CN101648969B - Preparation method of N-phosphonomethyliminodiacetic acid - Google Patents
Preparation method of N-phosphonomethyliminodiacetic acid Download PDFInfo
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- CN101648969B CN101648969B CN2009100350199A CN200910035019A CN101648969B CN 101648969 B CN101648969 B CN 101648969B CN 2009100350199 A CN2009100350199 A CN 2009100350199A CN 200910035019 A CN200910035019 A CN 200910035019A CN 101648969 B CN101648969 B CN 101648969B
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- pmida98
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- iminodiethanoic acid
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- iminodiethanoic
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Abstract
The invention discloses a preparation method of N-phosphonomethyliminodiacetic acid, and the method comprises the following steps: mixing iminodiacetic acid, acidic catalyst and water, then stirring, heating to more than 100 DEG C, then adding paraformaldehyde and adding phosphorous acid within 30-60min, keeping the temperature to perform a reaction for 2-7h to obtain the suspending liquid of N-phosphonomethyliminodiacetic acid and finally preparing N-phosphonomethyliminodiacetic acid by cooling, filtrating, washing and drying. The purity of the N-phosphonomethyliminodiacetic acid prepared by the method of the invention is more than 98% and the product yield is more than 94.5%.
Description
Technical field
The invention belongs to chemical field, be specifically related to a kind of preparation method of fine chemical product pmida98.
Background technology
Glyphosate 62 IPA Salt is output and the most salable organic phosphine weedicide in the world at present, characteristics such as it has efficiently, wide spectrum, low toxicity, safety.In recent years, because the large-scale promotion of the transgenic crop of resistance glyphosate, it is convenient to make it use, and the Glyphosate 62 IPA Salt market requirement increases rapidly, constantly substitutes the weedicide of other types, occupies the first place that world's agricultural chemicals is sold for years.Eighties of last century the seventies, it is the synthetic pmida98 of raw material that the U.S. develops with the iminodiethanoic acid, the technology of resynthesis Glyphosate 62 IPA Salt, this technology become ordinary method-iminodiethanoic acid (IDA) method of preparation Glyphosate 62 IPA Salt.
Patent CN 1916005A report utilizes the method for synthesizing N-phosphonomethyliminoacidetic acidetic (PMIDA) by iminodiacetonitrile, and this method needs control pressure to change, the operation relative complex, and the yield of pmida98 is not high simultaneously, has only about 90%.
Patent US 005688994A report utilizes the technology of iminodiacetic acid sodium salt for the synthetic pmida98 of raw material, and its technology can reduce this, but reaction back N-(phosphonomethyl) iminodiacetic acid wastewater is more, and actual recovery also has only about 91%.
Summary of the invention
The purpose of this invention is to provide a kind of method for preparing pmida98, this method is simple to operate, and obtains the pmida98 of higher yields.
The objective of the invention is to realize in the following manner:
Iminodiethanoic acid, an acidic catalyst and water mix at normal temperatures, carry out stirring heating then, stir and the condition of temperature >=100 ℃ under add Paraformaldehyde 96; In 30min-60min, add simultaneously phosphorous acid; Behind reinforced the finishing, insulation reaction 2-7 hour, the suspension-s of pmida98; Suspension-s makes pmida98 through cooling, filtration, washing and dry.
Iminodiethanoic acid of the present invention accounts for the 25%-30% of raw material gross weight.
The mol ratio of described an acidic catalyst and iminodiethanoic acid consumption between 1.1-1.7, preferred 1.3-1.5; The weight ratio of Total Water and iminodiethanoic acid is 0.95-1.7 in the system: 1, and preferred 1.2-1.4: 1.
The mol ratio of above-mentioned phosphorous acid and iminodiethanoic acid consumption between 1-1.5, preferred 1.1-1.3.The phosphorous acid solution mass percent concentration that the present invention adds is preferred 70%, drips the phosphorous acid solution time in the 30min-60min scope, preferably in 40min-50min, drips off.
