CN103012473B - A kind of synthetic method of pmida98 - Google Patents
A kind of synthetic method of pmida98 Download PDFInfo
- Publication number
- CN103012473B CN103012473B CN201210561150.0A CN201210561150A CN103012473B CN 103012473 B CN103012473 B CN 103012473B CN 201210561150 A CN201210561150 A CN 201210561150A CN 103012473 B CN103012473 B CN 103012473B
- Authority
- CN
- China
- Prior art keywords
- massfraction
- pmida98
- afterwards
- warming
- incubated
- 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.)
- Active
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of synthetic method of pmida98, take iminodiacetonitrile as raw material, comprise the following steps: take nitration mixture as hydrolytic reagent, first iminodiacetonitrile is hydrolyzed in the nitration mixture aqueous solution, obtain the hydrochlorate of iminodiethanoic acid, then hydrolyzed solution is carried out condensation reaction with phosphorous acid and formaldehyde in presence of hydrochloric acid and obtain pmida98, described nitration mixture is hydrochloric acid and sulfuric acid, or is hydrochloric acid and phosphorous acid.The present invention take nitration mixture as hydrolytic reagent, adopts high temperature simultaneously, high pressure is hydrolyzed, and hydrolysis is more thorough, simultaneously non-exhaust emission, and the whole building-up process cycle is short, simple to operate, raw material availability is high, by-product is few, energy consumption is low, the three wastes are few.
Description
Technical field
The present invention relates to a kind of synthetic method of pmida98, particularly relating to a kind of is raw material with iminodiacetonitrile, the synthetic method of the pmida98 of with short production cycle, simple to operate, good product quality.
Background technology
Pmida98 is the important intermediate of synthesizing glyphosate, and glyphosate has wide spectrum, efficient.The advantages such as low toxicity, along with its consumption of popularization of resistance glyphosate genetically modified crops is increasing, are the herbicide products that consumption is maximum in the world at present.
And pmida98 carries out condensation in acid condition by iminodiethanoic acid and phosphorous acid and formaldehyde obtains, the difference according to iminodiethanoic acid preparation method is divided into again iminodiacetonitrile method and diethanolamine method.At present domestic mainly adopt iminodiacetonitrile be raw material to prepare iminodiethanoic acid, and then synthesis pmida98.Be easy to get along with cheaper starting materials such as iminodiacetonitrile, the good and yield more advantages of higher of glyphosate used catalyst selectivity, make production cost lower, and its cleaner production degree is higher than glycine method, so this technique becomes prevailing technology at present.
Current iminodiacetonitrile carrys out synthesis of iminodiacetic acid sodium salt mainly through alkaline hydrolysis, period will be carried out the mode such as deamination gas, dehydration, decolouring, then acid neutralization iminodiacetic acid sodium salt and could be used for pmida98 synthesis, this technological operation is loaded down with trivial details, waste unnecessary liquid caustic soda, also to build huge ammonia absorption unit, and also there is amine waste gas in production process, affect environment.
The various advantages of acidolysis iminodiacetonitrile is described in patent CN101580517, but patent Introduction will add some solid catalysts (Manganse Dioxide, potassium permanganate) in acid hemolysis process, react complete also catalyst filtration to be removed, along with adding of catalyzer may bring material appearance poor and increase the trouble of filter progress, unavoidably have sour gas in acid hemolysis process to produce simultaneously, affect operating environment.
Summary of the invention
The present invention is directed to acidolysis iminodiacetonitrile and prepare the deficiency existed in pmida98 technique, provide a kind of synthetic method of pmida98 of improvement, present method does not use catalyzer in hydrolytic process, simple to operate, flow process is short, environmental pollution is little, and products obtained therefrom visual appearance is good.
