CN100417609C - Process for treating wastewater from preparation of N-(phosphonomethyl) iminodiacetic acid as synthetic intermediate of glyphosate - Google Patents
Process for treating wastewater from preparation of N-(phosphonomethyl) iminodiacetic acid as synthetic intermediate of glyphosate Download PDFInfo
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- CN100417609C CN100417609C CNB2005100600209A CN200510060020A CN100417609C CN 100417609 C CN100417609 C CN 100417609C CN B2005100600209 A CNB2005100600209 A CN B2005100600209A CN 200510060020 A CN200510060020 A CN 200510060020A CN 100417609 C CN100417609 C CN 100417609C
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- ammonium chloride
- pmida
- pmida98
- sodium bicarbonate
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Abstract
The present invention relates to a new method for treating wastewater in the process of preparing PMIDA as a synthetic intermediate body of glyphosate. In the process of preparing PMIDA, certain amounts of ammonium bicarbonate are added to residual filter liquid or concentrated filter liquid after PMIDA crystals are filtered and removed; sodium bicarbonate and filter liquid containing ammonium chloride are obtained through full reaction and filtration. The sodium bicarbonate can be used for recycling the preparation of the PMIDA, and the filter liquid is concentrated so as to obtain ammonium chloride by-products. The method can economically treat large amounts of acidic wastewater containing sodium chloride, which is generated in the process of preparing the PMIDA in a simple and practical mode, and the environment is protected.
Description
Technical field
The present invention relates to the method for wastewater treatment in the glyphosate synthetic intermediate pmida98 preparation process.
Background technology
The glyphosate chemical name is N-(phosphonomethyl) glycine (PMG), and molecular formula is:
It is a kind of steriland herbicide of wide spectrum efficiently, because of it has good interior suction conductive performance, very effective to the control of multiple dark root malignant weed, sales volume progressively increases in recent years, along with the popularization gradually of glyphosate tolerant acid genetically modified crops, its range of application further enlarges.Now become the maximum and the fastest weedicide of rate of growth of sales volume in the world.Now industrialized glyphosphonic acid production technique mainly contains two, and one what be that U.S. Monsanto Company adopts is the IDA route of starting raw material with prussic acid or diethanolamine; What another was that China generally adopts is the dialkyl phosphite route of starting raw material with the glycine.
N-phosphonomethyliminoacidetic acidetic (abbreviation pmida98) is the intermediate that the IDA legal system is equipped with glyphosate, and molecular structural formula is:
The existing technology of the intermediate pmida98 of preparation glyphosate is: produce Iminodiacetic acid sodium salt salt by the catalytic dehydrogenation in aqueous sodium hydroxide solution of diethanolamine, catalyzer, add then and react two sweet the seeing of generation with phosphorous acid, formaldehyde under acidic conditions after hydrochloric acid returns acid.The inevitable waste water that produces a large amount of acid sodium chloride-containing of this technology is handled comparatively difficulty of this kind waste water.
Summary of the invention
Purpose of the present invention just provides a kind of production technique of pmida98, can handle above-mentioned a large amount of acid sodium chloride-containing waste water with very economical, simple method, the protection environment.
Technical scheme of the present invention is: earlier sodium hydroxide, water, diethanolamine and catalyzer are joined in the reactor, feed nitrogen removing the air in the still in reactor, keep certain pressure to check the stopping property of reactor after the logical nitrogen deacration three times.Shed reactor pressure, stir and intensification.Along with pressure in the rising reactor of temperature of reaction also along with rising.When reaction pressure reaches 11 kilograms, begin to exit to pressure be 9 kilograms.After this, periodic blow down is to keep-up pressure between 9 kilograms ~ 11 kilograms.Think that reaction reaches terminal point when reaction pressure rises to time of 11 kilograms from 9 kilograms when reaching 30 minutes, stop to stir and cooling.When temperature drops to below 100 ℃, take out the upper strata reaction solution, adding hydrochloric acid adjustment pH value is about 7, adds the solution that the small amount of activated decolouring obtains iminodiethanoic acid one sodium salt again.
The reactor that iminodiethanoic acid one sodium salt, hydrochloric acid, water is added the band condenser, add phosphorous acid again, stir, heat up, control reaction temperature is at 80-100 ℃, again under refluxad (95-110 ℃) slowly adds formaldehyde, finishes back insulation 0.5-2 hour, crystallisation by cooling, filter filtrate collection; The crystal oven dry obtains the pmida98 product.
