CN1304402C - Process for treating cglyphosate mother liquor - Google Patents
Process for treating cglyphosate mother liquor Download PDFInfo
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- CN1304402C CN1304402C CN 200510049296 CN200510049296A CN1304402C CN 1304402 C CN1304402 C CN 1304402C CN 200510049296 CN200510049296 CN 200510049296 CN 200510049296 A CN200510049296 A CN 200510049296A CN 1304402 C CN1304402 C CN 1304402C
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- glyphosate
- mother liquor
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Abstract
The present invention provides a technique for processing glyphosate mother liquor. In the technical process of the glyphosate prepared by the glyphosate mother liquor through a phosphorous acid dialkyl ester method, after the acidic hydrolysis of the glyphosate is ended, the glyphosate raw medicine crystal is separated from the system, and the remain ed the mother liquor is the glyphosate mother liquor. The processing technique comprises the following order steps (1) alkali is added into the glyphosate mother liquor, the pH value is adjusted to 5-7, the glyphosate mother liquor is stratified to an upper layer of mother liquor and a lower layer of mother liquor, the upper layer is thin mother liquor, and the lower layer is thick mother liquor; (2) the thick mother liquor of the lower layer is added with alkali to adjust the pH valve to 8-12, and is stood to stratify, triethylamine of the upper layer is recovered, and the liquor of the lower layer is used for preparing gyphosate solution. The processing technique has the advantages of low production cost, saving of energy consumption and environmental protection, and can simultaneously enhance glyphosate utilization rate.
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 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, along with production-scale expansion, the glyphosate waste water amount also increases thereupon, brings very big pressure to environmental protection.Can produce a large amount of Cl that contains during preparing glyphosate by glycin method
-Acid mother liquid, the catalyst of triethylamine of using when containing a large amount of synthesizing in the mother liquor, domestic glyphosate by using glycine manufacturer is when handling this kind mother liquor and reclaim catalyst of triethylamine, usually adopting 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, it is synthetic that upper strata triethylamine recovery is re-used in glyphosate, a small amount of triethylamine is told in lower floor's mother liquor rectifying, remainder is removed part sodium-chlor through concentrating, and sodium chloride concentration is saturated in the concentrated mother liquor, 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 (glyphosate per ton produces about 6 tons of mother liquors), wastewater discharge is just big like this, bring very big pressure to environmental protection, and mother solution C ODcr (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.
(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 glyphosate utilization ratio 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) add alkali in glyphosate mother solution, adjust pH to 5～7 make it layering and obtain two-layer mother liquor up and down, and the upper strata is rare mother liquor, and lower floor is dense mother liquor;
(2) the dense mother liquor of lower floor adds adjusting PH with base to 8～12, and standing demix reclaims the upper strata triethylamine, and lower floor is used to prepare gyphosate solution.
In the treatment process of glyphosate mother solution, after obtaining the rare mother liquor in upper strata in the described step (1), add adjusting PH with base to 8～12 values, standing demix, it is synthetic that recovery upper strata triethylamine is re-used in glyphosate, and lower floor's mother liquor is told a small amount of triethylamine through rectifying, remaining partial discharge is to adding the calcium pond, to 3-4, the adding calcium hydroxide precipitation process is discharged after sedimentation filtration rear filtrate advances the biochemistry pool processing then with sour adjust pH.
Behind the standing demix, it is synthetic that the recovery of the triethylamine on upper strata is re-used in glyphosate in the described step (2); Before lower floor's mother liquor is used to prepare 10% gyphosate solution,, tells a small amount of triethylamine and reclaim that to be re-used in glyphosate synthetic earlier through rectifying.
It is one of following that described alkali is preferably: sodium hydroxide, potassium hydroxide, calcium hydroxide, ammonia, Isopropylamine etc.First toward glyphosate mother solution when adding alkali, can compound concentration during use at 30%～99% alkaline solution, also can directly add solid alkali; If the concentration that adds alkali was less than 30% o'clock, mother liquor is difficult to be divided into two-layer.Described alkali is preferably ammonia, and the gyphosate solution of preparation is preferably the ammonium glyphosate aqua.In the gyphosate solution of same concentrations, the ammonium salt aqua is more even better than the weeding usefulness (quick-acting and thoroughness) of the aqua of other salt.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 technology that the present invention handles mother liquor is to add toward in first adjusting PH with base to 5～7, after the glyphosate mother solution layering, most glyphosate all is enriched in the dense mother liquor of lower floor, ratio accounts for about 80% of whole mother liquor glyphosate, and through pre-treatment, dense mother liquor need not concentrate, the dense mother liquor of the system of providing and delivering aqua just can reach glyphosate content more than 3%, and glyphosate content has only about 1.0% in the mother liquor of former mother liquor treatment process delivery system aqua, through concentrating, also has only 2%-2.5%.