Above-mentioned Paraformaldehyde 96 divides 2～10 addings, and preferably 4～6 times, the adding temperature of Paraformaldehyde 96 is 100～130 ℃, preferably 110～120 ℃.
The mol ratio of described Paraformaldehyde 96 and iminodiethanoic acid consumption is between the 1.1-1.5, preferred 1.2-1.4.
Behind reinforced the finishing, temperature of reaction is 100～130 ℃, preferably 110～120 ℃, and preferred 3～5 hours of insulation reaction time.
Above-mentioned an acidic catalyst is a kind of in phosphoric acid, sulfuric acid, the hydrochloric acid, preferably hydrochloric acid.
The iminodiethanoic acid that above-mentioned reaction is adopted is preferably with the iminodiethanoic acid of quality percentage composition >=95%.
Pmida98 filters and behind cool to room temperature, carries out in the aforesaid method, filters and adopts decompress filter, and whizzer dries again.
Preparation principle of the present invention is: under the strong acid catalytic condition, and iminodiethanoic acid and phosphorous acid, the synthetic pmida98 of formolite reaction.
The present invention is through under higher temperature, adding Paraformaldehyde 96, thereby obtains active very high formaldehyde molecule and iminodiacetic acid (salt) acid-respons, need not need hydrionic repeatedly attack activation as 37% formaldehyde, thereby improve the yield that reacts.
Beneficial effect of the present invention compared with prior art:
The inventive method is simple to operate, and the pmida98 purity that makes is greater than 98%, and product yield is more than 94.5%.
Embodiment
Through instance the present invention is described below, but the present invention is not limited to these embodiment.Among the embodiment, if no special instructions, be mass concentration.
Embodiment 1
With the 140g mass concentration is that 95% iminodiethanoic acid adds and is equipped with in the 1000ml four-hole boiling flask of TM, whisking appliance, prolong, adds the hydrochloric acid 129.5g of mass percent concentration 31% simultaneously, water 100g; Begin heating and stirring, be warming up to 100 ℃ and begin 2 addings of branch Paraformaldehyde 96 33g, in 30min, dripping mass percent concentration simultaneously is 70% phosphorous acid solution 117g; After treating that phosphorous acid dropwises; 100 ℃ of insulation reaction are 2 hours again, and stopped reaction is cooled to room temperature; Again successively through filtering, obtaining pmida98 wet-milling 241g, mother liquor 278g after with water washing; Through 100 ℃ of dry pmida98 dry powder 213.5g that get content 98.1%, pmida98 content is 1.87% in the mother liquor again, is that benchmark calculates pmida98 yield 94.6% with the iminodiethanoic acid.
Embodiment 2
With 140g content is that 95% iminodiethanoic acid adds and is equipped with in the 1000ml four-hole boiling flask of TM, whisking appliance, prolong, adds the hydrochloric acid 170g of mass percent concentration 31% simultaneously, and water 10g begins heating and stirs.Be warming up to 130 ℃ and begin branch 10 times and add Paraformaldehyde 96 45g, in 60min, drip mass percent concentration 70% phosphorous acid solution 176g simultaneously, treat that phosphorous acid dropwises after; 130 ℃ of insulation reaction 7 hours; Stopped reaction is cooled to room temperature, filters; With obtaining pmida98 wet-milling 241g, mother liquor 300g after the water washing; 100 ℃ of drying treatment of pmida98 wet-milling warp get the pmida98 dry powder 219.2g of content 98.2%, and pmida98 content is 1.51% in the mother liquor, are that benchmark calculates pmida98 yield 96.7% with the iminodiethanoic acid.
Embodiment 3
With 140g content is that 95% iminodiethanoic acid adds and is equipped with in the 1000ml four-hole boiling flask of TM, whisking appliance, prolong, adds the hydrochloric acid 150g of mass percent concentration 31% simultaneously, and water 50g begins heating and stirs.Be warming up to 110 ℃ and begin branch 6 times and add Paraformaldehyde 96 40g, in 40min, drip mass percent concentration 70% phosphorous acid solution 146g simultaneously, treat that phosphorous acid dropwises after; 120 ℃ of insulation reaction 4 hours; Stopped reaction is cooled to room temperature, filters; With obtaining pmida98 wet-milling 236g, mother liquor 290g after the water washing; 100 ℃ of drying treatment of pmida98 wet-milling warp get the pmida98 dry powder 216.6g of content 98.6%, and pmida98 content is 1.63% in the mother liquor, are that benchmark calculates pmida98 yield 96.1% with the iminodiethanoic acid.