Filtrate or concentrate after filtrate in feed a certain amount of ammonium hydrogencarbonate, stir the back and produce white precipitate, filter the filtrate that obtains sodium bicarbonate crystal and contain ammonium chloride.
Sodium bicarbonate crystal can be used as the raw material of the first step dehydrogenation, and replace sodium hydroxide recycles, and reduces the consumption of alkali; The concentrating filter liquor that contains ammonium chloride can get the ammonium chloride by-product.
Characteristics of the present invention are that also the bicarbonate of ammonia that adds can be with logical ammonia, carbonic acid gas replace successively.Behind logical successively ammonia, the carbon dioxide, throw out (sodium bicarbonate) is removed in fully reaction in filtrate or the concentrated filtrate, and sodium bicarbonate reclaims the raw material as the first step dehydrogenation, recycles; Filtrate is rich in ammonium chloride, through concentrating, gets the ammonium chloride by-product, and the waste water that contains ammonium chloride is done the nitrogenous fertilizer sale.
The present invention adopts price lower sodium bicarbonate, carbonic acid gas and ammonia or ammonium hydrogencarbonate relatively, as reaction raw materials system pmida98, and can solve the waste water of a large amount of acid sodium chloride-containing that produces in the existing pmida98 synthetic technology, obtain containing the waste water of ammonium chloride, obtain the ammonium chloride by-product after concentrating, waste water after concentrating can be made nitrogenous fertilizer and sell, its economy is obviously better than traditional technology, and, and has good benefits in environment because it has consumed the by product that produces in the other products production process.
Embodiment
Below adopting sodium bicarbonate, carbonic acid gas and ammonia or ammonium hydrogencarbonate, is that example specifies embodiments of the present invention as reaction raw materials system pmida98, is limitation of the present invention but should not be construed as.
Embodiment 1: 85g sodium hydroxide and 239g distilled water, 100g diethanolamine, 82.5g catalyzer are joined in the reactor, feed nitrogen removing the air in the still in reactor, keep certain pressure to check the stopping property of reactor after the logical nitrogen deacration three times.Shed reactor pressure, stir and intensification.Along with pressure in the rising reactor of temperature of reaction also along with rising.When reaction pressure reaches 11 kilograms, begin to exit to pressure be 9 kilograms.After this, periodic blow down to be keep-uping pressure between 9 kilograms ~ 11 kilograms, thinks that reaction reaches terminal point when reaction pressure rises to time of 11 kilograms from 9 kilograms when reaching 30 minutes, stops to stir and cooling.When temperature drops to below 100 ℃, take out the upper strata reaction solution, adding hydrochloric acid adjustment pH value is about 7, adds the solution that the small amount of activated decolouring obtains iminodiethanoic acid one sodium salt again.Analyze iminodiacetic acid (salt) acid content and calculated yield in iminodiethanoic acid one sodium salt solution.
Iminodiethanoic acid one sodium salt solution is placed the four-hole boiling flask that thermometer, agitator, prolong are housed.Stir, add hydrochloric acid and the 83.5g phosphorous acid of 172.0g 36% more respectively, be warming up to 80-90 ℃, be incubated the formaldehyde that adds 85.0g 36% after 20-30 minute, reacted 2-10 hour, be cooled to room temperature at 90-100 ℃, filter the 192.6g wet-milling, mother liquor 532.9g.Getting 173.3g content after the wet-milling drying is 98.6% pmida98 dry powder.Filtrate feeds ammonia to alkalescence, adds ammonium hydrogencarbonate 183.5g, stirs, filters, and obtains the 152g sodium bicarbonate.Filtrate decompression concentrates, and obtains 102.5g ammonium chloride.
Embodiment 2: get the sodium bicarbonate 152g that embodiment 1 obtains and add the 26.5g sodium bicarbonate, join in the reactor with 239g distilled water, 100g diethanolamine, 82.5g catalyzer, in reactor, feed nitrogen removing the air in the still, keep certain pressure to check the stopping property of reactor after the logical nitrogen deacration three times.Shed reactor pressure, stir and intensification.Along with pressure in the rising reactor of temperature of reaction also along with rising.When reaction pressure reaches 11 kilograms, begin to exit to pressure be 9 kilograms.After this, periodic blow down to be keep-uping pressure between 9 kilograms ~ 11 kilograms, thinks that reaction reaches terminal point when reaction pressure rises to time of 11 kilograms from 9 kilograms when reaching 30 minutes, stops to stir and cooling.When temperature drops to below 100 ℃, take out the upper strata reaction solution, adding hydrochloric acid adjustment pH value is about 7, adds the solution that the small amount of activated decolouring obtains iminodiethanoic acid one sodium salt again.Analyze iminodiacetic acid (salt) acid content and calculated yield in iminodiethanoic acid one sodium salt solution.
