CN103012473A - Synthesis method of N-(Phosphonomethyl) iminodiacetic acid - Google Patents
Synthesis method of N-(Phosphonomethyl) iminodiacetic acid Download PDFInfo
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- CN103012473A CN103012473A CN2012105611500A CN201210561150A CN103012473A CN 103012473 A CN103012473 A CN 103012473A CN 2012105611500 A CN2012105611500 A CN 2012105611500A CN 201210561150 A CN201210561150 A CN 201210561150A CN 103012473 A CN103012473 A CN 103012473A
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- iminodiacetonitrile
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Abstract
The invention discloses a synthesis method of N-(Phosphonomethyl) iminodiacetic acid (PMIDA) using iminodiacetonitrile as the raw material. The method comprises the following steps: using mixed acid as a hydrolytic reagent, hydrolyzing the iminodiacetonitrile in the mixed acid water solution to obtain acid salt of the iminodiacetic acid, and then performing the condensation reaction of the hydrolyzation solution with phosphorous acid and formaldehyde at the presence of hydrochloric acid to obtain the N-(Phosphonomethyl) iminodiacetic acid, wherein the mixed acid is hydrochloric acid and sulfuric acid, or hydrochloric acid and orthophosphorous acid. According to the invention, the mixed acid is used as a hydrolytic reagent; meanwhile, high temperature and high pressure are adopted to enable the hydrolyzation to be more thorough; at the same time, no waste gas is emitted; and the periodic time of the whole synthesis process is short, the operation is simple, the utilization ratio of the raw materials is high, the side product is few, energy consumption is low and the three wastes are less.
Description
Technical field
The present invention relates to a kind of synthetic method of pmida98, relate in particular to a kind of take iminodiacetonitrile as raw material, with short production cycle, simple to operate synthetic method of pmida98 of, 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 weedicide products of in the world consumption maximum at present.
Obtain and pmida98 carries out condensation by iminodiethanoic acid and phosphorous acid and formaldehyde under acidic conditions, be divided into again iminodiacetonitrile method and diethanolamine method according to the difference of iminodiethanoic acid preparation method.At present domestic mainly is that the employing iminodiacetonitrile is that raw material prepares iminodiethanoic acid, and then synthetic pmida98.Be accompanied by that the raw materials such as iminodiacetonitrile are cheap and easy to get, glyphosate oxidation catalyst system therefor selectivity is good and yield advantages of higher more, make production cost lower, and its cleaner production degree is higher than glycine method, so this technique has become main flow technique at present.
Iminodiacetonitrile is mainly come the synthesis of iminodiacetic acid sodium salt by alkaline hydrolysis at present, to carry out during this time deamination gas, dehydration, decolouring, then the mode such as acid neutralization iminodiacetic acid sodium salt could to be used for pmida98 synthetic, this technological operation is loaded down with trivial details, wasted unnecessary liquid caustic soda, also to build huge ammonia absorption unit, and also there is amine waste gas in the production process, affects environment.
In patent CN101580517, narrated the various advantages of acidolysis iminodiacetonitrile, but patent Introduction will add some solid catalysts (Manganse Dioxide, potassium permanganate) in the acidolysis process, reacting complete also will remove by filter catalyzer, may bring the trouble of material appearance poor and increase filter progress along with the adding of catalyzer, unavoidably have sour gas in the simultaneously acidolysis process and produce, affect operating environment.
Summary of the invention
The present invention is directed to the acidolysis iminodiacetonitrile and prepare the deficiency that exists in the pmida98 technique, a kind of synthetic method of improved pmida98 is provided, present method is not used catalyzer in hydrolytic process, simple to operate, flow process is short, environmental pollution is little, and the products obtained therefrom visual appearance is good.
The present invention improves disclosed technique among the patent CN101580517, mainly be to improve hydrolysis (also to can be described as acidolysis, step down together), avoid the adding of solid catalyst that flow process and quality product are impacted, and the employing positive pressure operation has been avoided the waste gas operating environment that exerts an influence, and has shortened simultaneously flow process, simplify operation, improved raw material availability.The concrete technical scheme that realizes 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 may further comprise the steps: take nitration mixture as hydrolytic reagent, first iminodiacetonitrile is hydrolyzed in the nitration mixture aqueous solution, get the hydrochlorate of iminodiethanoic acid, then hydrolyzed solution is carried out condensation reaction with phosphorous acid and formaldehyde in the presence of hydrochloric acid and get pmida98, described nitration mixture is hydrochloric acid and sulfuric acid, perhaps is hydrochloric acid and phosphorous acid.