The present invention improves technique disclosed in patent CN101580517, mainly improve hydrolysis and (also can be described as acidolysis, step down together), avoid impact flow process and quality product adding of solid catalyst, and adopt positive pressure operation, avoid waste gas and to have an impact operating environment, shorten flow process simultaneously, simplify operation, improve raw material availability.The concrete technical scheme realizing advantage of the present invention is as follows:
A kind of synthetic method of pmida98, take iminodiacetonitrile as raw material, it is characterized in that comprising the following steps: take nitration mixture as hydrolytic reagent, first iminodiacetonitrile is hydrolyzed in the nitration mixture aqueous solution, obtain the hydrochlorate of iminodiethanoic acid, then hydrolyzed solution is carried out condensation reaction with phosphorous acid and formaldehyde in presence of hydrochloric acid and obtain pmida98, described nitration mixture is hydrochloric acid and sulfuric acid, or is hydrochloric acid and phosphorous acid.
In above-mentioned synthetic method, nitration mixture used is hydrochloric acid and sulfuric acid, or is hydrochloric acid and phosphorous acid, wherein H
2sO
4be 1:2-4, H with the mol ratio of HCl
3pO
3be 1:3-4 with the mol ratio of HCl.Take nitration mixture as hydrolytic reagent, can hydrolysis efficiency be improved, material can also be made in addition to be decoloured, make product appearance better.
In above-mentioned synthetic method, the H in iminodiacetonitrile and nitration mixture
+mol ratio be 1:3-5.
In above-mentioned synthetic method, acidolysis is carried out at high temperature under high pressure, and temperature is 130 DEG C-160 DEG C, and pressure is 0.5Mpa-10Mpa.When being hydrolyzed, adding rare gas element and maintaining high pressure, being preferably nitrogen.
In above-mentioned synthetic method, the time needed for hydrolysis is generally 1-10h.
In above-mentioned synthetic method, the massfraction of nitration mixture aqueous acid medium is 20%-50%, after hydrolysis, can be directly used in the synthesis of follow-up pmida98 without the need to dehydration, simple to operate.
The present invention mainly improves the step of hydrolysis, and the step that after hydrolysis, the salt of gained iminodiethanoic acid carries out condensation reaction under hydrochloric acid existence condition with phosphorous acid, formaldehyde adopts the method for prior art to realize.Because nitration mixture used is different during hydrolysis, the hydrochlorate of the iminodiethanoic acid of hydrolysis gained is hydrochloride or the phosphite of iminodiethanoic acid, nitration mixture be hydrochloric acid and sulfuric acid time, after hydrolysis, the product of gained is the hydrochloride of iminodiethanoic acid; Nitration mixture be hydrochloric acid and phosphorous acid time, after hydrolysis, the product of gained is the phosphite of iminodiethanoic acid.After hydrolysis, cool the temperature to 80-90 DEG C, then the rare gas element in reactor is discharged, Pressure Drop can be carried out the condensation reaction of lower step to normal pressure.During condensation reaction, the mol ratio of iminodiethanoic acid and formaldehyde, phosphorous acid is 1:1.2-1.5:1-1.2.Step of condensation is: after acidolysis, be cooled to less than 90 DEG C (being generally 80-90 DEG C), then emission gases is down to normal pressure, material is proceeded to condensation kettle, be warming up to backflow after adding phosphorous acid or hydrochloric acid and then drip formaldehyde, formaldehyde dropwises, insulation reaction, after reaction terminates, be cooled to less than 50 DEG C, then add liquid caustic soda and regulate pH to 0-1, be cooled to room temperature afterwards, suction filtration washing obtains pmida98 wet feed and filtrate, and in filtrate, ammonium chloride or ammonium sulfate are separated out as by-product process after evaporation concentration.
The invention has the beneficial effects as follows:
(1) take nitration mixture as hydrolytic reagent, adopt high temperature simultaneously, high pressure is hydrolyzed, hydrolysis is more thorough, simultaneously non-exhaust emission.
(2) not only the sulfuric acid in nitration mixture or phosphorous acid, as hydrolytic reagent but also as catalyzer, improve hydrolysis efficiency.
(3) carry out under protection of inert gas during hydrolysis, prevent raw material oxidized, decrease the generation of side reaction.
(4) in hydrolytic process due to the effect of nitration mixture, material is decoloured, and the pmida98 outward appearance of output is better.
