CN100551927C - The circulation recovery method of glyphosate mother solution - Google Patents
The circulation recovery method of glyphosate mother solution Download PDFInfo
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- CN100551927C CN100551927C CNB2007100164961A CN200710016496A CN100551927C CN 100551927 C CN100551927 C CN 100551927C CN B2007100164961 A CNB2007100164961 A CN B2007100164961A CN 200710016496 A CN200710016496 A CN 200710016496A CN 100551927 C CN100551927 C CN 100551927C
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Abstract
The present invention relates to a kind of treatment process of glycine method synthesizing glyphosate mother liquor, particularly a kind of circulation recovery method of glyphosate mother solution.This method is: 1) in the glyphosate crystal solution, add conditioning agent, regulate pH to 0.5-1.5,1-100 ℃ of reaction down, stirring makes it sufficient reacting and carries out solid-liquid separation, obtains wet-milling and separates out mother liquor; 2) add conditioning agent in separating out mother liquor, regulate pH to 9-12, standing demix reclaims triethylamine; Described conditioning agent is the bicarbonate of ammonia of wt70%-100% and the liquid caustic soda of wt0%-30%; 3) carbon dioxide recycle; 4) mother liquor behind the recovery triethylamine is mixed with gyphosate solution through concentrating.Of the present invention following in the recovery method uses all or part of replacement liquid caustic soda of bicarbonate of ammonia to carry out the recovery of triethylamine in the mother liquor, can reduce the waste water generation in a large number, effectively reduces environmental protection of enterprise pressure; By adopting neutralization, absorb, the technology of cyclically utilizing makes cost recovery greatly reduce, and operating environment is greatly improved.
Description
(1) technical field
The present invention relates to a kind of treatment process of glycine method synthesizing glyphosate mother liquor, particularly a kind of circulation recovery method of glyphosate mother solution.
(2) background technology
Glyphosate is a kind of natural disposition inner sucting conduction type weedicide that goes out, and is the maximum and the fastest a kind of weedicide of rate of growth of global sales at present.Generally make by glycine method or IDA method.Domestic common employing preparing glyphosate by glycin method promptly is equipped with glyphosate with the dialkyl phosphite legal system.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, and is higher such as energy consumption, to the equipment requirements height.Preparing glyphosate by glycin method is about to Paraformaldehyde 96 or formaldehyde heating for dissolving 5-10min in containing the methanol solvate of triethylamine, again glycine is added heating for dissolving in this solution, add dimethylphosphite behind the 30min, under 60-70 ℃, carry out condensation reaction, finish through the 30-120min afterreaction, adding hydrochloric acid again is hydrolyzed, generate the hydrochloride of glyphosate, the glyphosphonic acid crystallization was separated out after underpressure distillation removed solvent methanol and excessive hydrochloric acid again, filter after scouring, filter cake is glyphosphonic acid, contain triethylamine in the mother liquor, the glyphosate of hydrochloric acid and minimal amounts of dissolved, through liquid caustic soda neutralization and the mother liquor after reclaiming triethylamine, add the former powder of glyphosate after, prepare 10% glyphosate salt aqua.Because mother liquor contains solutes such as a lot of sodium-chlor, sodium hydroxide, the existence of these solutes has had a strong impact on the solubleness of the former powder of glyphosate in this solution, thus mother liquor can only to be mixed with content be 10% gyphosate solution.This technology exists handles back mother liquor total amount increase, wastewater discharge is just big like this, bring very big pressure to environmental protection, and the mother liquor chemical oxygen demand (COD) is up to more than the 50000mg/L, glyphosate contained in the mother liquor has restraining effect to the used anerobe of sewage disposal, should not directly carry out biochemical treatment.In addition, mother liquor concentrates and also consumes lot of energy.The method of seeking the more energy-conservation processing mother liquor of a kind of more environmental protection is present urgent problem.
In patent CN1308335C glyphosate and recoverying and utilizing method, the CN1308336C process for treating production mother liquor of glyphosate of mother liquor, the technical scheme of above-mentioned patent remains and neutralizes with liquid caustic soda earlier, the bicarbonate of ammonia that adds saturation capacity again, generate sodium bicarbonate, mother liquor can be made into the gyphosate solution of high density.But technique scheme though reached the purpose that sodium chloride content descends in the preparation aqua, does not fundamentally solve the big problem of mother liquor total amount.In addition, in the technique scheme, the large usage quantity of its bicarbonate of ammonia causes cost to improve.