Method for processing mother solution of glyphosate of the present invention is compared with existing technology and is had the following advantages:
1. glyphosate utilization ratio height is after pre-treatment in the mother liquor, and the dense mother liquor content of the system of providing and delivering can be brought up to more than 3%;
2. mother liquor need not to heat and concentrates, and the energy consumption that mother liquor is handled obviously descends;
3. discharging mother solution C ODcr total amount descends obviously.Because after the original nut liquid layering, most of Organic Matter Enrichment needs the mother solution C ODcr total amount of biochemical treatment less relatively in dense mother liquor in the mother liquor, can descend more than 30%, has alleviated the pressure of biochemical treatment.
(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 300g glyphosate original nut liquid, add 25g96% calcium hydroxide while cooling off, transferring pH is 7.Standing demix, upper strata are rare mother liquor, 203.6g, and glyphosate content 0.78%, lower floor is dense mother liquor, heavy 121.4g, glyphosate content 4.63%.Rare mother liquor is through adding 30% sodium hydroxide adjust pH to 12, standing demix, it is synthetic that upper strata triethylamine recovery is re-used in glyphosate, a small amount of triethylamine is told in lower floor's mother liquor rectifying, remainder is disposed to and adds the calcium pond, with 30% hydrochloric acid adjust pH to 4, adding calcium hydroxide is handled then, discharges after the sedimentation rear filtrate advances the biochemistry pool biochemical treatment.
Dense mother liquor is through adding 30% sodium hydroxide adjust pH to 12, and standing demix, upper strata triethylamine reclaim that to be re-used in glyphosate synthetic, a small amount of triethylamine is told in lower floor's mother liquor rectifying, the heavy 163.6g of the dense mother liquor of remainder, content 3.43% is used to prepare 10% gyphosate solution.
Embodiment 2
Get 300g glyphosate original nut liquid, feed the 18.5g ammonia while cooling off, transferring to pH is 5.6.Standing demix, upper strata are rare mother liquor, heavy 211.2g, and glyphosate content 0.97%, lower floor is dense mother liquor, heavy 107.3g, glyphosate content 4.81%.Rare mother liquor is transferred pH to 8 through feeding ammonia, standing demix, it is synthetic that upper strata triethylamine recovery is re-used in glyphosate, a small amount of triethylamine is told in lower floor's mother liquor rectifying, remainder is disposed to and adds the calcium pond, with 30% hydrochloric acid adjust pH to 3, adding calcium hydroxide is handled then, discharges after the sedimentation rear filtrate advances the biochemistry pool biochemical treatment.
Dense mother liquor is through feeding ammonia adjust pH to 8, and standing demix, upper strata triethylamine reclaim that to be re-used in glyphosate synthetic, and a small amount of triethylamine is told in lower floor's mother liquor rectifying, the heavy 116.3g of the dense mother liquor of remainder, and content 4.43% is used to prepare 10% gyphosate solution.
Embodiment 3
Get 300g glyphosate original nut liquid, add 36g95% potassium hydroxide while cooling off, transferring to pH is 6.8.Standing demix, upper strata are rare mother liquor, heavy 219.7g, and glyphosate content 0.69%, lower floor is dense mother liquor, heavy 116.3g, glyphosate content 4.89%.Rare mother liquor is through adding 30% potassium hydroxide adjust pH to 11, standing demix, it is synthetic that upper strata triethylamine recovery is re-used in glyphosate, a small amount of triethylamine is told in lower floor's mother liquor rectifying, remainder is disposed to and adds the calcium pond, with 30% hydrochloric acid adjust pH to 3, adding calcium hydroxide is handled then, discharges after the sedimentation rear filtrate advances the biochemistry pool biochemical treatment.