(5) ammonium chloride produced in hydrolytic process or ammonium sulfate are dissolved in reaction solution, can be easier to be recycled after condensation reaction, and sell as by-product, particularly ammonium sulfate has very high commercial value.
(6) the whole building-up process cycle is short, simple to operate, raw material availability is high, by-product is few, energy consumption is low, the three wastes are few.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described.It is to be understood that following explanation is only to explain the present invention, its content is not limited.
The method of synthesis pmida98 of the present invention, adopts following steps:
(1) mixed solution of sulfuric acid and hydrochloric acid or hydrochloric acid are dropped in autoclave with the mixed solution of phosphorous acid together with iminodiacetonitrile, then use rare gas element (preferred nitrogen) to replace still inner hollow body, airtight afterwards, heat up.
(2) temperature of reaction is maintained between 130 DEG C-160 DEG C, period passes into rare gas element (preferred nitrogen) and maintains reaction pressure within the scope of 0.5Mpa-10Mpa, be incubated the reaction that is hydrolyzed for 1 hour-10 hours, obtain hydrochloride or the phosphite of iminodiethanoic acid.
(3) after hydrolysis, be cooled to less than 90 DEG C (being generally 80-90 DEG C), then emptying gas, material is proceeded to condensation kettle, adds phosphorous acid when phosphorous acid is not enough, during salt subacidity, add hydrochloric acid, be warming up to backflow and then drip formaldehyde, when keeping condensation reaction, the mol ratio of iminodiethanoic acid and formaldehyde, phosphorous acid is 1:1.2-1.5:1-1.2, and before dripping formaldehyde, in system, the mol ratio of iminodiethanoic acid and the hydrochloric acid that has neither part nor lot in hydrolysis reaction is 1:1-2.
(4) after formaldehyde dropwises, condensation reaction is carried out in insulation, after insulation terminates, be cooled to less than 50 DEG C, then add liquid caustic soda and regulate pH to 0-1, be cooled to room temperature afterwards, suction filtration washing obtains pmida98 wet feed and filtrate, and in filtrate, ammonium chloride or ammonium sulfate are separated out as by-product process after evaporation concentration.
embodiment 1
In 1L still, drop into 100g water successively, massfraction is the hydrochloric acid 273g of 30%, and massfraction is the vitriol oil 55g of 98%, then slowly adds the iminodiacetonitrile 100g that massfraction is 95%.Backlash nitrogen replace gas reactor to 0.2Mpa, then emptying.Closed reactor is also warming up to 160 DEG C.In still, rush nitrogen to pressure is 1Mpa.Be incubated 6 hours afterwards, start cooling after insulation terminates, treat that temperature is down to 80 DEG C, pressure release, material is proceeded to 1000ml four-hole boiling flask, weigh, detect.Weight is 502.1g, IDA content is 25.81%.
In flask, add solid phosphorous acid 94.5g, be then warming up to backflow.Dripping massfraction is the formaldehyde solution 104g of 36.5%, time for adding 2 hours.Dropwise, be incubated 1 hour, then lower the temperature, fill into 100g water, add liquid caustic soda 80g when being down to 50 DEG C, pH is 1, is down to room temperature afterwards, and suction filtration washing, oven dry obtain white pmida98 208g, and hundred yields 90.3% rolled over by solid, content 98.56%.
embodiment 2
In 1L still, drop into 100g water successively, massfraction is the hydrochloric acid 273.3g of 30%, and massfraction is the vitriol oil 110g of 98%, then slowly adds the iminodiacetonitrile 100g that massfraction is 95%.Backlash nitrogen replace gas reactor to 0.2Mpa, then emptying.Closed reactor is also warming up to 160 DEG C.In still, rush nitrogen to pressure is 2Mpa.Be incubated 6 hours afterwards, start cooling after insulation terminates, treat that temperature is down to 80 DEG C, pressure release, material is proceeded to 1000ml four-hole boiling flask, in flask, add solid phosphorous acid 94.5g, be then warming up to backflow.Dripping massfraction is the formaldehyde solution 104g of 36.5%, time for adding 2 hours.Dropwise, be incubated 1 hour, then lower the temperature, fill into 100g water, add liquid caustic soda 80g when being down to 50 DEG C, pH is 1, is down to room temperature afterwards, and suction filtration washing, oven dry obtain white pmida98 208.9g, and hundred yields 90.52% rolled over by solid, content 98.36%.
