CN101525350B - Method for preparing N-(phosphonomethyl)iminodiacetic acid - Google Patents
Method for preparing N-(phosphonomethyl)iminodiacetic acid Download PDFInfo
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- CN101525350B CN101525350B CN2009100828942A CN200910082894A CN101525350B CN 101525350 B CN101525350 B CN 101525350B CN 2009100828942 A CN2009100828942 A CN 2009100828942A CN 200910082894 A CN200910082894 A CN 200910082894A CN 101525350 B CN101525350 B CN 101525350B
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Abstract
The invention relates to a novel economical energy-saving method for preparing, N-(phosphonomethyl)iminodiacetic acid. The method comprises the steps as follows: 1. phosphorus trichloride is hydrolyzed in nitrogen-passed environment, thereby generating phosphorous acid and chlorine hydride gases; 2. the chlorine hydride gas of step 1 is infused into iminodiacetic acid disodium salt solution of 43%-53%, so as to acidulate the solution directly to keep hydrion concentration of the acidulated solution higher than 4mol/L, thereby fully acidulating the iminodiacetic acid disodium salt into iminodiacetic acid hydrochlorid; 3. the phosphorous acid obtained in step 1 and formaldehyde are added into the acidulated solution of step 2 to carry out condensation reaction, thereby preparing N-(phosphonomethyl)iminodiacetic acid. The method has simple route, few energy consumption and device investment, convenient operation, high product yield and purity, and obvious economic benefits.
Description
Technical field
The invention belongs to the field of chemical synthesis, specifically, relate to a kind of novel method for preparing the economical and energy saving of pmida98.
Background technology
Pmida98 is the important intermediate of producing herbicide glyphosate (PMG).Glyphosate 62 IPA Salt is a kind of high-efficiency broad spectrum steriland herbicide; Because it is efficient, wide spectrum, low toxicity and noresidue; Have good performances such as interior suction conduction, very effective to the control of multiple dark root malignant weed, its range of application constantly enlarges; The market requirement increases rapidly, is the new variety agricultural chemicals of current national encourage growth.
Pmida98 carries out condensation reaction through iminodiethanoic acid, phosphorous acid and formaldehyde and obtains; Raw material according to the preparation iminodiethanoic acid is different, and the pmida98 production technique mainly contains technologies such as Mono Chloro Acetic Acid, prussic acid and diethylamine, all need pass through to separate like the iminodiethanoic acid of these several kinds of explained hereafter or its salt and purify; It is longer to exist operational path; Defectives such as transformation efficiency is low, and energy consumption and facility investment are bigger, and the three wastes are hard to manage.And be that the technology side reaction of feedstock production pmida98 is few with the NSC 263496, flow process is comparatively brief, and facility investment is few, and the yield and the purity of product are higher.
Operational path with iminodiacetic acid (salt) sodium salt production pmida98 mainly contains following two kinds at present:
1,, among the CN1132838C, directly phosphorus trichloride is joined hydrolysis in the solution of Iminodiacetic acid sodium salt salt like CN100400543C.Water reaction in phosphorus trichloride and the imino-diacetic sodium salt solution generates phosphorous acid and hydrogenchloride, and the latter carries out neutralization reaction with the imino-diacetic sodium salt, obtains the hydrochloride of iminodiethanoic acid, generates pmida98 with phosphorous acid and formaldehyde generation condensation reaction again.This technology operation easier in big production is bigger; Because a large amount of heat is emitted in these two reactions; The vaporization temperature of phosphorus trichloride is 75.5 ℃, so the hydrolysis of phosphorus trichloride has and very most of in gas phase, carry out, and temperature probably rises to 200 ℃ if the rate of addition of phosphorus trichloride is too fast; Cause the decomposition of phosphorous acid, generate phosphoric acid and phosphuret-(t)ed hydrogen.
2, like CN101284847A; Among US3288846A and the US4724103A, with strong acid Iminodiacetic acid sodium salt hydrochloric acid is turned to iminodiethanoic acid earlier, after concentrating; Add the phosphorous acid that the phosphorus trichloride hydrolysis prepares, add the formaldehyde back flow reaction again and obtain pmida98.Used strong acid mainly is that the absorption liquid of the hydrogenchloride (HCl) that produced by the phosphorus trichloride hydrolysis concentrates or directly adopt hydrochloric acid and sulfuric acid etc.; The concentration of the phosphorous acid that the phosphorus trichloride hydrolysis is prepared is lower; Water is excessive a lot, and the solubleness of HCl is very big, and the HCl that releases is not enough to direct utilization; Thereby adopt this arts demand to relate to recovery and the aftertreatment that produces HCl gas, and prepared phosphorous acid is concentrated; After the imido oxalic acid disodium salt acidifying simultaneously, need evaporate a part of water for the concentration that improves iminodiethanoic acid in the solution, this all needs very big energy consumption, is the big active demand of producing of industry so under the prerequisite of feasibility, transform this technology.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of energy-efficient, pmida98 that technology is simple, easy to operate.