In the above-mentioned synthetic method, used nitration mixture is hydrochloric acid and sulfuric acid, perhaps is hydrochloric acid and phosphorous acid, wherein H
2SO
4With the mol ratio of HCl be 1:2-4, H
3PO
3With the mol ratio of HCl be 1:3-4.Take nitration mixture as hydrolytic reagent, can improve hydrolysis efficiency, material is decoloured, make product appearance better.
In the above-mentioned synthetic method, the H in iminodiacetonitrile and the nitration mixture
+Mol ratio be 1:3-5.
In the above-mentioned synthetic method, acidolysis is carried out under High Temperature High Pressure, and temperature is 130 ℃-160 ℃, and pressure is 0.5Mpa-10Mpa.When hydrolysis, add rare gas element and keep high pressure, be preferably nitrogen.
In the above-mentioned synthetic method, be hydrolyzed the required time to be generally 1-10h.
In the above-mentioned synthetic method, the massfraction of nitration mixture aqueous acid medium is 20%-50%, be hydrolyzed complete after, need not dehydration can be directly used in follow-up pmida98 synthetic in, simple to operate.
The present invention improves the step of hydrolysis, and the salt of gained iminodiethanoic acid adopts the method for prior art to realize with step that phosphorous acid, formaldehyde carry out condensation reaction under the hydrochloric acid existence condition after the hydrolysis.Because nitration mixture used during hydrolysis is different, the hydrochlorate of the iminodiethanoic acid of hydrolysis gained is hydrochloride or the phosphite of iminodiethanoic acid, and when nitration mixture was hydrochloric acid and sulfuric acid, the product of gained was the hydrochloride of iminodiethanoic acid after the hydrolysis; When nitration mixture was hydrochloric acid and phosphorous acid, the product of gained was the phosphite of iminodiethanoic acid after the hydrolysis.After hydrolysis is complete, cool the temperature to 80-90 ℃, then the rare gas element in the reactor is discharged, Pressure Drop to normal pressure can be carried out the condensation reaction in lower step.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 is complete, be cooled to below 90 ℃ and (be generally 80-90 ℃), then emission gases is down to normal pressure, change material over to condensation kettle, be warming up to backflow behind adding phosphorous acid or the hydrochloric acid and then drip formaldehyde, formaldehyde dropwises, insulation reaction, after reaction finishes, be cooled to below 50 ℃, then add liquid caustic soda and regulate pH to 0-1, be cooled to afterwards room temperature, the suction filtration washing obtains pmida98 wet feed and filtrate, and ammonium chloride or ammonium sulfate are separated out after evaporation concentration as by-product and processed in the filtrate.
The invention has the beneficial effects as follows:
(1) take nitration mixture as hydrolytic reagent, adopt simultaneously high temperature, high pressure to be hydrolyzed, be hydrolyzed more thorough, non-exhaust emission simultaneously.
(2) sulfuric acid in the nitration mixture or phosphorous acid namely as hydrolytic reagent again as catalyzer, improved hydrolysis efficiency.
Under protection of inert gas, carry out when (3) being hydrolyzed, prevented that raw material is oxidized, reduced the generation of side reaction.
(4) in the hydrolytic process because the effect of nitration mixture is decoloured material, the pmida98 outward appearance of output is better.
(5) ammonium chloride that produces in the hydrolytic process or ammonium sulfate are dissolved in the reaction solution, can be easier to be recycled after condensation reaction is complete, sell as by-product, and 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
The invention will be further described below in conjunction with specific embodiment.Should be understood that following explanation only is in order to explain the present invention, its content not to be limited.
The method of synthetic pmida98 of the present invention, adopt following steps:
(1) sulfuric acid is dropped in the autoclave with iminodiacetonitrile with the mixed solution of hydrochloric acid or the hydrochloric acid mixed solution with phosphorous acid, then use rare gas element (preferred nitrogen) displacement still inner hollow body, airtight afterwards, heat up.
(2) keep temperature of reaction between 130 ℃-160 ℃, pass into during this time rare gas element (preferred nitrogen) and keep reaction pressure in the 0.5Mpa-10Mpa scope, the reaction that is hydrolyzed in-10 hours that is incubated 1 hour gets hydrochloride or the phosphite of iminodiethanoic acid.