Dense mother liquor is through adding 30% potassium hydroxide adjust pH to 11, and standing demix, upper strata triethylamine reclaim that to be re-used in glyphosate synthetic, a small amount of triethylamine is told in lower floor's mother liquor rectifying, the heavy 173.2g of the dense mother liquor of remainder, content 3.28% is used to prepare 10% gyphosate solution.
Claims (8)
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, comprise following sequential steps:
(1) add alkali in glyphosate mother solution, adjust pH to 5～7 make it layering and obtain two-layer mother liquor up and down, and the upper strata is rare mother liquor, and lower floor is dense mother liquor;
(2) the dense mother liquor of lower floor adds adjusting PH with base to 8～12, and standing demix reclaims the upper strata triethylamine, and lower floor is used to prepare gyphosate solution.
2, the treatment process of glyphosate mother solution as claimed in claim 1 is characterized in that: after obtaining the upper strata mother liquor in the described step (1), add adjusting PH with base to 8～12 values, standing demix, reclaim the upper strata triethylamine, lower floor tells a small amount of triethylamine through rectifying, and remaining part is advanced the biochemistry pool biochemical treatment.
3, the treatment process of glyphosate mother solution as claimed in claim 2, it is characterized in that: described after rectifying remaining part be disposed to earlier in the past and added the calcium pond entering the biochemistry pool biochemical treatment, with sour adjust pH to 3-4, the adding calcium hydroxide precipitation process is filtered rear filtrate through sedimentation and is advanced the biochemistry pool processing then.
4, the treatment process of glyphosate mother solution as claimed in claim 1, it is characterized in that: before lower floor's mother liquor is used to prepare gyphosate solution in the described step (2),, divides and remove triethylamine through rectifying, it is synthetic that recovery is re-used in glyphosate, and remaining cut is used to prepare gyphosate solution.
5, the treatment process of glyphosate mother solution as claimed in claim 1 or 2 is characterized in that described alkali is one of following: sodium hydroxide or potassium hydroxide or calcium hydroxide or ammonia or Isopropylamine.
6, the treatment process of glyphosate mother solution as claimed in claim 5 is characterized in that described alkali is ammonia.
7, the treatment process of glyphosate mother solution as claimed in claim 1 is characterized in that described gyphosate solution is the ammonium glyphosate aqua.
8,, it is characterized in that described gyphosate solution is 10% gyphosate solution as the treatment process of the described glyphosate mother solution of one of claim 1～4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510049296 CN1304402C (en) | 2005-01-31 | 2005-01-31 | Process for treating cglyphosate mother liquor |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510049296 CN1304402C (en) | 2005-01-31 | 2005-01-31 | Process for treating cglyphosate mother liquor |
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| CN1657532A CN1657532A (en) | 2005-08-24 |
| CN1304402C true CN1304402C (en) | 2007-03-14 |
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Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1775786B (en) * | 2005-11-28 | 2011-01-19 | 杭州天创净水设备有限公司 | Method for separating and concentrating glyphosate stock solution |
| 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 |
| CN101058586B (en) * | 2007-04-06 | 2013-04-24 | 杭州天创环境科技股份有限公司 | Method of concentrating and separating glyphosate in high salt content glyphosate mother liquor by film technique |
| CN101195639B (en) * | 2007-08-02 | 2011-11-16 | 莫一平 | Method for processing mother solution of glyphosate |
| CN101570324B (en) * | 2009-06-16 | 2013-05-08 | 吴伦飞 | Method for recovering phosphite from glyphosate mother liquor |
| CN102127112B (en) * | 2010-01-19 | 2013-06-26 | 浙江新安化工集团股份有限公司 | Method for separating glyphosine solid from glyphosate mother liquor |
| CN101985426B (en) * | 2010-09-06 | 2013-07-03 | 山东潍坊润丰化工有限公司 | Method for treating glyphosate mother solution |
| CN102079757B (en) * | 2010-12-13 | 2013-03-27 | 四川省乐山市福华通达农药科技有限公司 | Process for extracting glyphosate from acid mother liquor |
| CN102874786A (en) * | 2012-10-12 | 2013-01-16 | 山东潍坊润丰化工有限公司 | Processing method of glyphosate mother liquor |
| 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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