CN101955431B - Recovery process of catalyst triethylamine in process of synthesizing glyphosate - Google Patents
Recovery process of catalyst triethylamine in process of synthesizing glyphosate Download PDFInfo
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- CN101955431B CN101955431B CN2009101007064A CN200910100706A CN101955431B CN 101955431 B CN101955431 B CN 101955431B CN 2009101007064 A CN2009101007064 A CN 2009101007064A CN 200910100706 A CN200910100706 A CN 200910100706A CN 101955431 B CN101955431 B CN 101955431B
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- triethylamine
- glyphosate
- calcium hydroxide
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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Abstract
The invention relates to a recovery process of a catalyst triethylamine in a process of synthesizing glyphosate. The recovery process comprises the following steps of: heating glyphosate mother liquor to 50-60 DEG C, adding calcium hydroxide powder until a pH value is 7-12, distilling triethylamine and removing moisture in the collected triethylamine by adopting a membrane separation method so that the recovered triethylamine reaches the requirement for catalytically producing the glyphosate; separating a residential solid mixture with a small amount of an aqueous solution after the triethylamine is distilled, and applying the aqueous solution to the next batch of calcium hydroxide for neutralization treatment, wherein the solid mixture can be used as a filling for producing magnesium oxychloride cement, PVC (polyvinyl chloride), resin, and the like.
Description
Technical field
The present invention relates to the recovery technology of the catalyst of triethylamine of glyphosate in synthetic.
Technical background
Can produce a large amount of acid mother liquids that contains glycine when adopting preparing glyphosate by glycin method, contain a large amount of catalyst of triethylamine of using when synthetic in this mother liquor, mainly be that the form with Triethylammonium chloride exists.The technology that reclaims triethylamine at present mainly is to add 30% liquid caustic soda in this acid mother liquid, regulate pH value 10-12, layering, the upper strata triethylamine reclaims to be reused, a small amount of triethylamine is told in lower floor's mother liquor rectifying, remainder is removed part sodium-chlor through concentrating, and concentrates the back mother liquor and is used for preparation 10% sodium glyphosate aqua.Too much can cause soil bad dispersibility, soil property viscous but 10% sodium glyphosate aqua uses, become soda soil, cause crop failure and quality to descend, therefore country will forbid the production of 10% sodium glyphosate aqua in 2010.Like this, just caused the sodium glyphosate mother liquor very difficult, because go back the method for the effective processing high density of none sodium salt waste water at present.
Chinese patent CN101293840A has introduced a kind of technology that reclaims triethylamine from the Triethylammonium chloride aqueous solution, mainly be that Powdered calcium oxide is added in the Triethylammonium chloride aqueous solution, steam triethylamine in 50-150 ℃, the triethylamine that collection steams is by adding the powder calcium oxide, reflux removes moisture, obtains water content less than 0.5% triethylamine.Bamboo is turbid water solution except what remain in reactor behind the triethylamine, divide and remove solids, obtained aqueous solution transfers to neutrality with hydrochloric acid, removes discriminable calcium chloride hexahydrate behind the moisture, Calcium dichloride dihydrate and Calcium Chloride Powder Anhydrous, and the calcium oxide after the dry triethylamine can be applied mechanically the generation triethylamine.This method is applied to the deficiency that reclaims triethylamine in glyphosate mother liquid to be, in the process that reclaims triethylamine in glyphosate mother liquid, because calcium oxide at first must absorb moisture content, could neutralize with acid, and contain the glyphosate mother solution complicated component of triethylamine, after being combined with phosphate radical, calcium ion generates calcium phosphate precipitation, and adsorb a large amount of organism, to coat less than the calcium oxide of dissolving soon, stop continuation dissolving and the reaction of calcium oxide, thereby can not improve the pH value of glyphosate mother solution, also just can't extract triethylamine.Among this external patent CN 101293840A, reclaim the remaining aqueous solution of separating solid substances behind the triethylamine, evaporation is removed moisture and is prepared the calcium chloride series product after the furnishing neutrality.Yet for glyphosate mother solution, still contain a large amount of organism in the liquid, can't prepare the calcium chloride series product by evaporation.
Summary of the invention
The invention discloses the recovery technology of the catalyst of triethylamine of a kind of glyphosate in synthetic: glyphosate mother solution is warming up to 50-60 ℃, the slurry that adds powder calcium hydroxide or calcium oxide arrives 7-12 until PH, steam triethylamine again, the triethylamine employing membrane separation process that collection obtains is removed moisture wherein, and the triethylamine that recovery is obtained reaches the requirement of applying mechanically the catalytic production glyphosate.Steam the solid mixture of the remaining entrained less water solution behind the triethylamine, separate, aqueous solution cover is used next batch calcium hydroxide and is carried out neutralizing treatment, and solid mixture can be used as the filler of producing magnesia oxychloride cement, PVC, resin etc.