The preparation method of pmida98 provided by the invention, it comprises the steps:
1, phosphorus trichloride generates phosphorous acid and hydrogen chloride gas feeding hydrolysis under the nitrogen environment;
2, in the Iminodiacetic acid sodium salt salts solution of mass percentage concentration 43%-53%, feed the direct acidifying of hydrogen chloride gas of step 1; Make the Sorensen value of solution after the acidifying more than 4mol/L, the abundant acidifying of Iminodiacetic acid sodium salt salt is become the Iminodiacetate hydrochlorate;
3, in the solution after step 2 acidifying, add the phosphorous acid that step 1 makes, and formaldehyde or Paraformaldehyde 96 carry out condensation reaction, make pmida98.
Wherein, in the step 1, according to the mol ratio of Iminodiacetic acid sodium salt salt and phosphorus trichloride 1: 0.9-2.5, preferred 1: the mol ratio of 1.15-1.4 adds phosphorus trichloride.The mass percentage concentration of the phosphorous acid of step 1 preparation is 50%-90%, preferred 60%-80%.
Iminodiacetic acid sodium salt salt can directly use the Iminodiacetic acid sodium salt salt solid of commercially available acquisition or the mixture of Iminodiacetic acid sodium salt salt and iminodiethanoic acid; Also can come the synthesis of iminodiacetic acid disodium salt through chemical process; Obtain as NSC 263496 being carried out alkaline hydrolysis, perhaps make by diethylolamine and sodium hydroxide dehydrogenation under the condition of high temperature, catalyzer with sodium hydroxide.
In the step 2, controlled temperature is under 20 ℃-120 ℃, with 2.2 * 10
-4m
3/ s-1.1 * 10
-3m
3/ s, preferred 5.5 * 10
-4m
3The speed of/s feeds hydrogen chloride gas 1h-5h, preferred 1h-3h.
In the step 2; Before feeding the hydrogenchloride acidifying or after the acidifying; According to hydrochloric acid and Iminodiacetic acid sodium salt salt 0.1-1.5: 1; Preferred 0.3-1: it is 30%-36.5% that 1 mol ratio adds mass percentage concentration, and preferred 36.5% hydrochloric acid makes the Sorensen value of solution after the acidifying more than 4mol/L.
The concentration of formaldehyde described in the step 3 is 10%-40%, preferred 37%-40%, and it is according to formaldehyde or Paraformaldehyde 96 and Iminodiacetic acid sodium salt salt 1: 0.8-2, and preferred 1: the consumption of 1.2-1.5 mol ratio adds.
The preparation method of pmida98 provided by the invention has shortened the process step that traditional iminodiacetic acid (salt) sodium salt prepares pmida98, has reduced raw material consumption and energy consumption, has practiced thrift the time, has saved facility investment, has more remarkable economic efficiency.
Embodiment
Following examples further specify content of the present invention, but should not be construed as limitation of the present invention.
Embodiment 1
Take by weighing the 150g phosphorus trichloride and join in the 89mL water, it is 75% phosphorous acid 119.273g and hydrogen chloride gas that hydrolysis makes concentration.
In the Iminodiacetic acid sodium salt salts solution of 329.7g massfraction 48.27%, add 70g 36.5% hydrochloric acid, under 80 ℃ with 5.5 * 10
-4m
3The speed of/s feeds the hydrogen chloride gas 2h that above-mentioned reaction makes; When Sorensen value was greater than 4mol/L in the detection reaction solution, the complete acidifying of Iminodiacetic acid sodium salt salt was the imido oxalic acid hydrochloride.
After treating that the phosphorus trichloride hydrolysis finishes, disposable prepared phosphorous acid is all joined in the solution after the acidifying, be warming up to backflow after; Slowly drip the formaldehyde solution of 105g 37%, the dropping time must not be less than 1 hour, stirring and refluxing reaction 5 hours; With 20% sodium hydroxide transfer that alkali to pH value equals 0.8, crystallisation by cooling, filtration; With obtaining the wet article 205g of pmida98 after the 150mL water washing, to dry to such an extent that content is 99.05% pmida98 dry product 185g, yield is 90.31%.