(3) hydrolysis complete after, be cooled to below 90 ℃ and (be generally 80-90 ℃), then emptying gas, change material over to condensation kettle, add phosphorous acid when phosphorous acid is not enough, add hydrochloric acid during the salt subacidity, be warming up to backflow and then drip formaldehyde, the mol ratio of iminodiethanoic acid and formaldehyde, phosphorous acid is 1:1.2-1.5:1-1.2 when keeping condensation reaction, and before the dropping formaldehyde, iminodiethanoic acid is 1:1-2 with the mol ratio that has neither part nor lot in the hydrochloric acid of hydrolysis reaction in the system.
(4) after formaldehyde dropwises, condensation reaction is carried out in insulation, after insulation finishes, be cooled to below 50 ℃, then add liquid caustic soda and regulate pH to 0-1, be cooled to afterwards room temperature, the suction filtration washing obtains pmida98 wet feed and filtrate, and ammonium chloride or ammonium sulfate are separated out after evaporation concentration as by-product and processed in the filtrate.
Embodiment 1
Drop into successively 100g water in the 1L still, massfraction is 30% hydrochloric acid 273g, and massfraction is 98% vitriol oil 55g, then slowly adds massfraction and be 95% iminodiacetonitrile 100g.Rush afterwards nitrogen and replace gas reactor to 0.2Mpa, then emptying.Closed reactor also is warming up to 160 ℃.Rushing nitrogen to pressure in the still is 1Mpa.Be incubated afterwards 6 hours, begin cooling after insulation finishes, treat that temperature is down to 80 ℃, pressure release changes material over to the 1000ml four-hole boiling flask, weighs, and detects.Weight is 502.1g, and IDA content is 25.81%.
In flask, add solid phosphorous acid 94.5g, then be warming up to backflow.The dropping massfraction is 36.5% formaldehyde solution 104g, time for adding 2 hours.Dropwise, be incubated 1 hour, then cooling fills into 100g water, adds liquid caustic soda 80g when being down to 50 ℃, and pH is 1, is down to afterwards room temperature, and suction filtration washing, oven dry obtain white pmida98 208g, and solid is rolled over hundred yields 90.3%, content 98.56%.
Embodiment 2
Drop into successively 100g water in the 1L still, massfraction is 30% hydrochloric acid 273.3g, and massfraction is 98% vitriol oil 110g, then slowly adds massfraction and be 95% iminodiacetonitrile 100g.Rush afterwards nitrogen and replace gas reactor to 0.2Mpa, then emptying.Closed reactor also is warming up to 160 ℃.Rushing nitrogen to pressure in the still is 2Mpa.Be incubated afterwards 6 hours, begin cooling after insulation finishes, treat that temperature is down to 80 ℃, pressure release changes material over to the 1000ml four-hole boiling flask, adds solid phosphorous acid 94.5g in flask, then is warming up to backflow.The dropping massfraction is 36.5% formaldehyde solution 104g, time for adding 2 hours.Dropwise, be incubated 1 hour, then cooling fills into 100g water, adds liquid caustic soda 80g when being down to 50 ℃, and pH is 1, is down to afterwards room temperature, and suction filtration washing, oven dry obtain white pmida98 208.9g, and solid is rolled over hundred yields 90.52%, content 98.36%.
Embodiment 3
Drop into successively massfraction in the 1L autoclave and be 30% hydrochloric acid 427.7g, massfraction is 99% phosphorous acid 95g, then slowly adds massfraction and be 95% iminodiacetonitrile 100g.Rush afterwards nitrogen and replace gas reactor to 0.2Mpa, then emptying.Closed reactor also is warming up to 140 ℃.Rushing nitrogen to pressure in the still is 0.6Mpa.Be incubated afterwards 4 hours, begin cooling after insulation finishes, treat that temperature is down to 90 ℃, material is produced in pressure release, and weight is 570.4g.
Change above-mentioned material over to the 1000ml four-hole boiling flask, then be warming up to backflow.In two hours be that 36.5% 104g formaldehyde solution dropwises with massfraction, be incubated afterwards 1.5 hours, insulation finishes to add water 100g and continues to be cooled to 50 ℃, then adds liquid caustic soda 100g to pH=1.Continue to be cooled to room temperature, then suction filtration is washed, and dries to get white pmida98 209.3g, yield 91.04%, content 98.32%.
