CN101092369A - Method for preparing iminodiacetic acid by using raw material of hydroxy acetonitrile - Google Patents
Method for preparing iminodiacetic acid by using raw material of hydroxy acetonitrile Download PDFInfo
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- CN101092369A CN101092369A CN 200610090115 CN200610090115A CN101092369A CN 101092369 A CN101092369 A CN 101092369A CN 200610090115 CN200610090115 CN 200610090115 CN 200610090115 A CN200610090115 A CN 200610090115A CN 101092369 A CN101092369 A CN 101092369A
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- acid
- hydroxyacetonitrile
- ammonium
- salt
- iminodiethanoic
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Abstract
This invention provides a 'one-pot' method for preparing and separating iminodiacetic acid from hydroxyl acetonitrile. The method has such advantages as high yield, little waste discharge, and easy preparation and purification of the product.
Description
Technical field
The present invention relates to a kind of is the method for feedstock production iminodiethanoic acid and salt thereof with the hydroxyacetonitrile, and specifically, relating to the hydroxyacetonitrile is the method that raw material is synthetic by the acidolysis single stage method and separate iminodiethanoic acid.
Background technology
Domestic industry production iminodiethanoic acid method mainly contains three kinds of hydrocyanic acid method, chloroactic acid method and diethanolamine methods.The chloroactic acid method technical maturity, but long flow path, product purity is low, cost is high, " three wastes " are serious, has been to eliminate technology.Diethanolamine method is the new technology of the external exploitation nineties, and this method is main raw material with the diethanolamine, and in the presence of high temperature (170 ℃), high pressure (0.8Mp) and Cu-Ni alloy catalyst and sodium hydroxide, oxydehydrogenation generates iminodiacetic acid sodium.This method requires high to equipment, catalyzer, have potential safety hazard, and the raw material diethanolamine causes production cost higher because of influenced by crude oil price, has the restriction of economy such as the three wastes and catalyst deactivation, technology, environmental factors simultaneously, and the competitive power of this technology is not strong.
The prussic acid method is generally good both at home and abroad method, U.S. Pat P5,187,301 have reported with the hydroxyacetonitrile interrupter method and have prepared iminodiacetonitrile, use sodium hydroxide hydrolysis, acidifying then, crystallization, separate, prepare the method for iminodiethanoic acid, at present extensively good or employing by relevant producer, but this method reaction preference is poor, divide in the process to depolymerize seriously, easily produce tar, the aftertreatment complexity, the solid-liquid separation number of times is too many, the safety and environmental protection problem that exists a small amount of prussic acid and ammonia to overflow when having solid-liquid separation simultaneously, the waste water that aminoacetonitriles and iminodiacetonitrile produce are difficult to handle, and must handle by the incinerator of with high investment and highly energy-consuming; Ammonia recovery is low, and investment is big, and ammonia concn is low, and use value is poor; Iminodiethanoic acid has only about 60% the yield of hydroxyacetonitrile.
At above-mentioned defective, the contriver is through studying for a long period of time and exploring, invented that to be raw material with the hydroxyacetonitrile prepare the method for iminodiethanoic acid by the acidolysis single stage method, fundamentally overcome the deficiency of former alkali process, reached the purpose of cleaner production and comprehensive utilization of resources.
Summary of the invention
The purpose of this invention is to provide a kind of is the method for feedstock production iminodiethanoic acid with the hydroxyacetonitrile.The characteristics of this method are: ammonification, acidolysis " are treated different things alike ", without separating the salt that directly obtains iminodiethanoic acid, by adjusting the difference of acidity and product solubility, the dissolving difference of product and ammonium salt by product obtains the iminodiacetic acid (salt) acid product again, the present invention have the reaction and sepn process simple, the yield height, the use of having saved caustic soda can side product sodium chloride, three-waste free discharge, production cost is low, and many-sided advantages such as raw material availability height are a kind of preparation technologies of clean environment firendly.
In specific embodiments, when for example adopting hydrochloric acid as the acidolysis raw material, the inventive method can be represented with following reaction formula:
2HOCH
2CN+NH
3→NH(CH
2CN)
2+2H
2O
NH(CH
2CN)
2+3HCl+4H
2O→NH(CH
2COOH)
2HCl+2NH
4Cl
NH(CH
2COOH)
2HCl+NH
3→NH(CH
2COOH)
2+NH
4Cl.
Specifically, the invention provides a kind of is the novel method of raw material direct production iminodiethanoic acid with the hydroxyacetonitrile, and this method comprises the steps:
1) under heating condition, for example 60-180 ℃, be preferably 80-150 ℃, to hydroxyacetonitrile solution, be preferably in hydroxyacetonitrile and the ammonium salt in catalysis agent composition, dropping ammonia or feeding ammonia, reaction obtains ammonification liquid, is iminodiacetonitrile solution.
2) directly drip excessive mineral acid to preferred ammonification liquid without crystallisation by cooling, at 0-180 ℃, preferred 60-150 ℃ of reaction down, reaction obtains acid hydrolysis solution, is iminodiethanoic acid inorganic acid salt and ammonium salt mixed solution.
