CN103319359A - Production method of iminodiacetic acid - Google Patents
Production method of iminodiacetic acid Download PDFInfo
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- CN103319359A CN103319359A CN2013103085806A CN201310308580A CN103319359A CN 103319359 A CN103319359 A CN 103319359A CN 2013103085806 A CN2013103085806 A CN 2013103085806A CN 201310308580 A CN201310308580 A CN 201310308580A CN 103319359 A CN103319359 A CN 103319359A
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Abstract
The invention discloses a production method of iminodiacetic acid. The production method comprises the following steps of: 1) mixing iminodiacetonitrile with hydrochloric acid to carry out heating reaction, wherein the molar ratio of the hydrochloric acid to the iminodiacetonitrile is (3-5):1, keeping the reaction temperature at 75-100 DEG C and the reaction time at 1-5 hours, so as to generate iminodiacetic acid and ammonium chloride; 2) cooling and crystallizing a reaction liquid obtained in the step 1), separating out crystal and mother liquor, and taking the crystal as a crude product of the iminodiacetic acid; and 3) re-crystallizing and purifying the crude product of the iminodiacetic acid obtained in the step 2) to obtain the iminodiacetic acid product. By adopting the hydrochloric acid hydrolysis process, the defect that low-value sodium salt is generated by alkaline hydrolysis is avoided; meanwhile, the defects of a lot of by-products generated by sulfuric acid hydrolysis, and high possibility of carbonization, resulting in low product quality are avoided; the defect that mixed ammonium salt generated by mixed acid (hydrochloric acid and sulfuric acid or phosphorous acid) is difficultly processed also can be avoided; and the high-quality iminodiacetic acid product and ammonium chloride can be obtained.
Description
Technical field
The present invention relates to the synthesis technical field of iminodiethanoic acid, be specifically related to a kind of iminodiacetonitrile of utilizing and be the method for raw material production iminodiethanoic acid.
Background technology
Iminodiethanoic acid (being called for short IDA) has another name called Diglycocol, amino oxalic acid, and molecular formula is NH (CH
2COOH)
2Iminodiethanoic acid is important source material and the intermediate of agricultural chemicals, pharmacy, rubber, tensio-active agent, complexing agent, foodstuff additive, electroplating industry, synthetic metal conditioner and ion exchange resin thereof etc.
Domestic industry production iminodiethanoic acid method mainly contains three kinds, prussic acid method, chloroactic acid method, diethanolamine method.The chloroactic acid method technical maturity, but long flow path, product purity is low, cost is high, " three wastes " are serious, and can only produce aqua, be tending towards superseded.Diethanolamine method is one step of the diethanolamine new technology of the external exploitation nineties, China has also carried out the exploitation of this route, obtained success, now actively promoting this technology, these method raw material sources are extensive, and technical process is short, by product is few, product purity is high, still, the cost of material that this method is produced iminodiethanoic acid is high, and profit margin is little.Then prussic acid method production iminodiacetonitrile is hydrolyzed the production iminodiethanoic acid, is one of method of mainly taking both at home and abroad, is comparatively ripe operational path.
Number of patent application 200710090976.2 application people are " a kind of clean preparation method for preparing pmida98 take hydroxyacetonitrile as the raw material one kettle way " of Qinghuaziguang Yingli Chemical Technology Co. Ltd., Beijing, the method of narration is with the iminodiacetonitrile sodium hydroxide hydrolysis, the hcl acidifying synthesis of iminodiacetic acid, consume a large amount of sodium hydroxide and hydrochloric acid, the wastewater treatment difficulty of byproduct sodium chloride and sodium chloride-containing is large.
" a kind of clean preparation method for preparing pmida98 take hydroxyacetonitrile as the raw material one kettle way " technique shortcoming for the Qinghuaziguang Yingli Chemical Technology Co. Ltd., Beijing, number of patent application 201010011402.3 application people are " a kind of environmental-friendly new method that utilizes vinyl cyanide coproduct hydrogen cyanic acid to prepare N-phosphonomethyl iminodiethanoic acid " of Zibo Wan Chang Science and Technology Co., Ltd., the method of narration is to adopt the iminodiacetonitrile sulphuric acid hydrolysis, the Recycling Mother Solution of getting behind the ammonium salt is applied mechanically, and greatly reduces the discharging of waste water.But, sulphuric acid hydrolysis is two-step reaction, elder generation's amidate action generates imino-diacetic ethanamide vitriol, hydrolysis reaction generates iminodiethanoic acid again, two-step reaction easily produces more by product, and sulfuric acid process is hydrolyzed easy carbonization, and the iminodiethanoic acid and the ammonium sulfate that obtain are chocolate, and product quality is low.
