CN101805371A - Method for recycling glyphosate raw powder from glyphosate mother liquid - Google Patents
Method for recycling glyphosate raw powder from glyphosate mother liquid Download PDFInfo
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- CN101805371A CN101805371A CN200910114938A CN200910114938A CN101805371A CN 101805371 A CN101805371 A CN 101805371A CN 200910114938 A CN200910114938 A CN 200910114938A CN 200910114938 A CN200910114938 A CN 200910114938A CN 101805371 A CN101805371 A CN 101805371A
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- glyphosate
- mother liquid
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- triethylamine
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Abstract
The invention relates to a method for recycling glyphosate raw powder from glyphosate mother liquid. The method is characterized by including the following processing steps: (1) extractant triethylamine is added into glyphosate acid mother liquid, fully stirring to be uniform is carried out, standing and layering are carried out; (2) the glyphosate mother liquid is concentrated until glyphosate content is 4-5%, crystallization and separation are carried out, so as to obtain glyphosate concentrated mother liquid; (3) under the strong acid condition, sodium chloride and other inorganic salt are seeded out, solid-liquid separation is carried out, so as to obtain filter cake and filtrate; (4) crystallization, filtering and drying are carried out, so as to obtain the glyphosate raw powder. The invention has the advantages that: 1, the existing glyphosate mother liquid processing technology is broken through, glyphosate dissolved in mother liquid is directly converted into glyphosate raw powder, usage value of glyphosate in mother liquid is improved; 2, liquid caustic soda usage for recycling triethylamine in acid mother liquid after extraction is reduced, and treatment cost is reduced.
Description
Technical field
The present invention relates to a kind of method that reclaims the former powder of glyphosate, relate in particular to a kind of method that from glyphosate mother solution, reclaims the former powder of glyphosate.
Background technology
Glyphosate is a most popular weedicide on the present world market, also occupies significant proportion in the agricultural chemicals outlet of China simultaneously.Glyphosate production mainly contains two kinds of methods, and the one, the IDA method, offshore company generally adopts this method, another kind of glycine method, domestic big multiple enterprises adopts this method, and production capacity is above 300,000 tons/year.A large amount of Cl acid mother liquids that contain be can produce during preparing glyphosate by glycin method, glyphosate, phosphorous acid of triethylamine hydrochloride, 1-3% etc. contained in the mother liquor.The main method of present domestic glyphosate production business processes mother liquor is: add 30% sodium hydroxide solution in acid mother liquor, regulate pH value 10-12, standing demix, reclaim the upper strata catalyst of triethylamine, the residue alkali liquor is through concentrating, after removing part sodium-chlor, get the dense mother liquor that glyphosate content is about 2-5%, be used to prepare 10% sodium glyphosate aqua.Because contain a large amount of sodium-chlor in the sodium glyphosate aqua, weeding ratio is low in the use, environmental pollution is serious, and usage quantity will gradually reduce, even eliminates.
Summary of the invention
The invention provides a kind of method that from glyphosate mother solution, reclaims the former powder of glyphosate, improve the utilization ratio of glyphosate in the mother liquor, reduce the mother liquor processing cost.
The present invention is achieved in that and it is characterized in that processing step is:
A kind of method that reclaims the former powder of glyphosate from glyphosate mother solution is characterized in that processing step is:
(1) be under the 30-60 ℃ of condition in temperature of reaction, press extraction agent triethylamine and glyphosphonic acid aqueous mother liquor weight ratio 1: 2-5 mixes, after stirring, standing demix, the upper strata is a triethylamine salt solution, and lower floor is a glyphosate mother solution, separates back mother liquor glyphosate content 5%-8%;
(2) glyphosate alkaline mother liquor is concentrated into glyphosate content 4-5%, the sodium-chlor supersaturation produces crystallization, is cooled to 25-40 ℃, carries out solid-liquid separation, and the glyphosate concentrated mother liquor that obtains is used for step process down;
(3) mother liquor that step (1) or (2) are obtained is 1 with hydrochloric acid by weight: 1-5 mixes, and under strong acidic condition, sodium-chlor and other inorganic salt crystallizations are separated out, and carry out solid-liquid separation, obtain filter cake and filtrate;
(4) the filtrate alternative materials hydrochloric acid with step (3) joins in the hydrolysis reaction of glyphosate production, obtains the former powder of glyphosate through crystallization, filtration, drying again, and former powder yield is brought up to 75%-78%.
The triethylamine salt solution that obtains in the step of the present invention (1) adds alkali and transfers pH value 10-12, and standing demix reclaims the upper strata triethylamine, and a small amount of triethylamine is told in lower floor's rectifying, enters Sewage treatment systems.
Content of hydrochloric acid in the step of the present invention (3) is 20%-36%, and mother liquor and hydrochloric acid weight ratio are 1: 1-5, temperature of reaction 0-50 ℃.