embodiment 3
In 1L autoclave, drop into the hydrochloric acid 427.7g that massfraction is 30% successively, massfraction is the phosphorous acid 95g of 99%, then slowly adds the iminodiacetonitrile 100g that massfraction is 95%.Backlash nitrogen replace gas reactor to 0.2Mpa, then emptying.Closed reactor is also warming up to 140 DEG C.In still, rush nitrogen to pressure is 0.6Mpa.Be incubated 4 hours afterwards, start cooling after insulation terminates, treat that temperature is down to 90 DEG C, pressure release, produces material, and weight is 570.4g.
Above-mentioned material is proceeded to 1000ml four-hole boiling flask, is then warming up to backflow.In two hours by massfraction be 36.5% 104g formaldehyde solution dropwise, be incubated 1.5 hours afterwards, the insulation end 100g that adds water continues to be cooled to 50 DEG C, then adds liquid caustic soda 100g to pH=1.Continue to be cooled to room temperature, then suction filtration, washing, dries to obtain white pmida98 209.3g, yield 91.04%, content 98.32%.
embodiment 4
In 1L still, drop into the hydrochloric acid 377.7g that massfraction is 30% successively, massfraction is the phosphorous acid 82g of 99%, then slowly adds the iminodiacetonitrile 100g that massfraction is 95%.Backlash nitrogen replace gas reactor to 0.2Mpa, then emptying.Closed reactor is also warming up to 130 DEG C.In still, rush nitrogen to pressure is 10Mpa.Be incubated 4 hours afterwards, start cooling after insulation terminates, treat that temperature is down to 90 DEG C, pressure release, material is proceeded to 1000ml four-hole boiling flask, weight is 569.8g.Then add hydrochloric acid 40g, phosphorous acid 13g, is warming up to backflow by material.In 2.5 hours by massfraction be 36.5% 105g formaldehyde solution dropwise, be incubated 1 hour afterwards, the insulation end 100g that adds water continues to be cooled to 50 DEG C, then adds liquid caustic soda 110g and adjusts pH=1.Continue to be cooled to room temperature, then suction filtration, washing, dries to obtain white pmida98 207.6g, yield 90.23%, content 98.67%.
embodiment 5
In 1L still, drop into the hydrochloric acid 427.7g that massfraction is 30% successively, massfraction is the phosphorous acid 72.4g of 99%, then slowly adds the iminodiacetonitrile 100g that massfraction is 95%.Backlash nitrogen replace gas reactor to 0.2Mpa, then emptying.Closed reactor is also warming up to 130 DEG C.In still, rush nitrogen to pressure is 5Mpa.Be incubated 4 hours afterwards, start cooling after insulation terminates, treat that temperature is down to 90 DEG C, pressure release, material is proceeded to 1000ml four-hole boiling flask, then add phosphorous acid 22.6g, material is warming up to backflow.In 2.5 hours by massfraction be 36.5% 105g formaldehyde solution dropwise, be incubated 1 hour afterwards, the insulation end 100g that adds water continues to be cooled to 50 DEG C, then adds liquid caustic soda 110g and adjusts pH=1.Continue to be cooled to room temperature, then suction filtration, washing, dries to obtain white pmida98 206.9g, yield 89.75%, content 98.47%.
Known by above embodiment, the present invention is hydrolyzed iminodiacetonitrile and only can completes with nitration mixture, does not need catalyzer, and during hydrolysis, temperature can a step control, and do not need employing two sections of temperature controls, simple to operate, product appearance is good.The present invention, without catalyzer, eliminates catalyst removal step and dehydrating step, further simplify technique, can not produce sour gas in acid hemolysis process, and environment is more friendly, and the three wastes are less, are beneficial to cleaner production, have good industrial value.