Number of patent application 201210561150.0 application people be mixing acid under high pressure hydrolysis iminodiethanoic acid and then the synthetic pmida98 of " a kind of synthetic method of pmida98 " employing hydrochloric acid of Shandong Weifang Rainbow Chemical Co., Ltd. and sulfuric acid or phosphorous acid, this method has been avoided the shortcoming of alkali process hydrolysis, but the mixture of side product sodium chloride and ammonium sulfate or ammonium phosphite, there is more unmanageable shortcoming in mixed-ammonium salt.
More than utilize the iminodiacetonitrile hydrolysis to prepare the method for iminodiethanoic acid, all be faced with sodium hydroxide at present and be hydrolyzed, want to obtain iminodiethanoic acid and all must carry out acidifying, produce a large amount of large sodium salts of value reduction process difficulty, cause the partial loss of product iminodiethanoic acid and the generation of a large amount of brine waste.Also there are various defectives in the acid system direct hydrolysis of having reported.
Summary of the invention
In view of this, the invention provides a kind of iminodiethanoic acid production method, can avoid basic hydrolysis to produce the shortcoming of low value sodium salt, also can avoid sulfuric acid process hydrolysis prods quality to hang down with nitration mixture simultaneously and be hydrolyzed the shortcoming that produces mixed-ammonium salt.
The production method of iminodiethanoic acid of the present invention may further comprise the steps:
1) with iminodiacetonitrile and mixed in hydrochloric acid reacting by heating, the mol ratio of hydrochloric acid and iminodiacetonitrile is 3～5:1, and temperature of reaction keeps 75～100 ℃, in 1～5 hour reaction times, generates iminodiethanoic acid and ammonium chloride;
2) the reaction solution crystallisation by cooling that step 1) is obtained is isolated crystal and mother liquor, and crystal is the iminodiacetic acid (salt) acid crude;
3) with step 2) obtain the iminodiacetic acid (salt) acid product behind the iminodiacetic acid (salt) acid crude recrystallization purifying that obtains.
Further, in the described step 1), the hybrid mode of iminodiacetonitrile and hydrochloric acid is: after iminodiacetonitrile is heated to molten state, drip hydrochloric acid under the confined reaction system, perhaps under the confined reaction system with after the hydrochloric acid heating, add iminodiacetonitrile in batches.
Further, in the described step 1), the mass concentration of hydrochloric acid is 20%～37%.
Further, with step 2) the crude product crystalline mother solution underpressure distillation of gained is concentrated, and crystallisation by cooling is then isolated ammonium chloride and has been separated the residual mother liquor behind the ammonium chloride and return and apply mechanically to step 1).
Further, in the described step 3), the iminodiacetic acid (salt) acid crude is added the water heating for dissolving, add activated carbon decolorizing, then remove by filter gac, filtrate is regulated pH to 2.0～3.0 with ammoniacal liquor or ammonia, cools off recrystallization again, isolate recrystallization crystal and recrystallization mother liquor, obtain the iminodiacetic acid (salt) acid product after the washing of recrystallization crystal, the drying.
Further, with the recrystallization mother liquor recycled of step 3) gained in iminodiacetic acid (salt) acid crude recrystallization.
Beneficial effect of the present invention is:
1) the present invention adopts hydrochloric acid hydrolysis technique, and its reaction formula is:
Hydrochloric acid and iminodiacetonitrile direct reaction generate iminodiethanoic acid and ammonium chloride, avoided basic hydrolysis to produce the shortcoming of low value sodium salt, thereby can avoid many, the easy carbonization of sulfuric acid process hydrolysising by-product to cause the low shortcoming of product quality simultaneously, also can avoid nitration mixture (hydrochloric acid and sulfuric acid or phosphorous acid) to produce the reluctant shortcoming of mixed-ammonium salt, can obtain high-quality iminodiacetic acid (salt) acid product and ammonium chloride;
2) the crude product crystalline mother solution behind the concentration and recovery ammonium chloride and recrystallization mother liquor are applied mechanically respectively to lower batch of reaction corresponding steps, reaction mother liquor can be applied mechanically fully, the iminodiethanoic acid that wherein contains utilizes recovery fully again, increased yield, and greatly reducing the consumption of water, is environment-friendly clean process;
3) iminodiethanoic acid greatly reduces the accumulation of foreign pigment through behind the activated carbon decolorizing, and the iminodiacetic acid (salt) acid product that obtains is white powder, superior product quality.