Recovery method of the present invention utilizes in strong acid the solubleness of sodium-chlor and other inorganic salt lower, and the higher characteristics of glyphosate solubleness; After mother liquor and the mixed in hydrochloric acid, sodium-chlor and other inorganic salt crystallizations of being dissolved in the mother liquor are separated out, and can remove sodium-chlor a large amount of in the mother liquor and other inorganic salt.With the hydrochloric acid alternative materials hydrochloric acid that the has dissolved glyphosate reaction that is hydrolyzed; Mother liquor amount and pH value do not change in the glyphosate crystallizing system simultaneously, and the quantity of mother liquor dissolving glyphosate is identical, and glyphosate is separated out in crystallization to be increased, thereby the former powder yield of realization glyphosate is brought up to 75-78% by 72-73%.
Advantage of the present invention is: 1, break through existing glyphosate mother solution treatment process, the glyphosate that directly will be dissolved in the mother liquor is transformed into the former powder of glyphosate, has improved the use value of glyphosate in the mother liquor; Liquid caustic soda consumption when 2, the acid mother liquor after extraction reclaims triethylamine reduces, and has reduced processing cost.
Embodiment
Embodiment one
Get glyphosphonic acid mother liquor 300g, glyphosate content 1.85% adds extraction agent triethylamine 100g, 50 ℃ of control reaction temperature, and standing demix obtains triethylamine salt solution 312.5g, obtains glyphosate mother solution 87.5g, glyphosate content 6.05%.
It is in 32.1% the concentrated hydrochloric acid that above-mentioned 87.5g glyphosate mother solution is joined 320g content, cool to 20 ℃, because sodium chloride salt and the solubleness of inorganic salt in strong acid is little and crystallization is separated out, carry out solid-liquid separation, get sodium-chlor and inorganic salt mixt 18.5g, dilute hydrochloric acid 389g, content of hydrochloric acid 25.2%, glyphosate content 1.34%.
Get methyl alcohol 320g, triethylamine 82.0g, Paraformaldehyde 96 51.25g, glycine 61.0g, dimethylphosphite 107.5g carries out the glyphosate building-up reactions, must synthesize liquid.With above-mentioned 389g hydrochloric acid, join in the synthetic liquid 40 ℃ of temperature, slowly be warmed up to 117 ℃ of reactions that are hydrolyzed.Hydrolysis reaction finishes to add an amount of crystal water, slowly cools to 80 ℃, and the liquid caustic soda of adding 30% is regulated pH value to 1.0-1.2, continues to cool to 30 ℃.Filter, get glyphosphonic acid aqueous mother liquor 308.5g, glyphosate content 1.92%; Get glyphosate wet-milling 127.2g, get the former powder 109.8g of glyphosate after the drying, glyphosate content 95.4%, calculating former powder yield is 77.4%.
Embodiment two
Get glyphosate alkali liquor 500g, glyphosate content 1.15% adds hydrochloric acid and regulates pH value 7-8, is heated to 100-110 ℃ and concentrates about 2 hours, cools to 30 ℃, and solid-liquid separation gets glyphosate concentrated mother liquor 121.5g, glyphosate content 4.35%.
It is in 35.1% the concentrated hydrochloric acid that above-mentioned 121.5g glyphosate mother solution is joined 330g content, cool to about 20 ℃, sodium chloride salt and inorganic salt crystallization are separated out, carry out solid-liquid separation, get sodium-chlor and inorganic salt mixt 45.5g, dilute hydrochloric acid 406g, content of hydrochloric acid 23.5%, glyphosate content 1.25%.
Get methyl alcohol 320g, triethylamine 82.0g, Paraformaldehyde 96 51.25g, glycine 61.0g, dimethylphosphite 107.5g carries out the glyphosate building-up reactions, must synthesize liquid.With above-mentioned 406g hydrochloric acid, join in the synthetic liquid 40 ℃ of temperature, slowly be warmed up to 117 ℃ of reactions that are hydrolyzed.Hydrolysis reaction finishes to add an amount of crystal water, slowly cools to 80 ℃, and the liquid caustic soda of adding 30% is regulated pH value to 1.0-1.2, continues to cool to 30 ℃.Filter, get glyphosphonic acid aqueous mother liquor 315g, glyphosate content 1.85% gets glyphosate wet-milling 125.2g, gets the former powder 109.5g of glyphosate after the drying, glyphosate content 95.3%, and calculating former powder yield is 77.1%.
