CN102321119A - A kind of post-treating method with dichloride waste water acidifying ammonium glyphosate - Google Patents
A kind of post-treating method with dichloride waste water acidifying ammonium glyphosate Download PDFInfo
- Publication number
- CN102321119A CN102321119A CN201110188804A CN201110188804A CN102321119A CN 102321119 A CN102321119 A CN 102321119A CN 201110188804 A CN201110188804 A CN 201110188804A CN 201110188804 A CN201110188804 A CN 201110188804A CN 102321119 A CN102321119 A CN 102321119A
- Authority
- CN
- China
- Prior art keywords
- glyphosate
- waste water
- ipa salt
- acidifying
- dichloride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The invention discloses a kind of post-treating method with dichloride waste water acidifying ammonium glyphosate.The acid waste water that promptly adopts O-methyl thio-phosphoryl dichloride production process to produce replaces the vitriol oil to be used for the acidifying ammonium glyphosate, and crystallization obtains Glyphosate 62 IPA Salt.Adopt this method both to reduce the sulfuric acid consumption of glyphosate production process, reduced in the dichloro acid wastewater consumption with required alkali simultaneously, adopt Glyphosate 62 IPA Salt content that this method obtains greater than 96%, former powder yield is greater than 82%.This method can reduce the production cost of Glyphosate 62 IPA Salt and O-methyl thio-phosphoryl dichloride simultaneously.
Description
Technical field
The present invention relates to a kind of post-treating method with dichloride waste water acidifying ammonium glyphosate.
Background technology
Glyphosate 62 IPA Salt (PMG), formal name used at school N one ((phosphonomethyl)) glycocoll has 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 62 IPA Salt is to be raw material with the imido grpup diacetonitrile; Obtain pmida98 through alkaline hydrolysis, condensation; Pmida98 is that catalyzer obtains Glyphosate 62 IPA Salt through atmospheric oxidation with the gac, for catalyzer is separated from Glyphosate 62 IPA Salt, usually reaction product is fed ammonia after filter to isolate activated-carbon catalyst; Filtrating is ammonium glyphosate; Vitriol oil acidifying is adopted in the aftertreatment of ammonium glyphosate, obtains Glyphosate 62 IPA Salt after the crystallization, obtains product after the drying.
In the production process of sterilant acephate midbody O-methyl thio-phosphoryl dichloride; With phosphorus thiochloride and methyl alcohol is raw material; Production process water washing reaction product; 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 with waste water in HCl, be behind neutrality or the meta-alkalescence rectifying recovery methyl alcohol wherein again to waste water, remaining effluent brine is discharged into biochemistry pool and carries out WWT.
The conventional post-treating method of above-mentioned two processes, exist: the yield of Glyphosate 62 IPA Salt is low, and O-methyl thio-phosphoryl dichloride acid waste water is handled needs to consume a large amount of alkali, and production cost is high.
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 water washing reaction product; 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 through 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 62 IPA Salt crystallization under (preferred 0～20 ℃) condition; Filtering separation obtains Glyphosate 62 IPA Salt, 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 to go up high by about 5% with the Glyphosate 62 IPA Salt yield of vitriol oil acidifying gained through the yield of the resulting Glyphosate 62 IPA Salt of method of the present invention than industry.
The Glyphosate 62 IPA Salt suitability for industrialized production is used vitriol oil acidifying at present; And the washing acid waste water that produces in the production process of sterilant acephate midbody O-methyl thio-phosphoryl dichloride often needs a large amount of alkali neutralizations, and the wastewater treatment expense is high.
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 practiced thrift the required vitriol oil of ammonium glyphosate acidization; Practiced thrift 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 62 IPA Salt in water; Therefore, improve Glyphosate 62 IPA Salt crystalline yield, had tangible economic benefit.
Embodiment
Below in conjunction with embodiment the present invention is further specified, the invention is not restricted to embodiment, 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, and at room temperature, slowly adding concentration of hydrochloric acid is 10%; Methanol content is 20% O-methyl thio-phosphoryl dichloride washing acid waste water, and the pH of control souring soln is 2, is cooled to 20 ℃; Crystallization 3～4h, after the filtration, drying obtains the Glyphosate 62 IPA Salt crystal; The content of Glyphosate 62 IPA Salt is 97.89%, and in pmida98, the former powder yield of Glyphosate 62 IPA Salt is 86.74%.Filter the mother liquor behind the Glyphosate 62 IPA Salt, using the NaOH solution pH that continues to neutralize is 8～9, and neutralizer gets into methanol rectifying tower and reclaims methyl alcohol.