Embodiment
Below will be described in detail the preferred embodiments of the present invention.
Embodiment 1
The production method of the iminodiethanoic acid of the present embodiment may further comprise the steps:
1) in 2000mL four-hole round bottom reaction flask, adds iminodiacetonitrile 200g (content 95%, 2mol), being heated to 75 ℃ makes it be in molten state, the confined reaction system, stir the lower 37% hydrochloric acid 690.5g (7mol) of dropping, add rear 100 ℃ of insulations 2 hours, the iminodiacetonitrile primitive reaction is complete, generates iminodiethanoic acid and ammonium chloride;
2) reaction solution that step 1) is obtained is cooled to 20 ℃ and keep crystallization in 2 hours, filters, and filter cake 100g water washing gets iminodiacetic acid (salt) acid crude 275g, crude product crystalline mother solution 660g;
3) with step 2) the iminodiacetic acid (salt) acid crude of gained and 3g gac, 550g water adds in the 2000mL four-hole boiling flask, is heated to boiling, stirred 1 hour, filtered while hot is removed gac, filtrate is regulated pH=2.0 with ammoniacal liquor, is cooled to 20 ℃ and keep 3 hours recrystallizations, separates out a large amount of solids, filter, filter cake 30g water washing, dry iminodiacetic acid (salt) acid product 249.5g, the content 98.5% of getting, yield 92.4%, recrystallization mother liquor 550g;
4) with step 2) the crude product crystalline mother solution underpressure distillation of gained is concentrated, steams 380g water, is cooled to 10 ℃ of crystallizations, filters, dry ammonium chloride 175g, residual mother liquor 101g.
Embodiment 2
The production method of the iminodiethanoic acid of the present embodiment may further comprise the steps:
1) in 2000mL four-hole round bottom reaction flask, adds the residual mother liquor of step 4) among the 101g embodiment 1, then add iminodiacetonitrile 200g (content 95%, 2mol), be heated to 75 ℃, the confined reaction system stirs the lower 37% hydrochloric acid 690.5g (7mol) of dropping, adds rear 100 ℃ of insulations 2.5 hours, the iminodiacetonitrile primitive reaction is complete, generates iminodiethanoic acid and ammonium chloride;
2) reaction solution that step 1) is obtained is cooled to 20 ℃ and keep crystallization in 2 hours, filters, and filter cake 100g water washing gets iminodiacetic acid (salt) acid crude 288g, crude product crystalline mother solution 750g;
3) with step 2) step 3) gained recrystallization mother liquor 550g adds in the 2000mL four-hole boiling flask among the iminodiacetic acid (salt) acid crude of gained and 3g gac, the embodiment 1, is heated to boiling, stirred 1 hour, filtered while hot is removed gac, filtrate is regulated pH=2.0 with ammoniacal liquor, is cooled to 20 ℃ and keep 3 hours recrystallizations, separates out a large amount of solids, filter, filter cake 30g water washing, dry iminodiacetic acid (salt) acid product 253.8g, the content 98.2% of getting, yield 93.7%, recrystallization mother liquor 564g;
4) with step 2) the crude product crystalline mother solution underpressure distillation of gained is concentrated, steams 427g water, is cooled to 10 ℃ of crystallizations, filters, dry ammonium chloride 187g, residual mother liquor 116g.
Among the present invention, the mol ratio of hydrochloric acid and iminodiacetonitrile is 3～5:1, and temperature of reaction keeps 75～100 ℃, in 1～5 hour reaction times, all can realize purpose of the present invention; And the hybrid mode of iminodiacetonitrile and hydrochloric acid drips the hydrochloric acid after iminodiacetonitrile being heated to molten state under the confined reaction system, can also under the confined reaction system with after the hydrochloric acid heating, add iminodiacetonitrile in batches, the confined reaction system has been avoided the pollution of unlimited system hydrochloric acid volatilization and operating environment, and the mass concentration of used hydrochloric acid is 20%～37%.
Explanation is at last, above embodiment is only unrestricted in order to technical scheme of the present invention to be described, although by invention has been described with reference to the preferred embodiments of the present invention, but those of ordinary skill in the art is to be understood that, can make various changes to it in the form and details, and not depart from the spirit and scope of the present invention that appended claims limits.