(3) summary of the invention
Purpose of the present invention just provides a kind of circulation recovery method of glyphosate mother solution, and this method can be eliminated a large amount of glyphosate mother solutions and discharge the pollution that causes to environment, can prepare the better gyphosate solution of drug effect, also can effectively reduce production costs simultaneously.
The circulation recovery method of glyphosate mother solution of the present invention, adopt following step in proper order:
1) is being equipped with the dialkyl phosphite legal system in the technological process of glyphosate, in the glyphosate crystal solution after the glyphosate hydrolysis finishes, adding conditioning agent, regulate pH to 0.5-1.5,1-100 ℃ of reaction down, stirring makes it sufficient reacting and carries out solid-liquid separation, obtains wet-milling and separates out mother liquor;
2) add conditioning agent in separating out mother liquor, regulate pH to 9-12, standing demix reclaims triethylamine; Step 1) and step 2) described in conditioning agent be the bicarbonate of ammonia of wt70%-100% and the saturated caustic lye of soda of wt0%-30%;
3) above-mentioned 1) 2) carbon dioxide that produces of two steps feeds in the ammoniacal liquor, obtains bicarbonate of ammonia, cyclically utilizing to 1) 2) in two steps;
4) mother liquor behind the recovery triethylamine is mixed with gyphosate solution through concentrating.
The circulation recovery method of the invention described above, in step 1), the add-on of described conditioning agent is the wt10%-50% of glyphosate crystal solution; Be preferably wt10%-30%.Step 2) in, the add-on of described conditioning agent is the wt30%-150% that separates out mother liquor; Be preferably wt30%-100%.
Of the present invention following in the recovery method uses all or part of replacement liquid caustic soda of bicarbonate of ammonia to carry out the recovery of triethylamine in the mother liquor, can reduce the waste water generation in a large number, effectively reduces environmental protection of enterprise pressure.
Described glyphosate mother solution circulation and recovery process does not add or has added a spot of moisture, makes that the wastewater flow rate in producing obviously reduces, and has solved the problem that glyphosate waste water is difficult to handle.Owing to adopt neutralization, absorb, the technology of cyclically utilizing makes cost recovery greatly reduce, and operating environment is greatly improved.
(4) embodiment:
The present invention will be further described below by embodiment, but protection scope of the present invention is not limited to this.
Embodiment 1
Be equipped with the dialkyl phosphite legal system in the technological process of glyphosate, the glyphosate hydrolysis finishes, and gets the glyphosate crystal solution after the glyphosate crystallization is separated out.Get above-mentioned 200g glyphosate crystal solution, add 20g bicarbonate of ammonia, regulate pH to 1.2,50 ℃ of reactions down, the crystallization suction filtration is taken out crystallization, must separate out mother liquor.
In separating out mother liquor, add 100g bicarbonate of ammonia, regulate PH to 10.Standing demix gets upper strata triethylamine 45.8g.The carbon dioxide of above-mentioned generation feeds in the ammoniacal liquor and absorbs, and is back to use aforementioned process after concentrating.Reclaiming mother liquor behind the triethylamine, can be mixed with content be 10% gyphosate solution.
Embodiment 2
Be equipped with the dialkyl phosphite legal system in the technological process of glyphosate, the glyphosate hydrolysis finishes, and gets the glyphosate crystal solution after the glyphosate crystallization is separated out.Get above-mentioned 200g glyphosate crystal solution, add 25g bicarbonate of ammonia, regulate pH to 1.3,80 ℃ of reactions down, the crystallization suction filtration is taken out crystallization, must separate out mother liquor.
In separating out mother liquor, add 105g bicarbonate of ammonia and 10g liquid caustic soda (saturated caustic lye of soda, down together), regulate PH to 11.Standing demix gets upper strata triethylamine 48.8g.The carbon dioxide of above-mentioned generation feeds in the ammoniacal liquor and absorbs, and is back to use aforementioned process after concentrating.Reclaiming mother liquor behind the triethylamine, can be mixed with content be 20% gyphosate solution.