Embodiment 2
Take by weighing the 142g phosphorus trichloride and join in the 112.5mL water, hydrolysis makes the phosphorous acid 141.45g and the hydrogen chloride gas of concentration 60%.
The Iminodiacetic acid sodium salt salts solution of getting 370.47g massfraction 43% joins in the reaction vessel, and the speed with 5.5 * 10-4m3/s under 40 ℃ feeds the hydrogen chloride gas 3h that above-mentioned reaction makes, and adds the hydrochloric acid of 27g 36.5% again; When Sorensen value was greater than 4mol/L in the detection reaction solution, the complete acidifying of Iminodiacetic acid sodium salt salt was the imido oxalic acid hydrochloride.
After treating that the phosphorus trichloride hydrolysis finishes, disposable prepared phosphorous acid is joined in the reactor drum, be warming up to backflow after; Slowly drip the formaldehyde solution of 109.46g 37%, the dropping time must not be less than 1 hour, stirring and refluxing reaction 5 hours; Strong sodium hydroxide solution with 20% transfers that alkali to pH value equals 0.8, crystallisation by cooling, filtration; With obtaining the wet article 210.94g of pmida98 after the 150mL water washing, to dry to such an extent that content is 99.27% dry product 176.35g, yield is 85.69%.
Embodiment 3
Take by weighing the 142g phosphorus trichloride and join in the 77.12mL water, it is 80% phosphorous acid 106.09g and hydrogen chloride gas that hydrolysis makes concentration.
In the Iminodiacetic acid sodium salt salts solution of 370.47g massfraction 43%, add 36.5% hydrochloric acid 90g, under 80 ℃ with 4.4 * 10
-4m
3The speed of/s feeds the hydrogen chloride gas 2.5h that above-mentioned reaction makes; When Sorensen value was greater than 4mol/L in the detection reaction solution, the complete acidifying of Iminodiacetic acid sodium salt salt was the imido oxalic acid hydrochloride.
After treating that the phosphorus trichloride hydrolysis finishes, disposable prepared phosphorous acid is joined in the reactor drum, be warming up to the back of refluxing after; Slowly drip the formaldehyde solution of 109.46g 37%, the dropping time must not be less than 1 hour, stirring and refluxing reaction 4 hours; With 20% sodium hydroxide solution transfer that alkali to pH value equals 0.8, crystallisation by cooling, filtration; With obtaining the wet article 208.21g of pmida98 after the 150mL water washing, to dry to such an extent that content is 98.5% dry product 179.06g, yield is 86.33%.
Embodiment 4
Take by weighing the 173.25g phosphorus trichloride and join in the 143.57mL water, it is 60% phosphorous acid 172.2g and hydrogen chloride gas that hydrolysis makes concentration.
In the Iminodiacetic acid sodium salt salts solution of 370.47g 43%, add 36.5% hydrochloric acid 90g, under 80 ℃ with 5.5 * 10
-4m
3The speed of/s feeds the hydrogen chloride gas 2h that above-mentioned reaction makes; When Sorensen value was greater than 4mol/L in the detection reaction solution, the complete acidifying of Iminodiacetic acid sodium salt salt was the imido oxalic acid hydrochloride.
After treating that the phosphorus trichloride hydrolysis finishes, disposable prepared phosphorous acid is joined in the reactor drum, be warming up to the back of refluxing after; Slowly drip the formaldehyde solution of 87.57g37%, the dropping time must not be less than 1 hour, stirring and refluxing reaction 4 hours; With 20% sodium hydroxide solution transfer that alkali to pH value equals 0.8, crystallisation by cooling, filtration; With obtaining the wet article 214.28g of pmida98 after the 150mL water washing, to dry to such an extent that content is 98.43% dry product 180.85g, yield is 87.13%.
Embodiment 5
Take by weighing the 173.25g phosphorus trichloride and join in the 86.74mL water, it is 80% phosphorous acid 129.15g and hydrogen chloride gas that hydrolysis makes concentration.
In the Iminodiacetic acid sodium salt salts solution of 370.47g 43%, add 36.5% hydrochloric acid 27g, under 80 ℃ with 2.2 * 10
-4m
3The speed of/s feeds the hydrogen chloride gas 5h that above-mentioned reaction makes; When Sorensen value was greater than 4mol/L in the detection reaction solution, the complete acidifying of Iminodiacetic acid sodium salt salt was the imido oxalic acid hydrochloride.