Claims (4)
1. the synthetic method of a pmida98, it is characterized in that: in 1L still, drop into 100g water successively, massfraction is the hydrochloric acid 273g of 30%, massfraction is the vitriol oil 55g of 98%, then the iminodiacetonitrile 100g that massfraction is 95% is slowly added, inflated with nitrogen replaces gas reactor to 0.2Mpa afterwards, then emptying, and closed reactor is also warming up to 160 DEG C, in still, inflated with nitrogen to pressure is 1Mpa, be incubated 6 hours afterwards, start cooling after insulation terminates, treat that temperature is down to 80 DEG C, pressure release, material is proceeded to 1000ml four-hole boiling flask, weigh, detect; Solid phosphorous acid 94.5g is added in flask, then be warming up to backflow, dripping massfraction is the formaldehyde solution 104g of 36.5%, time for adding 2 hours, dropwise, be incubated 1 hour, then lower the temperature, fill into 100g water, liquid caustic soda 80g is added when being down to 50 DEG C, pH is 1, is down to room temperature afterwards, and suction filtration washing, oven dry obtain white pmida98.
2. the synthetic method of a pmida98, it is characterized in that: in 1L still, drop into 100g water successively, massfraction is the hydrochloric acid 273.3g of 30%, massfraction is the vitriol oil 110g of 98%, then the iminodiacetonitrile 100g that massfraction is 95% is slowly added, inflated with nitrogen replaces gas reactor to 0.2Mpa afterwards, then emptying, closed reactor is also warming up to 160 DEG C, in still, inflated with nitrogen to pressure is 2Mpa, be incubated 6 hours afterwards, cooling is started after insulation terminates, treat that temperature is down to 80 DEG C, pressure release, material is proceeded to 1000ml four-hole boiling flask, solid phosphorous acid 94.5g is added in flask, then backflow is warming up to, dripping massfraction is the formaldehyde solution 104g of 36.5%, time for adding 2 hours, dropwise, be incubated 1 hour, then lower the temperature, fill into 100g water, liquid caustic soda 80g is added when being down to 50 DEG C, pH is 1, be down to room temperature afterwards, suction filtration is washed, oven dry obtains white pmida98.
3. the synthetic method of a pmida98, it is characterized in that: in 1L autoclave, drop into the hydrochloric acid 427.7g that massfraction is 30% successively, massfraction is the phosphorous acid 95g of 99%, then the iminodiacetonitrile 100g that massfraction is 95% is slowly added, inflated with nitrogen replaces gas reactor to 0.2Mpa afterwards, then emptying, closed reactor is also warming up to 140 DEG C, in still, inflated with nitrogen to pressure is 0.6Mpa, be incubated 4 hours afterwards, start cooling after insulation terminates, treat that temperature is down to 90 DEG C, pressure release, produces material; Above-mentioned material is proceeded to 1000ml four-hole boiling flask, then backflow is warming up to, in two hours by massfraction be 36.5% 104g formaldehyde solution dropwise, be incubated 1.5 hours afterwards, the insulation end 100g that adds water continues to be cooled to 50 DEG C, then adds liquid caustic soda 100g to pH=1, continue to be cooled to room temperature, then suction filtration, washing, dries to obtain white pmida98.
