-31 | 2008-10-22 | 杭州天创净水设备有限公司 | Process for concentrating pesticide mother liquor by film method |
| CN101570324A (en) * | 2009-06-16 | 2009-11-04 | 吴伦飞 | Method for recovering phosphite from glyphosate mother liquor |
| CN101591353B (en) * | 2008-05-28 | 2011-09-07 | 北京紫光英力化工技术有限公司 | Novel process for recycling mother solution of glyphosate prepared by glycin method |
| CN101440106B (en) * | 2008-12-19 | 2012-02-29 | 安徽锦邦化工股份有限公司 | Novel process for recovering waste acid from glyphosate production |
| CN101690868B (en) * | 2009-09-28 | 2012-03-14 | 安徽国星生物化学有限公司 | Method for processing glyphosate esterification mother liquor |
| CN101570547B (en) * | 2009-06-16 | 2012-07-04 | 吴伦飞 | Method for processing glyphosate mother liquor |
| CN101955431B (en) * | 2009-07-17 | 2013-08-21 | 浙江新安化工集团股份有限公司 | Recovery process of catalyst triethylamine in process of synthesizing glyphosate |
| CN101704843B (en) * | 2009-04-27 | 2013-09-18 | 南通泰禾化工有限公司 | Glyphosate continuous desolventizing production process |
| CN103421043A (en) * | 2012-10-31 | 2013-12-04 | 上海理工大学 | Hydrosis process improvement method for synthesizing glyphosate by alkyl ester process |
| CN103665035A (en) * | 2013-12-11 | 2014-03-26 | 鹤壁市农林制药有限公司 | Method for treating glyphosate mother liquor |
-
2004
- 2004-12-23 CN CN 200410099086 patent/CN1277835C/en active Active
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100427184C (en) * | 2006-03-31 | 2008-10-22 | 杭州天创净水设备有限公司 | Process for concentrating pesticide mother liquor by film method |
| CN100371338C (en) * | 2006-04-07 | 2008-02-27 | 捷马化工股份有限公司 | Process for separation and purification of glyphosate from glyphosate solution by membrane technology |
| CN101591353B (en) * | 2008-05-28 | 2011-09-07 | 北京紫光英力化工技术有限公司 | Novel process for recycling mother solution of glyphosate prepared by glycin method |
| CN101440106B (en) * | 2008-12-19 | 2012-02-29 | 安徽锦邦化工股份有限公司 | Novel process for recovering waste acid from glyphosate production |
| CN101704843B (en) * | 2009-04-27 | 2013-09-18 | 南通泰禾化工有限公司 | Glyphosate continuous desolventizing production process |
| CN101570547B (en) * | 2009-06-16 | 2012-07-04 | 吴伦飞 | Method for processing glyphosate mother liquor |
| CN101570324B (en) * | 2009-06-16 | 2013-05-08 | 吴伦飞 | Method for recovering phosphite from glyphosate mother liquor |
| CN101570324A (en) * | 2009-06-16 | 2009-11-04 | 吴伦飞 | Method for recovering phosphite from glyphosate mother liquor |
| CN101955431B (en) * | 2009-07-17 | 2013-08-21 | 浙江新安化工集团股份有限公司 | Recovery process of catalyst triethylamine in process of synthesizing glyphosate |
| CN101690868B (en) * | 2009-09-28 | 2012-03-14 | 安徽国星生物化学有限公司 | Method for processing glyphosate esterification mother liquor |
| CN103421043A (en) * | 2012-10-31 | 2013-12-04 | 上海理工大学 | Hydrosis process improvement method for synthesizing glyphosate by alkyl ester process |
| CN103665035A (en) * | 2013-12-11 | 2014-03-26 | 鹤壁市农林制药有限公司 | Method for treating glyphosate mother liquor |
| CN103665035B (en) * | 2013-12-11 | 2016-08-17 | 鹤壁市农林制药有限公司 | A kind of processing method of glyphosate mother solution |
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| CN1277835C (en) | 2006-10-04 |
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Assignee: Zhenjiang Jiangnan Chemical Co., Ltd. Assignor: Xin'an Chemical Industry Group Co., Ltd., Zhejiang Contract fulfillment period: 2009.1.6 to 2019.1.6 contract change Contract record no.: 2009320000381 Denomination of invention: Process for treating glyphosate mother liquid Granted publication date: 20061004 License type: Exclusive license Record date: 2009.3.16 |
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| LIC | Patent licence contract for exploitation submitted for record |
Free format text: EXCLUSIVE LICENSE; TIME LIMIT OF IMPLEMENTING CONTACT: 2009.1.6 TO 2019.1.6; CHANGE OF CONTRACT Name of requester: ZHENJIANG JIANGNAN CHEMICALS CO.,LTD Effective date: 20090316 |