After treating that the phosphorus trichloride hydrolysis finishes, disposable prepared phosphorous acid is joined in the reactor drum, be warming up to the back of refluxing after; Slowly drip the formaldehyde solution of 109.46g 37%, the dropping time must not be less than 1 hour, stirring and refluxing reaction 4 hours; With 20% sodium hydroxide solution transfer that alkali to pH value equals 0.8, crystallisation by cooling, filtration; With obtaining the wet article 217.43g of pmida98 after the 150mL water washing, to dry to such an extent that content is 98.61% dry product 187.64g, yield is 90.57%.
Embodiment 6
Take by weighing the 142g phosphorus trichloride and join in the 112.5mL water, it is 80% phosphorous acid 141.45g and hydrogen chloride gas that hydrolysis makes concentration.
In the Iminodiacetic acid sodium salt salts solution of 300.57g 53%, add 36.5% hydrochloric acid 27g, under 80 ℃ with 5.5 * 10
-4m
3The speed of/s feeds the hydrogen chloride gas 2h that above-mentioned reaction makes; When Sorensen value was greater than 4mol/L in the detection reaction solution, the complete acidifying of Iminodiacetic acid sodium salt salt was the imido oxalic acid hydrochloride.
After treating that the phosphorus trichloride hydrolysis finishes, disposable prepared phosphorous acid is joined in the reactor drum, be warming up to the back of refluxing after; Slowly drip the formaldehyde solution of 87.57g 37%, the dropping time must not be less than 1 hour, stirring and refluxing reaction 4 hours; With 20% sodium hydroxide solution transfer that alkali to pH value equals 0.8, crystallisation by cooling, filtration; With obtaining the wet article 210.2g of pmida98 after the 150mL water washing, to dry to such an extent that content is 97.73% dry product 178.67g, yield is 85.47%.
Embodiment 7
Take by weighing the 142g phosphorus trichloride and join in the 77.12mL water, it is 80% phosphorous acid 106.09g and hydrogen chloride gas that hydrolysis makes concentration.
In the Iminodiacetic acid sodium salt salts solution of 300.57g 53%, add 36.5% hydrochloric acid 90g, under 80 ℃ with 4 * 10
-4m
3The speed of/s feeds the hydrogen chloride gas 2.75h that above-mentioned reaction makes; When Sorensen value was greater than 4mol/L in the detection reaction solution, the complete acidifying of Iminodiacetic acid sodium salt salt was the imido oxalic acid hydrochloride.
After treating that the phosphorus trichloride hydrolysis finishes, disposable prepared phosphorous acid is joined in the reactor drum, be warming up to the back of refluxing after; Slowly drip the formaldehyde solution of 109.46g 37%, the dropping time must not be less than 1 hour, stirring and refluxing reaction 4 hours; With 20% sodium hydroxide solution transfer that alkali to pH value equals 0.8, crystallisation by cooling, filtration; With obtaining the wet article 222.96g of pmida98 after the 150mL water washing, to dry to such an extent that content is 99.03% dry product 188.62g, yield is 91.43%.
Embodiment 8
Take by weighing the 173.25g phosphorus trichloride and join in the 143.57mL water, it is 60% phosphorous acid 172.2g and hydrogen chloride gas that hydrolysis makes concentration.
In the Iminodiacetic acid sodium salt salts solution of 300.57g 53%, add 36.5% hydrochloric acid 90g, under 80 ℃ with 5.5 * 10
-4m
3The speed of/s feeds the hydrogen chloride gas 2h that above-mentioned reaction makes; When Sorensen value was greater than 4mol/L in the detection reaction solution, the complete acidifying of Iminodiacetic acid sodium salt salt was the imido oxalic acid hydrochloride.
After treating that the phosphorus trichloride hydrolysis finishes, disposable prepared phosphorous acid is joined in the reactor drum, be warming up to the back of refluxing after; Slowly drip the formaldehyde solution of 87.57g 37%, the dropping time must not be less than 1 hour, stirring and refluxing reaction 4 hours; With 20% sodium hydroxide solution transfer that alkali to pH value equals 0.8, crystallisation by cooling, filtration; With obtaining the wet article 211.94g of pmida98 after the 150mL water washing, to dry to such an extent that content is 98.57% dry product 181.21g, yield is 87.43%.
Embodiment 9
Take by weighing the 173.25g phosphorus trichloride and join in the 86.74mL water, it is 80% phosphorous acid 129.15g and hydrogen chloride gas that hydrolysis makes concentration.