Embodiment 2
The 100g content that the pmida98 oxidation obtains is 40% ammonium glyphosate salts solution, and at room temperature, slowly adding concentration of hydrochloric acid is 15%; Methanol content is 25% O-methyl thio-phosphoryl dichloride washing acid waste water, and the pH of control souring soln is 1, is cooled to 0 ℃; Crystallization 4～5h, after the filtration, drying obtains the Glyphosate 62 IPA Salt crystal; The content of Glyphosate 62 IPA Salt is 96.58%, in pmida98, and the former powder yield 88.64% of Glyphosate 62 IPA Salt.Filter the mother liquor behind the Glyphosate 62 IPA Salt, using the gas ammonia pH that neutralizes is 9～10, then, gets into methanol rectifying tower and reclaims methyl alcohol.
Embodiment 3
The 100g content that the pmida98 oxidation obtains is 10% ammonium glyphosate salts solution, and at room temperature, slowly adding concentration of hydrochloric acid is 5%; Methanol content is 10% O-methyl thio-phosphoryl dichloride washing acid waste water, and the pH of control souring soln is 4, is cooled to 10 ℃; Crystallization 4～5h, after the filtration, drying obtains the Glyphosate 62 IPA Salt crystal; The content of Glyphosate 62 IPA Salt is 98.74%, in pmida98, and the former powder yield 82.64% of Glyphosate 62 IPA Salt.Filter the mother liquor behind the Glyphosate 62 IPA Salt, using the gas ammonia pH that neutralizes is 8～9, then, gets into 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 62 IPA Salt crystallization under 1～4,0～30 ℃ of condition during acidifying; Filtering separation obtains Glyphosate 62 IPA Salt, 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 62 IPA Salt Tc is 0～20 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110188804 CN102321119B (en) | 2011-07-07 | 2011-07-07 | Post treatment method for acidifying ammonium glyphosate by dichloride wastewater |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110188804 CN102321119B (en) | 2011-07-07 | 2011-07-07 | Post treatment method for acidifying ammonium glyphosate by dichloride wastewater |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102321119A true CN102321119A (en) | 2012-01-18 |
| CN102321119B CN102321119B (en) | 2013-07-31 |
Family
ID=45448976
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110188804 Expired - Fee Related CN102321119B (en) | 2011-07-07 | 2011-07-07 | Post treatment method for acidifying ammonium glyphosate by dichloride wastewater |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102321119B (en) |
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 |
-
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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102321119B (en) | 2013-07-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101525121B (en) | Method for analyzing chlorine hydride in hydrochloric acid | |
| CN101391848B (en) | Comprehensive treatment method of ammonia-containing waste water in production of metiram type products | |
| CN102795734A (en) | Process of treating glyphosate mother solution by catalytic air oxidation method | |
| CN110092396B (en) | Method and system for recycling waste sulfuric acid of graphene | |
| CN104944398B (en) | Glyphosate mother solution recoverying and utilizing method | |
| CN103408460B (en) | Method for recovering secondary iminodiacetonitrile product and method for treating mother liquor thereof | |
| CN103864040A (en) | Process for preparing disodium hydrogen phosphate from glyphosate mother liquor | |
| CN102079605A (en) | Novel process for zero discharge of glyphosate production waste water | |
| CN102745791A (en) | Method for treating industrial wastewater | |
| CN109607570A (en) | A kind of recycling treatment process of ammonium chloride abraum salt | |
| CN101357911B (en) | Method for synthesizing (z)-2-(alpha-methoxyimino)furan-ammonium acetate | |
| CN102633382A (en) | 4,6-dichloropyrimidine waste water treatment and resource recovery method | |
| CN105541906A (en) | Purification method for glufosinate-ammonium | |
| CN101619077B (en) | Method for preparing N-Phosphonomethyl iminodiacetic acid through hydrolyzing iminodiacetonitrile | |
| CN108569812B (en) | Treatment system and treatment method for wastewater containing low-concentration sulfuric acid | |
| CN102910775B (en) | Carbendazim production wastewater pretreatment method | |
| CN102115281A (en) | Method for pretreating wastewater generated in production of N-(Phosphonomethyl) iminodiaceticacid (PMIDA) | |
| CN101531352B (en) | Method for using phosphoric oxide to concentrate diluted phosphoric acid to prepare crystal polyphosphoric acid | |
| CN101591084B (en) | Method for treating glyphosate waste water and reducing the emission of carbon dioxide | |
| CN102757356A (en) | Splitting process of racemic para hydroxybenzene glycine | |
| CN109851096B (en) | Chemical treatment method of hydrolysis process wastewater in ethyl chloride production process capable of being recycled | |
| CN107792840A (en) | A kind of method that accessory substance ferrophosphorus using industrial yellow phosphorus production prepares ferric phosphate | |
| CN102321119B (en) | Post treatment method for acidifying ammonium glyphosate by dichloride wastewater | |
| CN103265443A (en) | Industrial production method of high-purity iminodiacetic acid | |
| CN102701286A (en) | Potassium ferrate disinfectant and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130731 Termination date: 20150707 |
|
| EXPY | Termination of patent right or utility model |