CN102321119B - Post treatment method for acidifying ammonium glyphosate by dichloride wastewater - Google Patents
Post treatment method for acidifying ammonium glyphosate by dichloride wastewater Download PDFInfo
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- CN102321119B CN102321119B CN 201110188804 CN201110188804A CN102321119B CN 102321119 B CN102321119 B CN 102321119B CN 201110188804 CN201110188804 CN 201110188804 CN 201110188804 A CN201110188804 A CN 201110188804A CN 102321119 B CN102321119 B CN 102321119B
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Abstract
The invention discloses a post treatment method for acidifying ammonium glyphosate by dichloride wastewater, i.e. the acidic wastewater generated in the O-methyl thiophosphoryl dichlone production process replaces concentrated sulfuric acid for acidifying the ammonium glyphosate, and glyphosate is obtained through crystallization. When the method is adopted, the sulfuric acid consumption in the glyphosate production process is reduced, simultaneously, the alkali consumption required by dichlone acidic wastewater neutralization is reduced, the content of the glyphosate required by the method is greater than 96 percent, and the raw powder yield is greater than 82 percent. The method has the advantage that the production cost of the glyphosate and the O-methyl thiophosphoryl dichlone can be simultaneously reduced.
Description
Technical field
The present invention relates to a kind of post-treating method with dichloride waste water acidifying ammonium glyphosate.
Background technology
Glyphosate (PMG); formal name used at school N one ((phosphonomethyl)) glycine; having another name called that glyphosate, farming reach, farming is prosperous, is a kind of efficient, low toxicity, low residue, wide spectrum, the environment amenable natural disposition inner sucting herbicide that goes out, and is the pesticide species of worldwide production amount and usage quantity maximum.At present an important production route of the industrialized preparing process of preparation glyphosate is to be raw material with the imido grpup diacetonitrile, obtain pmida98 through alkaline hydrolysis, condensation, pmida98 is that catalyzer obtains glyphosate through atmospheric oxidation with the gac, for catalyzer is separated from glyphosate, usually reaction product is fed ammonia after filter to isolate activated-carbon catalyst, filtrate is ammonium glyphosate, vitriol oil acidifying is adopted in the aftertreatment of ammonium glyphosate, obtain glyphosate after the crystallization, obtain product after the drying.
In the production process of sterilant acephate intermediate O-methyl thio-phosphoryl dichloride, with phosphorus thiochloride and methyl alcohol is raw material, production process washes reaction product with water, obtain the O-methyl thio-phosphoryl dichloride, it is 10%～25% that generation simultaneously contains the methanol quality mark in a large number, and the hydrochloric acid massfraction is the acid waste water of 5%-20%.
The ordinary method of handling at present O-methyl thio-phosphoryl dichloride acid waste water is: with among the 30%NaOH and the HCl in the waste water, be behind neutrality or the meta-alkalescence rectifying again to waste water and reclaim wherein methyl alcohol, remaining effluent brine is discharged into biochemistry pool and carries out sewage disposal.
The conventional post-treating method of above-mentioned two processes, exist: the yield of glyphosate is low, and O-methyl thio-phosphoryl dichloride acid waste water is handled needs to consume a large amount of alkali, production cost height.
Summary of the invention
The object of the present invention is to provide a kind of low cost, the method for the acid waste water that high efficiency comprehensive treating process ammonium glyphosate and O-methyl thio-phosphoryl dichloride production process produce.
The present invention carries out integrated innovation with the aftertreatment of the acid waste water that the aftertreatment of ammonium glyphosate and O-methyl thio-phosphoryl dichloride production process produce, reduce the raw material consumption of above-mentioned two processes, thereby reducing the production cost of above-mentioned two processes, is again utilization of waste material simultaneously, simple environmental protection.
The acid waste water that O-methyl thio-phosphoryl dichloride production process produces is to be raw material with phosphorus thiochloride and methyl alcohol, production process washes reaction product with water, obtain the O-methyl thio-phosphoryl dichloride, it is 10%～25% that generation simultaneously contains the methanol quality mark in a large number, and the hydrochloric acid massfraction is the acid waste water of 5%-20%.
The objective of the invention is to realize by following measure:
A kind of post-treating method of ammonium glyphosate, replace the vitriol oil to be used for the acidifying of ammonium glyphosate with the acid waste water in the O-methyl thio-phosphoryl dichloride production process, control pH value is 1～4 during acidifying, (preferred 1～2), 0～30 ℃, make the glyphosate crystallization under (preferred 0～20 ℃) condition; Filtering separation obtains glyphosate, and mother liquor adds NaOH or ammonia again, and further to be neutralized to the pH value be 8～10, reclaims methyl alcohol through methanol rectifying tower.
The hydrochloric acid massfraction is 5%～20% in the described acid waste water, and the methanol quality mark is 10%～25%.
The concentration of described ammonium glyphosate is 10%～40%.
Souring temperature is a normal temperature.
The hydrochloric acid waste water that the present invention adopts O-methyl thio-phosphoryl dichloride water washing process to produce replaces vitriol oil acidifying ammonium glyphosate, has greatly improved the utility value of resource.And what the contriver did not more reckon with is higher by about 5% than industrial glyphosate yield with vitriol oil acidifying gained by the yield of the resulting glyphosate of method of the present invention.
Glyphosate suitability for industrialized production vitriol oil acidifying at present; And the washing acid waste water that produces in the production process of sterilant acephate intermediate O-methyl thio-phosphoryl dichloride often needs a large amount of alkali neutralizations, wastewater treatment expense height.