In the Iminodiacetic acid sodium salt salts solution of 300.57g 53%, add 36.5% hydrochloric acid 27g, under 80 ℃ with 5.5 * 10
-4m
3The speed of/s feeds the hydrogen chloride gas 2h that above-mentioned reaction makes; When Sorensen value was greater than 4mol/L in the detection reaction solution, the complete acidifying of Iminodiacetic acid sodium salt salt was the imido oxalic acid hydrochloride.
After treating that the phosphorus trichloride hydrolysis finishes, disposable prepared phosphorous acid is joined in the reactor drum, be warming up to the back of refluxing after; Slowly drip the formaldehyde solution of 109.46g 37%, the dropping time must not be less than 1 hour, stirring and refluxing reaction 4 hours; With 20% sodium hydroxide solution transfer that alkali to pH value equals 0.8, crystallisation by cooling, filtration; With obtaining the wet article 231.33g of pmida98 after the 150mL water washing, to dry to such an extent that content is 97.87% dry product 189.69g, yield is 90.87%.
Embodiment 10
Take by weighing the 147g phosphorus trichloride and join in the 86.95mL water, it is 75% phosphorous acid 116.88g and hydrogen chloride gas that hydrolysis makes concentration.
In the Iminodiacetic acid sodium salt salts solution of 306.35g 52%, add 36.5% hydrochloric acid 50g, under 80 ℃ with 4.4 * 10
-4m
3The speed of/s feeds the hydrogen chloride gas 2.5h that above-mentioned reaction makes; When Sorensen value was greater than 4mol/L in the detection reaction solution, the complete acidifying of Iminodiacetic acid sodium salt salt was the imido oxalic acid hydrochloride.
After treating that the phosphorus trichloride hydrolysis finishes, disposable prepared phosphorous acid is joined in the reactor drum, be warming up to the back of refluxing after; Slowly drip the formaldehyde solution of 103g 37%, the dropping time must not be less than 1 hour, stirring and refluxing reaction 4 hours; With 20% sodium hydroxide solution transfer that alkali to pH value equals 0.8, crystallisation by cooling, filtration; With obtaining the wet article 220.27g of pmida98 after the 150mL water washing, to dry to such an extent that content is 98.83% dry product 188.11g, yield is 91%.
Embodiment 11
Take by weighing the 150g phosphorus trichloride and join in the 81.27mL water, it is 80% phosphorous acid 111.82g and hydrogen chloride gas that hydrolysis makes concentration.
In the Iminodiacetic acid sodium salt salts solution of 306.35g 52%, add 36.5% hydrochloric acid 70g, under 80 ℃ with 4.4 * 10
-4m
3The speed of/s feeds the hydrogen chloride gas 2.5h that above-mentioned reaction makes; When Sorensen value was greater than 4mol/L in the detection reaction solution, the complete acidifying of Iminodiacetic acid sodium salt salt was the imido oxalic acid hydrochloride.
After treating that the phosphorus trichloride hydrolysis finishes, disposable prepared phosphorous acid is joined in the reactor drum, be warming up to the back of refluxing after; Slowly drip the formaldehyde solution of 103g 37%, the dropping time must not be less than 1 hour, stirring and refluxing reaction 4 hours; With 20% sodium hydroxide solution transfer that alkali to pH value equals 0.8, crystallisation by cooling, filtration; With obtaining the wet article 225.26g of pmida98 after the 150mL water washing, to dry to such an extent that content is 99.18% dry product 189.90g, yield is 92.19%.
Embodiment 12
Take by weighing the 143g phosphorus trichloride and join in the 77.48mL water, it is 80% phosphorous acid 106.6g and hydrogen chloride gas that hydrolysis makes concentration.
In the Iminodiacetic acid sodium salt salts solution of 318.6g 43%, add 36.5% hydrochloric acid 50g, under 80 ℃ with 5.5 * 10
-4m
3The speed of/s feeds the hydrogen chloride gas 2h that above-mentioned reaction makes; When Sorensen value was greater than 4mol/L in the detection reaction solution, the complete acidifying of Iminodiacetic acid sodium salt salt was the imido oxalic acid hydrochloride.
After treating that the phosphorus trichloride hydrolysis finishes, disposable prepared phosphorous acid is joined in the reactor drum, be warming up to the back of refluxing after; Slowly add the 37.74g Paraformaldehyde 96, the joining day must not be less than 1 hour, stirring and refluxing reaction 4 hours; With 20% sodium hydroxide solution transfer that alkali to pH value equals 0.8, crystallisation by cooling, filtration; With obtaining the wet article 212.57g of pmida98 after the 150mL water washing, to dry to such an extent that content is 98.5% dry product 182.81g, yield is 88.14%.