4. the synthetic method of a pmida98, it is characterized in that: in 1L still, drop into the hydrochloric acid 377.7g that massfraction is 30% successively, massfraction is the phosphorous acid 82g of 99%, then the iminodiacetonitrile 100g that massfraction is 95% is slowly added, inflated with nitrogen replaces gas reactor to 0.2Mpa afterwards, then emptying, closed reactor is also warming up to 130 DEG C, in still, inflated with nitrogen to pressure is 10Mpa, be incubated 4 hours afterwards, cooling is started after insulation terminates, treat that temperature is down to 90 DEG C, pressure release, material is proceeded to 1000ml four-hole boiling flask, then hydrochloric acid 40g is added, phosphorous acid 13g, material is warming up to backflow, in 2.5 hours by massfraction be 36.5% 105g formaldehyde solution dropwise, be incubated 1 hour afterwards, the insulation end 100g that adds water continues to be cooled to 50 DEG C, then add liquid caustic soda 110g and adjust pH=1, continue to be cooled to room temperature, then suction filtration, washing, dry to obtain white pmida98.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210561150.0A CN103012473B (en) | 2012-12-21 | 2012-12-21 | A kind of synthetic method of pmida98 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210561150.0A CN103012473B (en) | 2012-12-21 | 2012-12-21 | A kind of synthetic method of pmida98 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103012473A CN103012473A (en) | 2013-04-03 |
| CN103012473B true CN103012473B (en) | 2016-03-02 |
Family
ID=47961623
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210561150.0A Active CN103012473B (en) | 2012-12-21 | 2012-12-21 | A kind of synthetic method of pmida98 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103012473B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105524107B (en) * | 2014-09-30 | 2017-12-29 | 北京紫光英力化工技术有限公司 | A kind of PMIDA clean manufacturing and accessory substance novel process for recycling |
| CN104402924A (en) * | 2014-11-26 | 2015-03-11 | 杭州上拓环境科技有限公司 | Novel process for producing sodium-free pmida |
| CN108912168A (en) * | 2018-08-10 | 2018-11-30 | 泰兴市飞天化工有限公司 | A method of preparing pmida |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1944444A (en) * | 2005-10-08 | 2007-04-11 | 北京清华紫光英力化工技术有限责任公司 | Synthetic method for N-phosphonyl methyl imino diacetic acid |
| CN101092369A (en) * | 2006-06-23 | 2007-12-26 | 北京清华紫光英力化工技术有限责任公司 | Method for preparing iminodiacetic acid by using raw material of hydroxy acetonitrile |
| CN101580517A (en) * | 2009-06-25 | 2009-11-18 | 山东潍坊润丰化工有限公司 | Clean production method for N-(Phosphonomethyl)iminodiacetic acid |
| CN101676292A (en) * | 2008-09-15 | 2010-03-24 | 李坚 | Method for preparing N-(phosphonomethyl) iminodiacetic acid and glyphosate by using non-alkali metal |
| CN101735269A (en) * | 2008-11-07 | 2010-06-16 | 南京工业大学 | Synthesis method of N-phosphonomethyliminodiacetic acid |
| CN101747369A (en) * | 2010-01-05 | 2010-06-23 | 淄博万昌科技股份有限公司 | Environmental-friendly new method for preparing N-phosphonomethyl iminodiacetic acid by utilizing acrylonitrile byproduct hydrocyanic acid |
| CN102101873A (en) * | 2011-01-14 | 2011-06-22 | 捷马化工股份有限公司 | Preparation method of N-(phosphonomethyl)iminodiacetic acid |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52144656A (en) * | 1976-05-26 | 1977-12-02 | Nissan Chem Ind Ltd | N-(diphenylphosphonomethyl)-imino-diacetonitrile and its preparation |
-
2012
- 2012-12-21 CN CN201210561150.0A patent/CN103012473B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1944444A (en) * | 2005-10-08 | 2007-04-11 | 北京清华紫光英力化工技术有限责任公司 | Synthetic method for N-phosphonyl methyl imino diacetic acid |
| CN101092369A (en) * | 2006-06-23 | 2007-12-26 | 北京清华紫光英力化工技术有限责任公司 | Method for preparing iminodiacetic acid by using raw material of hydroxy acetonitrile |
| CN101676292A (en) * | 2008-09-15 | 2010-03-24 | 李坚 | Method for preparing N-(phosphonomethyl) iminodiacetic acid and glyphosate by using non-alkali metal |