Claims (6)
1. the production method of an iminodiethanoic acid is characterized in that: may further comprise the steps:
1) with iminodiacetonitrile and mixed in hydrochloric acid reacting by heating, the mol ratio of hydrochloric acid and iminodiacetonitrile is 3～5:1, and temperature of reaction keeps 75～100 ℃, in 1～5 hour reaction times, generates iminodiethanoic acid and ammonium chloride;
2) the reaction solution crystallisation by cooling that step 1) is obtained is isolated crystal and mother liquor, and crystal is the iminodiacetic acid (salt) acid crude;
3) with step 2) obtain the iminodiacetic acid (salt) acid product behind the iminodiacetic acid (salt) acid crude recrystallization purifying that obtains.
2. the production method of iminodiethanoic acid according to claim 1, it is characterized in that: in the described step 1), the hybrid mode of iminodiacetonitrile and hydrochloric acid is: after iminodiacetonitrile is heated to molten state, drip hydrochloric acid under the confined reaction system, perhaps under the confined reaction system with after the hydrochloric acid heating, add iminodiacetonitrile in batches.
3. the production method of iminodiethanoic acid according to claim 1, it is characterized in that: in the described step 1), the mass concentration of hydrochloric acid is 20%～37%.
4. the production method of iminodiethanoic acid according to claim 1, it is characterized in that: with step 2) the crude product crystalline mother solution underpressure distillation of gained is concentrated, then crystallisation by cooling is isolated ammonium chloride, has separated the residual mother liquor behind the ammonium chloride and has returned and apply mechanically to step 1).
5. the production method of iminodiethanoic acid according to claim 1, it is characterized in that: in the described step 3), the iminodiacetic acid (salt) acid crude is added the water heating for dissolving, add activated carbon decolorizing, then remove by filter gac, filtrate is regulated pH to 2.0～3.0 with ammoniacal liquor or ammonia, cools off recrystallization again, isolate recrystallization crystal and recrystallization mother liquor, obtain the iminodiacetic acid (salt) acid product after the washing of recrystallization crystal, the drying.
6. the production method of iminodiethanoic acid according to claim 5 is characterized in that: with the recrystallization mother liquor recycled of step 3) gained in iminodiacetic acid (salt) acid crude recrystallization.
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Cited By (7)
| 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 |
| CN105017047A (en) * | 2015-06-16 | 2015-11-04 | 重庆紫光化工股份有限公司 | Iminodiacetic acid production method and iminodiacetic acid production apparatus |
| CN105175444A (en) * | 2015-09-11 | 2015-12-23 | 重庆华歌生物化学有限公司 | Novel method of preparing N-phosphonomethyl iminodiacetic acid |
| CN108912168A (en) * | 2018-08-10 | 2018-11-30 | 泰兴市飞天化工有限公司 | A method of preparing pmida |
| CN111100022A (en) * | 2019-10-30 | 2020-05-05 | 石家庄市栾城区华英工贸有限责任公司 | Method for preparing carboxylic acid compounds by catalyzing nitrile compounds to hydrolyze with Lewis acid |
| TWI779994B (en) * | 2022-01-21 | 2022-10-01 | 臺灣永光化學工業股份有限公司 | Method for purification of iminodiacetic acid |
| CN115141111A (en) * | 2022-07-29 | 2022-10-04 | 苏州科熔新材料技术研究有限公司 | Technology for preparing IDA from ammonium bicarbonate |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
2013
- 2013-07-22 CN CN2013103085806A patent/CN103319359A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Cited By (8)
| 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 |
| CN105017047A (en) * | 2015-06-16 | 2015-11-04 | 重庆紫光化工股份有限公司 | Iminodiacetic acid production method and iminodiacetic acid production apparatus |
| CN105175444A (en) * | 2015-09-11 | 2015-12-23 | 重庆华歌生物化学有限公司 | Novel method of preparing N-phosphonomethyl iminodiacetic acid |
| CN105175444B (en) * | 2015-09-11 | 2018-01-19 | 重庆华歌生物化学有限公司 | A kind of new method for preparing 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 |
| CN111100022A (en) * | 2019-10-30 | 2020-05-05 | 石家庄市栾城区华英工贸有限责任公司 | Method for preparing carboxylic acid compounds by catalyzing nitrile compounds to hydrolyze with Lewis acid |
| TWI779994B (en) * | 2022-01-21 | 2022-10-01 | 臺灣永光化學工業股份有限公司 | Method for purification of iminodiacetic acid |
| CN115141111A (en) * | 2022-07-29 | 2022-10-04 | 苏州科熔新材料技术研究有限公司 | Technology for preparing IDA from ammonium bicarbonate |
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Application publication date: 20130925 |