The present invention carries out integrated innovation with above-mentioned two processes, has following advantage: adopt the washing hydrochloric acid waste water of O-methyl thio-phosphoryl dichloride to replace the used sulfuric acid of ammonium glyphosate acidifying, both saved the required vitriol oil of ammonium glyphosate acidization, saved the required most of alkali of O-methyl thio-phosphoryl dichloride waste water N-process again, the production cost of above-mentioned two processes is reduced significantly, simultaneously because O-methyl thio-phosphoryl dichloride washing hydrochloric acid waste water contains the methyl alcohol about 20%, because there is salting-out effect in methyl alcohol, reduced the solubleness of glyphosate in water, therefore, improve glyphosate crystalline yield, had tangible economic benefit.
Embodiment
The present invention will be further described below in conjunction with embodiment, the invention is not restricted to embodiment, and its embodiment can be described any mode of summary of the invention.
Embodiment 1
The 100g content that the pmida98 oxidation obtains is 20.3% ammonium glyphosate salts solution, at room temperature, slowly adding concentration of hydrochloric acid is 10%, and methanol content is 20% O-methyl thio-phosphoryl dichloride washing acid waste water, the pH of control souring soln is 2, be cooled to 20 ℃, crystallization 3～4h is after the filtration, drying obtains the glyphosate crystal, the content of glyphosate is 97.89%, and in pmida98, the former powder yield of glyphosate is 86.74%.Filtering the mother liquor behind the glyphosate, is 8～9 with the NaOH solution pH that continues to neutralize, and neutralizer enters methanol rectifying tower recovery methyl alcohol.
Embodiment 2
The 100g content that the pmida98 oxidation obtains is 40% ammonium glyphosate salts solution, at room temperature, slowly adding concentration of hydrochloric acid is 15%, and methanol content is 25% O-methyl thio-phosphoryl dichloride washing acid waste water, the pH of control souring soln is 1, be cooled to 0 ℃, crystallization 4～5h is after the filtration, drying obtains the glyphosate crystal, the content of glyphosate is 96.58%, in pmida98, and the former powder yield 88.64% of glyphosate.Filtering the mother liquor behind the glyphosate, is 9～10 with the gas ammonia pH that neutralizes, and then, enters methanol rectifying tower and reclaims methyl alcohol.
Embodiment 3
The 100g content that the pmida98 oxidation obtains is 10% ammonium glyphosate salts solution, at room temperature, slowly adding concentration of hydrochloric acid is 5%, and methanol content is 10% O-methyl thio-phosphoryl dichloride washing acid waste water, the pH of control souring soln is 4, be cooled to 10 ℃, crystallization 4～5h is after the filtration, drying obtains the glyphosate crystal, the content of glyphosate is 98.74%, in pmida98, and the former powder yield 82.64% of glyphosate.Filtering the mother liquor behind the glyphosate, is 8～9 with the gas ammonia pH that neutralizes, and then, enters methanol rectifying tower and reclaims methyl alcohol.
Claims (5)
1. post-treating method with dichloride waste water acidifying ammonium glyphosate is characterized in that:
Replace the vitriol oil to be used for the acidifying of ammonium glyphosate with the acid waste water in the O-methyl thio-phosphoryl dichloride production process, control pH value is to make the glyphosate crystallization under 1～4,0～30 ℃ of condition during acidifying; Filtering separation obtains glyphosate, and mother liquor adds NaOH or ammonia again, and further to be neutralized to the pH value be 8～10, reclaims methyl alcohol through methanol rectifying tower.
2. method according to claim 1 is characterized in that: the hydrochloric acid massfraction is 5%～20% in the described acid waste water, and the methanol quality mark is 10%～25%.
3. method according to claim 1 is characterized in that: the concentration of described ammonium glyphosate is 10%～40%.
4. method according to claim 1 is characterized in that: souring temperature is a normal temperature, and control pH value is 1～2 during acidifying.
5. method according to claim 1 is characterized in that: the glyphosate Tc is 0～20 ℃.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 201110188804 CN102321119B (en) | 2011-07-07 | 2011-07-07 | Post treatment method for acidifying ammonium glyphosate by dichloride wastewater |
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| Application Number | Priority Date | Filing Date | Title |
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| CN 201110188804 CN102321119B (en) | 2011-07-07 | 2011-07-07 | Post treatment method for acidifying ammonium glyphosate by dichloride wastewater |
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| CN102321119A CN102321119A (en) | 2012-01-18 |
| CN102321119B true CN102321119B (en) | 2013-07-31 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101088934A (en) * | 2007-06-21 | 2007-12-19 | 山东潍坊润丰化工有限公司 | Process of treating glyphosate producing effluent |
| CN101786735A (en) * | 2010-02-11 | 2010-07-28 | 浙江新安化工集团股份有限公司 | Film treatment method of glyphosate mother liquor |
| CN101843255A (en) * | 2010-05-28 | 2010-09-29 | 吴伦飞 | Deepen processing method of glyphosate mother liquid |
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2011
- 2011-07-07 CN CN 201110188804 patent/CN102321119B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101088934A (en) * | 2007-06-21 | 2007-12-19 | 山东潍坊润丰化工有限公司 | Process of treating glyphosate producing effluent |
| CN101786735A (en) * | 2010-02-11 | 2010-07-28 | 浙江新安化工集团股份有限公司 | Film treatment method of glyphosate mother liquor |
| CN101843255A (en) * | 2010-05-28 | 2010-09-29 | 吴伦飞 | Deepen processing method of glyphosate mother liquid |
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| CN102321119A (en) | 2012-01-18 |
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