| CN101735269A (en) * | 2008-11-07 | 2010-06-16 | 南京工业大学 | Synthesis method of N-phosphonomethyliminodiacetic acid |
| CN101580517A (en) * | 2009-06-25 | 2009-11-18 | 山东潍坊润丰化工有限公司 | Clean production method for N-(Phosphonomethyl)iminodiacetic acid |
| CN101747369A (en) * | 2010-01-05 | 2010-06-23 | 淄博万昌科技股份有限公司 | Environmental-friendly new method for preparing N-phosphonomethyl iminodiacetic acid by utilizing acrylonitrile byproduct hydrocyanic acid |
| CN102101873A (en) * | 2011-01-14 | 2011-06-22 | 捷马化工股份有限公司 | Preparation method of N-(phosphonomethyl)iminodiacetic acid |
Non-Patent Citations (1)
| Title |
|---|
| 腈纶废丝的水解及其应用;周国伟;《曲阜师范大学学报》;19970415;第23卷(第2期);第81-83页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103012473A (en) | 2013-04-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104327115B (en) | A kind of energy-saving clean production method of high-purity glufosinate-ammonium | |
| CN102898382B (en) | Method for synthesizing 2-amino-4,6-dimethoxypyrimidine | |
| CN103012473B (en) | A kind of synthetic method of pmida98 | |
| CN104119243B (en) | A kind of energy-saving clean production method of iminodiethanoic acid | |
| CN104649965A (en) | Preparation method of 3,4,5,6-tetrachloropyridine-2-carboxylic acid | |
| CN103058899B (en) | Synthetic method for methyl-sulfuryl benzaldehyde | |
| CN105254575A (en) | Synthetic method for sulfadiazine | |
| CN108246277B (en) | Method for efficiently synthesizing trifluoroiodomethane | |
| CN101565400B (en) | Preparation method of 4-amino-3, 5, 6-chloropyridine-2-methanoic acid | |
| CN105985251B (en) | A kind of amino acids process for cleanly preparing such as iminodiacetic acid | |
| CN101735167B (en) | Preparation method of 6-nitrosaccharin | |
| CN1990460B (en) | Comprehensive treatment of glycine crystallization mother liquid | |
| CN101972642A (en) | Solid base catalyst and method for synthesizing 3-chloro-2-hydroxypropyl-trimethyl-ammonium chloride based on solid base catalyst | |
| CN103012215B (en) | Azo dodecanedioic acid dialkyl ester preparation method | |
| CN112939893B (en) | Synthesis method of 4- (4-aminophenyl) -3-morpholinone | |
| CN104513197A (en) | 2-aminonicotinic acid synthetic method | |
| CN104447290B (en) | A kind of method preparing 2,4 dichlorophenoxyacetic acid | |
| CN104876889A (en) | A synthesis method of a compound | |
| CN102924346A (en) | Method for synthesizing methyl sulfone base dibromo toluene | |
| CN104262160B (en) | A kind of preparation method of 2-nitro-2-methyl isophthalic acid-propyl alcohol | |
| CN102838482B (en) | Preparation method of 3,6-dichlorosalicylic acid | |
| CN103252239B (en) | Catalyst for synthesizing glycerol carbonic, preparation method for catalyst and application of catalyst | |
| CN104672279A (en) | Improved pmida energy-saving synthesis method | |
| CN106167469A (en) | A kind of method of synthesis 2 amino 4,6 dihydroxy-pyrimidines | |
| CN114409556B (en) | Preparation method of 3, 4-disubstituted-2-aminobenzaldehyde |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C53 | Correction of patent for invention or patent application | ||
| CB02 | Change of applicant information |
Address after: Haiyuan Binhai Economic Development Zone, Shandong province Weifang city 262737 Street No. 600 Applicant after: Shandong Weifang Rainbow Chemical Co., Ltd. Address before: Haiyuan Binhai Economic and Technological Development Zone in Shandong province Weifang City 600 street 262737 No. 1 ranked No. 1 Applicant before: Shandong Weifang Rainbow Chemical Co., Ltd. |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CP02 | Change in the address of a patent holder | ||
| CP02 | Change in the address of a patent holder |
Address after: No. 03001, chlor alkali Road, Weifang Coastal Economic Development Zone, Shandong, Shandong Patentee after: Shandong Weifang Rainbow Chemical Co.,Ltd. Address before: Haiyuan Binhai Economic Development Zone, Shandong province Weifang city 262737 Street No. 600 Patentee before: Shandong Weifang Rainbow Chemical Co.,Ltd. |