Embodiment 3
Be equipped with the dialkyl phosphite legal system in the technological process of glyphosate, the glyphosate hydrolysis finishes, and gets the glyphosate crystal solution after the glyphosate crystallization is separated out.Get above-mentioned 200g glyphosate crystal solution, add 11g bicarbonate of ammonia and 10g liquid caustic soda, regulate pH to 1.2,20 ℃ of reactions down, the crystallization suction filtration is taken out crystallization, must separate out mother liquor.
In separating out mother liquor, add 110g bicarbonate of ammonia and 15g liquid caustic soda, regulate PH to 12.Standing demix gets upper strata triethylamine 50.1g.The carbon dioxide of above-mentioned generation feeds in the ammoniacal liquor and absorbs, and is back to use aforementioned process after concentrating.Reclaiming mother liquor behind the triethylamine, can be mixed with content be 10% gyphosate solution.
Embodiment 4
Be equipped with the dialkyl phosphite legal system in the technological process of glyphosate, the glyphosate hydrolysis finishes, and gets the glyphosate crystal solution after the glyphosate crystallization is separated out.Get above-mentioned 200g glyphosate crystal solution, add 60g bicarbonate of ammonia, regulate pH to 1.5,50 ℃ of reactions down, the crystallization suction filtration is taken out crystallization, must separate out mother liquor.
In separating out mother liquor, add 70g bicarbonate of ammonia and 30g liquid caustic soda, regulate PH to 12.Standing demix gets upper strata triethylamine g.The carbon dioxide of above-mentioned generation feeds in the ammoniacal liquor and absorbs, and is back to use aforementioned process after concentrating.Reclaiming mother liquor behind the triethylamine, can be mixed with content be 25% gyphosate solution.
Claims (3)
1, a kind of circulation recovery method of glyphosate mother solution is characterized in that adopting the step of following order:
1) is being equipped with the dialkyl phosphite legal system in the technological process of glyphosate, in the glyphosate crystal solution after the glyphosate hydrolysis finishes, adding conditioning agent, regulate pH to 0.5-1.5,1-100 ℃ of reaction down, stirring makes it sufficient reacting and carries out solid-liquid separation, obtains wet-milling and separates out mother liquor;
2) add conditioning agent in separating out mother liquor, regulate pH to 9-12, standing demix reclaims triethylamine; Step 1) and step 2) described in conditioning agent be the bicarbonate of ammonia of wt70%-100% and the saturated caustic lye of soda of wt0%-30%;
3) above-mentioned 1) 2) carbon dioxide that produces of two steps feeds in the ammoniacal liquor, obtains bicarbonate of ammonia, cyclically utilizing to 1) 2) in two steps;
4) mother liquor behind the recovery triethylamine is mixed with gyphosate solution through concentrating.
2, circulation recovery method as claimed in claim 1 is characterized in that: in the step 1), the add-on of described conditioning agent is the wt10%-50% of glyphosate crystal solution; Step 2) in, the add-on of described conditioning agent is the wt30%-150% that separates out mother liquor.
3, circulation recovery method as claimed in claim 1 is characterized in that: in the step 1), the add-on of described conditioning agent is the wt10%-30% of glyphosate crystal solution; Step 2) in, the add-on of described conditioning agent is the wt30%-100% that separates out mother liquor.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2007100164961A CN100551927C (en) | 2007-08-27 | 2007-08-27 | The circulation recovery method of glyphosate mother solution |
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| CNB2007100164961A CN100551927C (en) | 2007-08-27 | 2007-08-27 | The circulation recovery method of glyphosate mother solution |
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| CN100551927C true CN100551927C (en) | 2009-10-21 |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN101486732B (en) * | 2009-02-17 | 2011-11-16 | 南京师范大学 | Two-stage condensation crystallization method for recycling glyphosate from glyphosate production wastewater |
| CN101875670B (en) * | 2009-04-28 | 2012-05-30 | 苏州佳辉化工有限公司 | Synthesis method capable of improving purity of glyphosate |
| CN101671363B (en) * | 2009-09-30 | 2012-02-22 | 四川省乐山市福华通达农药科技有限公司 | Hydrolyzation post-processing technique during preparation of glyphosate through glycin method |
| 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 |
| CN108358763B (en) * | 2018-04-20 | 2023-05-02 | 湖北泰盛化工有限公司 | Alkyl ester method glyphosate solvent recovery system and process based on three-stage condensation |
| CN110396048A (en) * | 2018-04-25 | 2019-11-01 | 刘德亮 | The comprehensive recovering process of glyphosate mother solution |
| 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 |
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