Claims (3)
1. method that reclaims the former powder of glyphosate from glyphosate mother solution is characterized in that processing step is:
(1) be under the 30-60 ℃ of condition in temperature of reaction, press extraction agent triethylamine and glyphosphonic acid aqueous mother liquor weight ratio 1: 2-5 mixes, after stirring, standing demix, the upper strata is a triethylamine salt solution, and lower floor is a glyphosate mother solution, separates back mother liquor glyphosate content 5%-8%;
(2) glyphosate alkaline mother liquor is concentrated into glyphosate content 4-5%, the sodium-chlor supersaturation produces crystallization, is cooled to 25-40 ℃, carries out solid-liquid separation, and the glyphosate concentrated mother liquor that obtains is used for step process down;
(3) mother liquor that step (1) or (2) are obtained is 1 with hydrochloric acid by weight: 1-5 mixes, and under strong acidic condition, sodium-chlor and other inorganic salt crystallizations are separated out, and carry out solid-liquid separation, obtain filter cake and filtrate;
(4) the filtrate alternative materials hydrochloric acid with step (3) joins in the hydrolysis reaction of glyphosate production, obtains the former powder of glyphosate through crystallization, filtration, drying again, and former powder yield is brought up to 75%-78%.
2. a kind of method that from glyphosate mother solution, reclaims the former powder of glyphosate according to claim 1, it is characterized in that: the triethylamine salt solution that obtains in the described step (1), add alkali and transfer pH value 10-12, standing demix, reclaim the upper strata triethylamine, a small amount of triethylamine is told in lower floor's rectifying, enters Sewage treatment systems.
3. a kind of method that from glyphosate mother solution, reclaims the former powder of glyphosate according to claim 1, it is characterized in that: the content of hydrochloric acid in the described step (3) is 20%-36%, mother liquor and hydrochloric acid weight ratio are 1: 1-5, temperature of reaction 0-50 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910114938A CN101805371A (en) | 2009-02-17 | 2009-02-17 | Method for recycling glyphosate raw powder from glyphosate mother liquid |
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| CN200910114938A CN101805371A (en) | 2009-02-17 | 2009-02-17 | Method for recycling glyphosate raw powder from glyphosate mother liquid |
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| CN101805371A true CN101805371A (en) | 2010-08-18 |
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| CN200910114938A Pending CN101805371A (en) | 2009-02-17 | 2009-02-17 | Method for recycling glyphosate raw powder from glyphosate mother liquid |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103275119A (en) * | 2013-05-27 | 2013-09-04 | 四川省乐山市福华通达农药科技有限公司 | Crystallization process for producing glyphosate |
| 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 |
| CN110330037A (en) * | 2019-07-17 | 2019-10-15 | 江苏汉凯工程技术有限公司 | The method of sodium chloride is recycled in a kind of glyphosate mother solution |
| CN110393189A (en) * | 2018-04-25 | 2019-11-01 | 刘德亮 | The comprehensive processing technique of glyphosate mother solution |
| CN111333519A (en) * | 2020-03-11 | 2020-06-26 | 陈兴华 | Comprehensive treatment and resource recycling method for glyphosate mother liquor |
| CN111715658A (en) * | 2020-06-01 | 2020-09-29 | 湖北泰盛化工有限公司 | Waste treatment process in glyphosate technical production process |
| CN113072580A (en) * | 2021-04-19 | 2021-07-06 | 浙江新安化工集团股份有限公司 | Method for recovering glyphosate from glyphosate acid mother liquor by glycine method |
-
2009
- 2009-02-17 CN CN200910114938A patent/CN101805371A/en active Pending
Non-Patent Citations (2)
| Title |
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| 林佳楷: "固体草甘膦酸的清洁生产评述", 《福建化工》 * |
| 薛光才等: "草甘膦结晶母液处理新工艺", 《湖北化工》 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103275119A (en) * | 2013-05-27 | 2013-09-04 | 四川省乐山市福华通达农药科技有限公司 | Crystallization process for producing glyphosate |
| CN103275119B (en) * | 2013-05-27 | 2016-05-25 | 四川省乐山市福华通达农药科技有限公司 | A kind of crystallization processes of glyphosate production |
| 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 |
| CN110393189A (en) * | 2018-04-25 | 2019-11-01 | 刘德亮 | The comprehensive processing technique of glyphosate mother solution |
| CN110330037A (en) * | 2019-07-17 | 2019-10-15 | 江苏汉凯工程技术有限公司 | The method of sodium chloride is recycled in a kind of glyphosate mother solution |
| CN111333519A (en) * | 2020-03-11 | 2020-06-26 | 陈兴华 | Comprehensive treatment and resource recycling method for glyphosate mother liquor |
| CN111715658A (en) * | 2020-06-01 | 2020-09-29 | 湖北泰盛化工有限公司 | Waste treatment process in glyphosate technical production process |
| CN111715658B (en) * | 2020-06-01 | 2022-04-22 | 湖北泰盛化工有限公司 | Waste treatment process in glyphosate technical production process |
| CN113072580A (en) * | 2021-04-19 | 2021-07-06 | 浙江新安化工集团股份有限公司 | Method for recovering glyphosate from glyphosate acid mother liquor by glycine method |
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Application publication date: 20100818 |