The basic technology that glycine method is produced glyphosate comprises: the depolymerization under catalyst of triethylamine, solvent methanol of glycine, Paraformaldehyde 96 is finished, add the dimethylphosphite building-up reactions, add hydrochloric acid hydrolysis after finishing, obtain glyphosate wet-milling and mother liquor of the present invention.Mother liquor of the present invention, complicated component, pH value is about 1, contains glyphosate about 1.5% (1-3%), increases sweet phosphine, methyl glyphosate, aminomethyl phosphonic acid, dimethylphosphite, inorganic phosphate and synthetic intermediate etc., the COD value is more than 50,000, and TP2 is more than ten thousand.
Because mother liquor composition complexity of the present invention contains a large amount of phosphate radicals.If directly add the powder calcium oxide, calcium oxide needs earlier and big water gaging reaction could be better and acid-respons, and triethylamine is spun off from hydrochloric acid system, separates obtaining triethylamine then.After Powdered calcium oxide adds in the mother liquor of the present invention, surface oxidation calcium and water reaction generate calcium ion, calcium ion phosphate radical in mother liquor is combined and is generated calcium phosphate precipitation, adsorb organism a large amount of in the mother liquor simultaneously, there is not the calcium oxide of dissolving to wrap up nexine, stop the continuation dissolving and reaction of calcium oxide, do not reach the purpose of separating triethylamine.
The present invention is directed to these deficiencies, triethylamine in glyphosate mother liquor is reclaimed technology improve, at first is the slurry that utilizes Powdered calcium hydroxide or adopt calcium oxide, handles the glyphosate mother solution that is heated to about 50-60 ℃.Adopt the slurry of Powdered calcium hydroxide or calcium oxide, avoided powder calcium oxide and water underaction, can not get the defective of calcium ion and the acid-respons of greater amt, react faster, more thorough, the rate of recovery of triethylamine is higher.
Secondly, the triethylamine that steams is removed moisture content by the way of membrane sepn, and the water content that obtains triethylamine after the processing is less than 0.1% (w/w).
The solid mixture that steams the remaining entrained less water solution behind the triethylamine separates by press filtration or suction filtration, the aqueous solution cover that separates is used and is used for neutralizing treatment in next batch calcium hydroxide or the calcium oxide slurry, and solid mixture is as producing fillers such as magnesia oxychloride cement, PVC, resin.
With respect to the treatment process of present glyphosate catalyst of triethylamine, adopt solid hydrogen calcium oxide or calcium oxide slurry to substitute liquid caustic soda, significantly reduced the treatment capacity of mother liquor.In the old technology, one ton of glyphosate adopts 30% liquid caustic soda processing can produce alkali liquor about 5.5 tons, after reclaiming triethylamine, produce 1 ton of left and right sides solid sodium chloride salt, 1-1.5 the ton concentrated mother liquor is used for preparation 10% aqua, contain a large amount of sodium salts in this 10% aqua simultaneously, the soil is caused salinization, therefore country will completely forbid the production of 10% sodium salt aqua in 2010.And after adopting novel process of the present invention, 1 ton of glyphosate produces 3-3.5 ton acid mother liquor, after reclaiming triethylamine, produce 2 tons of calcium salts can the filler for the production of magnesia oxychloride cement, PVC, resin after, the aqueous solution that has only 0.4 ton of very small amount of less than can be applied mechanically the calcium hydroxide treating processes to the front.
Embodiment:
Embodiment 1
Be 99% Powdered calcium hydroxide and the water of 50kg with 220kg content, put in the glyphosphonic acid aqueous mother liquor that 1000kg contains triethylamine, steaming content at 70-100 ℃ is 95.5% triethylamine 218.95kg, namely reclaim triethylamine 209.10kg/ ton glyphosphonic acid mother liquor, the triethylamine that steams is purified with membrane separation process, purity reaches more than 99.5%, and water content is less than 0.1%.Adopt the glyphosate mother solution after the method for pumping filtration separation steams triethylamine, Gu slag is for the production of the filler of magnesia oxychloride cement, PVC, resin.