Embodiment 4
With 140g content is that 95% iminodiethanoic acid adds and is equipped with in the 1000ml four-hole boiling flask of TM, whisking appliance, prolong, adds the hydrochloric acid 145g of mass percent concentration 31% simultaneously, and water 50g begins heating and stirs.Be warming up to 120 ℃ and begin branch 4 times and add Paraformaldehyde 96 42g, in 50min, drip mass percent concentration 70% phosphorous acid solution 151g simultaneously, treat that phosphorous acid dropwises after; 120 ℃ of insulation reaction 5 hours; Stopped reaction is cooled to room temperature, filters; With obtaining pmida98 wet-milling 234g, mother liquor 294g after the water washing; 100 ℃ of drying treatment of pmida98 wet-milling warp get the pmida98 dry powder 214.9g of content 98.4%, and pmida98 content is 1.55% in the mother liquor, are that benchmark calculates pmida98 yield 95.1% with the iminodiethanoic acid.
Embodiment 5
With 140g content is that 95% iminodiethanoic acid adds and is equipped with in the 1000ml four-hole boiling flask of TM, whisking appliance, prolong, adds the phosphatase 11 38g of mass percent concentration 85% simultaneously, and water 100g begins heating and stirs.Be warming up to 120 ℃ and begin branch 4 times and add Paraformaldehyde 96 41g, in 50min, drip mass percent concentration 70% phosphorous acid solution 152g simultaneously, treat that phosphorous acid dropwises after; 120 ℃ of insulation reaction 5 hours; Stopped reaction is cooled to room temperature, filters; Obtain pmida98 wet-milling 231g after the washing, mother liquor 340g; 100 ℃ of drying treatment of pmida98 wet-milling warp get the pmida98 dry powder 212.4g of content 98.4%, and pmida98 content is 1.74% in the mother liquor, are that benchmark calculates pmida98 yield 94.7% with the iminodiethanoic acid.
Embodiment 6
With 140g content is that 95% iminodiethanoic acid adds and is equipped with in the 1000ml four-hole boiling flask of TM, whisking appliance, prolong, adds the sulfuric acid 121g of mass percent concentration 98% simultaneously, and water 100g begins heating and stirs.Be warming up to 120 ℃ and begin branch 4 times and add Paraformaldehyde 96 40g, in 50min, drip mass percent concentration 70% phosphorous acid solution 152g simultaneously, treat that phosphorous acid dropwises after; 120 ℃ of insulation reaction 4 hours; Stopped reaction is cooled to room temperature, filters; With obtaining pmida98 wet-milling 236g, mother liquor 317g after the water washing; 100 ℃ of drying treatment of pmida98 wet-milling warp get the pmida98 dry powder 215.3g of content 98.2%, and pmida98 content is 1.61% in the mother liquor, are that benchmark calculates pmida98 yield 95.4% with the iminodiethanoic acid.
Claims (12)
1. method for preparing pmida98 is characterized in that this method may further comprise the steps:
Iminodiethanoic acid, an acidic catalyst and water are mixed, carry out stirring heating then, treat to add Paraformaldehyde 96 under 100～130 ℃ of conditions of temperature; In 30min-60min, add simultaneously phosphorous acid, behind reinforced the finishing, temperature is between 100 ℃-130 ℃; After insulation reaction 2-7 hour; Get the suspension-s of pmida98, suspension-s makes pmida98 through cooling, filtration, washing and dry; The mol ratio of described an acidic catalyst and iminodiethanoic acid consumption is between 1.1-1.7; The weight ratio of Total Water and iminodiethanoic acid is 0.95-1.7 in the system: 1.