Claims (2)
1. a method for preparing pmida98 is characterized in that, comprises the steps:
(1) phosphorus trichloride generates phosphorous acid and hydrogen chloride gas feeding hydrolysis under the nitrogen environment;
(2) in the Iminodiacetic acid sodium salt salts solution of mass percentage concentration 43%-53%, feed the direct acidifying of hydrogen chloride gas of step (1); Make the Sorensen value of solution after the acidifying more than 4mol/L, the abundant acidifying of Iminodiacetic acid sodium salt salt is become the Iminodiacetate hydrochlorate;
(3) in the solution after step (2) acidifying, add the phosphorous acid that step (1) makes, and formaldehyde or Paraformaldehyde 96, carry out condensation reaction, make pmida98;
Wherein, the mol ratio according to Iminodiacetic acid sodium salt salt and phosphorus trichloride 1: 0.9-2.5 adds phosphorus trichloride in step (1); The mass percentage concentration of the phosphorous acid of step (1) preparation is 50%-90%; Controlled temperature is under 20 ℃-120 ℃, with 2.2 * 10 in step (2)
-4m
3/ s-1.1 * 10
-3m
3The speed of/s feeds hydrogen chloride gas 1h-5h.
2. the method for claim 1 is characterized in that, the concentration of formaldehyde is 10%-40% described in the step (3), and it is according to formaldehyde or Paraformaldehyde 96 and Iminodiacetic acid sodium salt salt 1: the consumption of 0.8-2 mol ratio adds.
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| CN101648969B (en) * | 2009-09-14 | 2012-03-14 | 安徽国星生物化学有限公司 | Preparation method of N-phosphonomethyliminodiacetic acid |
| CN101974159B (en) * | 2010-01-28 | 2012-08-08 | 深圳诺普信农化股份有限公司 | Preparation method of glyphosate polymer |
| 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 |
| CN102276648B (en) * | 2011-09-02 | 2014-01-15 | 浙江拜克开普化工有限公司 | Production process for preparing N-phosphonomethyl iminodiacetic acid |
| CN105669744B (en) * | 2016-02-25 | 2017-09-19 | 宁夏格瑞精细化工有限公司 | A kind of green synthesis process of PMIDA |
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| US4724103A (en) * | 1984-02-27 | 1988-02-09 | Monsanto Company | Process for preparing N,N-diacetic acid aminomethylenephosphonic acid |
| CN101208348A (en) * | 2005-04-25 | 2008-06-25 | 孟山都技术公司 | Altering the crystal size distribution of N-(phosphonomethyl) iminodiacetic acid for improved filtration and product quality |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4724103A (en) * | 1984-02-27 | 1988-02-09 | Monsanto Company | Process for preparing N,N-diacetic acid aminomethylenephosphonic acid |
| CN101208348A (en) * | 2005-04-25 | 2008-06-25 | 孟山都技术公司 | Altering the crystal size distribution of N-(phosphonomethyl) iminodiacetic acid for improved filtration and product quality |
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| 张海滨等.三氯化磷替代亚磷酸合成双甘膦工艺改进.《现代农药》.2007,第6卷(第5期),第19-21页. * |
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Effective date of registration: 20100928 Address after: 100192 Beijing, Haidian District West Road, No. 66, building D-1 Applicant after: Nutrichem International Co., Ltd. Address before: 100085 B308 room, Zhongguancun biological medicine Park, No. 5, Pioneer Road, Beijing, Haidian District Applicant before: Nutrichem Laboratory Co., Ltd. |
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Owner name: BEIJING NUTRICHEM BIOTECHNOLOGY CO., LTD. Free format text: FORMER NAME: BEIJING NUTRICHEM INTERNATIONAL CO., LTD. |
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Address after: 100192 Beijing, Haidian District West Road, No. 66, building D-1 Patentee after: Nutrichem Co., Ltd. Address before: 100192 Beijing, Haidian District West Road, No. 66, building D-1 Patentee before: Nutrichem International Co., Ltd. |
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Address after: 100192 Beijing, Haidian District West Road, No. 66, building D-1 Patentee after: BEIJING NUTRICHEM COMPANY LIMITED Address before: 100192 Beijing, Haidian District West Road, No. 66, building D-1 Patentee before: Nutrichem Co., Ltd. |