Embodiment 2:
With the glyphosate mother solution 110kg behind the embodiment 1 extraction triethylamine, with 220kg content be 99% Powdered calcium hydroxide, put in the glyphosphonic acid aqueous mother liquor that 1000kg contains triethylamine, steaming content at 70-100 ℃ is 96.1% triethylamine 221.03kg, namely reclaims triethylamine 212.41kg/ ton glyphosphonic acid mother liquor.The triethylamine that steams is purified with membrane separation process, and purity reaches more than 99.8%, and water content is less than 0.1%.Adopt method of pumping filtration to separate to steam the glyphosate mother solution behind the triethylamine, Gu slag for the production of the filler of magnesia oxychloride cement, PVC, resin, filtrate is applied mechanically to next batch and is handled.
Embodiment 3
To form slurry in the 170kg calcium oxide adding 60kg water, put in the glyphosphonic acid aqueous mother liquor that 1000kg contains triethylamine, steaming content at 70-100 ℃ is 95.5% triethylamine 215.56kg, namely reclaim triethylamine 205.86kg/ ton glyphosphonic acid mother liquor, the triethylamine that steams is purified with membrane separation process, purity reaches more than 99.5%, and water content is less than 0.1%.Adopt the glyphosate mother solution after the method for pumping filtration separation steams triethylamine, Gu slag is for the production of the filler of magnesia oxychloride cement, PVC, resin.
Comparative Examples 1
30% liquid caustic soda of 545kg is put in the glyphosphonic acid aqueous mother liquor that 1000kg contains triethylamine, and steaming content at 70-100 ℃ is 93% triethylamine 215.2kg, namely reclaims triethylamine 200.14kg.
Comparative Examples 2
Be that 99% Powdered calcium oxide stirs and puts into down in the glyphosphonic acid aqueous mother liquor that 1000kg contains triethylamine with 220kg content, steaming content at 50-150 ℃ is 88.5% triethylamine 201.95kg, namely reclaim triethylamine 178.73kg/ ton glyphosphonic acid mother liquor, the triethylamine adding purity that steams is 90% Powdered calcium oxide 185kg, water content is 0.56%, remaining then can't separate, and is the pulpous state coagulum.
Claims (2)
1. the recovery technology of the catalyst of triethylamine during a glyphosate synthesizes, it may further comprise the steps: glyphosate mother solution is warming up to 50-60 ℃, the slurry that adds powder calcium hydroxide or calcium oxide arrives 7-12 until pH, steam triethylamine again, the triethylamine employing membrane separation process that collection obtains is removed moisture wherein, and the triethylamine that recovery is obtained reaches the requirement of applying mechanically the catalytic production glyphosate.
2. according to the technology of claim 1, it comprises that further the solid mixture that will steam the remaining entrained less water solution behind the triethylamine separates, the aqueous solution that separates joins in the calcium hydroxide of next batch and is used for neutralizing treatment, and solid mixture is as the filler of producing magnesia oxychloride cement, PVC, resin.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2009101007064A CN101955431B (en) | 2009-07-17 | 2009-07-17 | Recovery process of catalyst triethylamine in process of synthesizing glyphosate |
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| Application Number | Priority Date | Filing Date | Title |
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| CN2009101007064A CN101955431B (en) | 2009-07-17 | 2009-07-17 | Recovery process of catalyst triethylamine in process of synthesizing glyphosate |
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| CN101955431A CN101955431A (en) | 2011-01-26 |
| CN101955431B true CN101955431B (en) | 2013-08-21 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| CN112094195B (en) * | 2020-04-15 | 2023-04-07 | 王闻伟 | Separation method of volatile organic alkali |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1648131A (en) * | 2004-12-23 | 2005-08-03 | 浙江新安化工集团股份有限公司 | Process for treating glyphosate mother liquid |
| CN1657531A (en) * | 2005-02-05 | 2005-08-24 | 杭州金帆达化工有限公司 | Process for treating production mother liquor of glyphosate |
| CN101293840A (en) * | 2008-04-11 | 2008-10-29 | 兖州市天成化工有限公司 | Process for recovering triethylamine from aqueous solution of triethylamine hydrochloride |
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- 2009-07-17 CN CN2009101007064A patent/CN101955431B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1648131A (en) * | 2004-12-23 | 2005-08-03 | 浙江新安化工集团股份有限公司 | Process for treating glyphosate mother liquid |
| CN1657531A (en) * | 2005-02-05 | 2005-08-24 | 杭州金帆达化工有限公司 | Process for treating production mother liquor of glyphosate |
| CN101293840A (en) * | 2008-04-11 | 2008-10-29 | 兖州市天成化工有限公司 | Process for recovering triethylamine from aqueous solution of triethylamine hydrochloride |
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| CN101955431A (en) | 2011-01-26 |
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