Iminodiethanoic acid one sodium salt solution is placed the four-hole boiling flask that thermometer, agitator, prolong are housed.Stir, add hydrochloric acid and the 83.5g phosphorous acid of 172.0g 36% more respectively, be warming up to 80-90 ℃, be incubated the formaldehyde that adds 85.0g 36% after 20-30 minute,, be cooled to room temperature, get wet-milling 189.8g, mother liquor 546.2g 90-100 ℃ of reaction 2-10 hour.Get dry powder 171.9g after the oven dry, pmida98 content is 98.3%.Mother liquor is evaporated to 225g, and cooling, crystallization get sodium-chlor 37.3g, feeds ammonia and carbonic acid gas, stirs, filters, and obtains the 99.6g sodium bicarbonate.But the filtrate reconcentration obtains the ammonium chloride by-product, and the waste water after concentrating can be made nitrogenous fertilizer and sell.
Claims (4)
1. the technology of wastewater treatment in the glyphosate synthetic intermediate pmida98 preparation process is characterized in that: after removing the pmida98 crystal, add bicarbonate of ammonia toward remaining filtrate or concentrated rear filtrate in, fully react, filtration; Sodium bicarbonate crystal precipitation and contain the filtrate of ammonium chloride.
2. waste water treatment process as claimed in claim 1 is characterized in that the recovery of by-product sodium bicarbonate is reused for pmida98 and prepares in the catalytic dehydrogenation processes.
3. waste water treatment process as claimed in claim 1 is characterized in that the concentrating filter liquor that contains ammonium chloride gets the ammonium chloride by-product, contains ammonium chloride waste-water and sells as nitrogenous fertilizer.
4. waste water treatment process as claimed in claim 1, described bicarbonate of ammonia are to replace to feed ammonia and carbonic acid gas.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100600209A CN100417609C (en) | 2005-03-24 | 2005-03-24 | Process for treating wastewater from preparation of N-(phosphonomethyl) iminodiacetic acid as synthetic intermediate of glyphosate |
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|---|---|---|---|
| CNB2005100600209A CN100417609C (en) | 2005-03-24 | 2005-03-24 | Process for treating wastewater from preparation of N-(phosphonomethyl) iminodiacetic acid as synthetic intermediate of glyphosate |
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| CN1837105A CN1837105A (en) | 2006-09-27 |
| CN100417609C true CN100417609C (en) | 2008-09-10 |
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| CN101838067B (en) * | 2010-04-07 | 2011-10-19 | 中国科学院南京土壤研究所 | Method for treating high-concentration sodium chloride in N-(Phosphonomethyl)iminodiacetic acid waste water |
| CN103880879A (en) * | 2014-04-08 | 2014-06-25 | 广西金穗农药有限公司 | Preparation method of glyphosate isopropylamine salt aqueous solution |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5606107A (en) * | 1995-06-07 | 1997-02-25 | Monsanto Company | Formic acid and formaldehyde destruction in waste streams |
| US20020148786A1 (en) * | 2001-04-13 | 2002-10-17 | Phillips Scott G. | Removal and recovery of chloride from phosphonomethyliminodiacetic acid process brine |
| CN1422275A (en) * | 2000-04-14 | 2003-06-04 | 美国陶氏益农公司 | Removal of chloride from phosphonomethyliminodiacetic acid process |
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2005
- 2005-03-24 CN CNB2005100600209A patent/CN100417609C/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5606107A (en) * | 1995-06-07 | 1997-02-25 | Monsanto Company | Formic acid and formaldehyde destruction in waste streams |
| CN1422275A (en) * | 2000-04-14 | 2003-06-04 | 美国陶氏益农公司 | Removal of chloride from phosphonomethyliminodiacetic acid process |
| US20020148786A1 (en) * | 2001-04-13 | 2002-10-17 | Phillips Scott G. | Removal and recovery of chloride from phosphonomethyliminodiacetic acid process brine |
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