Embodiment 4
Drop into successively massfraction in the 1L still and be 30% hydrochloric acid 377.7g, massfraction is 99% phosphorous acid 82g, then slowly adds massfraction and be 95% iminodiacetonitrile 100g.Rush afterwards nitrogen and replace gas reactor to 0.2Mpa, then emptying.Closed reactor also is warming up to 130 ℃.Rushing nitrogen to pressure in the still is 10Mpa.Be incubated afterwards 4 hours, begin cooling after insulation finishes, treat that temperature is down to 90 ℃, pressure release changes material over to the 1000ml four-hole boiling flask, and weight is 569.8g.Then add hydrochloric acid 40g, phosphorous acid 13g is warming up to backflow with material.2.5 in hour be that 36.5% 105g formaldehyde solution dropwises with massfraction, be incubated afterwards 1 hour, insulation finishes to add water 100g and continues to be cooled to 50 ℃, then adds liquid caustic soda 110g and transfers pH=1.Continue to be cooled to room temperature, then suction filtration is washed, and dries to get white pmida98 207.6g, yield 90.23%, content 98.67%.
Embodiment 5
Drop into successively massfraction in the 1L still and be 30% hydrochloric acid 427.7g, massfraction is 99% phosphorous acid 72.4g, then slowly adds massfraction and be 95% iminodiacetonitrile 100g.Rush afterwards nitrogen and replace gas reactor to 0.2Mpa, then emptying.Closed reactor also is warming up to 130 ℃.Rushing nitrogen to pressure in the still is 5Mpa.Be incubated afterwards 4 hours, begin cooling after insulation finishes, treat that temperature is down to 90 ℃, pressure release changes material over to the 1000ml four-hole boiling flask, then adds phosphorous acid 22.6g, and material is warming up to backflow.2.5 in hour be that 36.5% 105g formaldehyde solution dropwises with massfraction, be incubated afterwards 1 hour, insulation finishes to add water 100g and continues to be cooled to 50 ℃, then adds liquid caustic soda 110g and transfers pH=1.Continue to be cooled to room temperature, then suction filtration is washed, and dries to get white pmida98 206.9g, yield 89.75%, content 98.47%.
By above embodiment as can be known, the present invention is hydrolyzed iminodiacetonitrile and only can finishes with nitration mixture, does not need catalyzer, and when hydrolysis temperature can step control, need not adopt two sections temperature controls, simple to operate, product appearance is good.The present invention has saved catalyst removal step and dehydrating step without catalyzer, has more simplified technique, can not produce sour gas in the acidolysis process, and environment is more friendly, and the three wastes still less are beneficial to cleaner production, has good industrial value.
Claims (8)
1. the synthetic method of a pmida98, take iminodiacetonitrile as raw material, it is characterized in that may further comprise the steps: take nitration mixture as hydrolytic reagent, first iminodiacetonitrile is hydrolyzed in the nitration mixture aqueous solution, get the hydrochlorate of iminodiethanoic acid, then hydrolyzed solution is carried out condensation reaction with phosphorous acid and formaldehyde in the presence of hydrochloric acid and get pmida98, described nitration mixture is hydrochloric acid and sulfuric acid, perhaps is hydrochloric acid and phosphorous acid.
2. synthetic method according to claim 1 is characterized in that: H in the nitration mixture
2SO
4With the mol ratio of HCl be 1:2-4, H
3PO
3With the mol ratio of HCl be 1:3-4.
3. synthetic method according to claim 1 is characterized in that: the H in iminodiacetonitrile and the nitration mixture
+Mol ratio be 1:3-5.
4. according to claim 1,2 or 3 described synthetic methods, it is characterized in that: the hydrolysis under High Temperature High Pressure, carry out, temperature is 130 ℃-160 ℃, pressure is 0.5Mpa-10Mpa.
5. synthetic method according to claim 4, it is characterized in that: hydrolysis time is 1-10h.
6. synthetic method according to claim 4 is characterized in that: during hydrolysis, add rare gas element and keep high pressure.
7. synthetic method according to claim 4 is characterized in that: be hydrolyzed complete after, reacting liquid temperature is down to 80-90 ℃, Pressure Drop is carried out next step reaction to normal pressure again.
8. synthetic method according to claim 1, it is characterized in that: the massfraction of nitration mixture aqueous acid medium is 20%-50%.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN105524107A (en) * | 2014-09-30 | 2016-04-27 | 北京紫光英力化工技术有限公司 | New process for clean production of pmida and cyclic utilization of byproducts |
| CN108912168A (en) * | 2018-08-10 | 2018-11-30 | 泰兴市飞天化工有限公司 | A method of preparing pmida |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105524107A (en) * | 2014-09-30 | 2016-04-27 | 北京紫光英力化工技术有限公司 | New process for clean production of pmida and cyclic utilization of byproducts |
| 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 |
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