2. the method for preparing pmida98 according to claim 1 is characterized in that described iminodiethanoic acid accounts for the 25%-30% of raw material gross weight.
3. the method for preparing pmida98 according to claim 1, the mol ratio that it is characterized in that described an acidic catalyst and iminodiethanoic acid consumption is between 1.3-1.5; The weight ratio of Total Water and iminodiethanoic acid is 1.2-1.4 in the system: 1.
4. method according to claim 1, the mol ratio that it is characterized in that described phosphorous acid and iminodiethanoic acid consumption is between 1-1.5.
5. method according to claim 4, the mol ratio that it is characterized in that described phosphorous acid and iminodiethanoic acid consumption is between 1-1.3.
6. method according to claim 1, the mol ratio that it is characterized in that described Paraformaldehyde 96 and iminodiethanoic acid consumption is between the 1.1-1.5.
7. method according to claim 6, the mol ratio that it is characterized in that described Paraformaldehyde 96 and iminodiethanoic acid consumption is 1.2-1.4.
8. the method for preparing pmida98 according to claim 1, the adding temperature that it is characterized in that described Paraformaldehyde 96 is 110～120 ℃; Paraformaldehyde 96 divides 2-10 to criticize and adds in the reactor drum.
9. the method for preparing pmida98 according to claim 8 is characterized in that described Paraformaldehyde 96 divides 4-6 time and adds in the reactor drum.
10. the method for preparing pmida98 according to claim 1, it is characterized in that reinforced finishing after, temperature of reaction is between 110 ℃-120 ℃, the insulation reaction time is 3-5 hour.
11. the method for preparing pmida98 according to claim 1 is characterized in that described an acidic catalyst is a kind of in phosphoric acid, sulfuric acid, the hydrochloric acid.
12. the method for preparing pmida98 according to claim 1 is characterized in that filtering and behind cool to room temperature, carries out, and filters and adopts decompress filter, dries with whizzer again.
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| CN2009100350199A CN101648969B (en) | 2009-09-14 | 2009-09-14 | Preparation method of N-phosphonomethyliminodiacetic acid |
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| CN101891764B (en) * | 2010-06-30 | 2011-11-30 | 湖北汇达科技发展有限公司 | Method for preparing N-phosphonomethyliminodiacetic acid |
| CN103539816B (en) * | 2013-09-24 | 2016-09-07 | 重庆紫光化工股份有限公司 | The production method of PMIDA |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1721422A (en) * | 2004-07-15 | 2006-01-18 | 四川贝尔实业有限责任公司 | Process for preparing PMIDA |
| CN101307074A (en) * | 2008-06-24 | 2008-11-19 | 山东潍坊润丰化工有限公司 | Process for preparing N-phosphonomethyliminodiacetic acid |
| CN101525350A (en) * | 2009-04-22 | 2009-09-09 | 北京颖泰嘉和科技股份有限公司 | Method for preparing N-(phosphonomethyl)iminodiacetic acid |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1721422A (en) * | 2004-07-15 | 2006-01-18 | 四川贝尔实业有限责任公司 | Process for preparing PMIDA |
| CN101307074A (en) * | 2008-06-24 | 2008-11-19 | 山东潍坊润丰化工有限公司 | Process for preparing N-phosphonomethyliminodiacetic acid |
| CN101525350A (en) * | 2009-04-22 | 2009-09-09 | 北京颖泰嘉和科技股份有限公司 | Method for preparing N-(phosphonomethyl)iminodiacetic acid |
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Owner name: ANHUI GUOXING BIOCHEMICAL CO., LTD. Free format text: FORMER OWNER: NANJING FIRST PESTICIDE GROUP CO., LTD. Effective date: 20110922 |
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Effective date of registration: 20110922 Address after: 243100 Dangtu Economic Development Zone in Anhui Applicant after: Anhui Guoxing Biochemistry Co., Ltd. Address before: 211300 Pagoda Road 269, Gaochun County, Jiangsu, Nanjing Applicant before: Nanjing First Pesticide Group Co., Ltd. |
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