3) preferably in the presence of excess acid, acid hydrolysis solution is carried out aftertreatment, obtain the inorganic acid salt of iminodiethanoic acid, perhaps iminodiethanoic acid for example, cools off, crystallization, separation, obtain the inorganic acid salt and the ammonium salt mixture crude product of iminodiethanoic acid, through the pure product that obtain the iminodiethanoic acid inorganic acid salt that recrystallization gets final product, also acid hydrolysis solution or above-mentioned crude product (for example adopting ammoniacal liquor) can be regulated about pH value to 2, obtain the pure product of iminodiethanoic acid.
In the above-mentioned steps, the mol ratio of hydroxyacetonitrile and ammonia is 1: 0.1～1 to be preferably 1: 0.3-0.8; The mol ratio of hydroxyacetonitrile and ammonium salt in catalysis agent is 1: 0.01～0.5, is preferably 1: 0.1-0.4; The mol ratio of hydroxyacetonitrile and mineral acid is 1: 1～2.5, is preferably 1: 1.4-2.
The ammonium salt in catalysis agent can be the inorganic acid ammonium salt that is selected from ammonium sulfate, ammonium chloride, volatile salt, ammonium nitrate or ammonium phosphate etc., also can be the organic acid ammonium salt that is selected from ammonium acetate or ammonium formiate etc.; Mineral acid can be selected from sulfuric acid, hydrochloric acid, nitric acid or phosphoric acid etc.Look the ammonium salt in catalysis agent of employing and the situation of mineral acid, the ammonium salt in catalysis agent can be identical or different with the ammonium salt that reaction generates, and the ammonium chloride of by-product can be used as preferred catalyzer.
The iminodiethanoic acid product analysis content of the inventive method preparation can reach more than 98.5%, meets the service requirements of pmida98 fully, and can reach more than 80% the hydroxyacetonitrile yield.
The present invention adopts behind the first synthesizing iminodiacetic acid (salt) nitrile the directly method of acid hydrolysis, the reaction conditions gentleness, reduced steps such as separating and add liquid caustic soda, reduced investment and reduced raw materials cost, this reaction has the selectivity height, light-colored characteristics, can prevent effectively that side reactions such as polymerization, decomposition from taking place, need not specific installation, can reduce investment outlay widely, simplify the operation, reduce cost.Mother liquor can recycled because of effective separation of ammonium chloride, has fundamentally solved hydroxyacetonitrile technology and has been difficult to the problem handling and utilize because of waste water, and the ammonium chloride of generation can be used as commodity selling, perhaps as the raw material of synthetic hydrochloric acid and ammonia and other ammonium salt.
In sum, to be raw material with the hydroxyacetonitrile prepare the method for iminodiethanoic acid by the acidolysis single stage method to the inventive method, fundamentally overcome the deficiency of former alkali process, and raw materials used preparation purifying is easy, and security is good, is easy to transportation and storage.
Application of the present invention is not limited only to the method for the treatment of different things alike, and adopts iminodiacetonitrile and synthesis mother liquid thereof to carry out the synthetic and COMPREHENSIVE UTILIZATION OF WASTES FROM of iminodiethanoic acid, is a kind of remodeling form of the inventive method.Therefore, in another embodiment, the ammonification liquid of step 1) of the present invention can adopt iminodiacetonitrile solution or other method synthetic iminodiacetonitrile and synthesis mother liquid thereof to substitute.
Embodiment
Embodiment 1
In 1000 milliliters reaction flask, add hydroxyacetonitrile (50%) 500 gram (4.39mol), stir and add ammonium chloride 38.5 grams (0.72mol) down, heat to system then, when being heated to 110 ℃, begin to add ammoniacal liquor, the rate of addition of control ammoniacal liquor, between 5～8, the temperature of controlling reaction system simultaneously is between 110～130 ℃ with the pH value that guarantees reaction solution.After adding ammoniacal liquor (25%) 158 gram (2.3mol), can stop to drip, continue 110-130 ℃ of insulation 2 hours, reaction solution is transferred in 2000 milliliters the reaction flask.36% the concentrated hydrochloric acid that adds 865 grams (8.53mol) is after hydrochloric acid adds, 80～150 ℃ of following insulation reaction 4 hours, cool then, when temperature dropped to 10 ℃, suction filtration obtained mixture 484.8 grams of Iminodiacetate hydrochlorate and ammonium chloride, and folding hundred yields in kind are 75%.Reaction mother liquor is applied mechanically, and crude product can obtain qualified product through recrystallization.
The gained crude product is with 485 gram water recrystallizations, obtains content and be 98.3% pure product 94.5 grams (0.55mol) of Iminodiacetate hydrochlorate, and yield is 25%.Mother liquid obtainedly transfer pH value to 2 with ammonia, separate out solid, stirring suction filtration after 0.5 hour, to obtain content be that 98.2% iminodiethanoic acid 149 restrains (1.1mol), and yield is 48%, and then total yield is 73%.Crystalline mother solution is waited until down to criticize and is applied mechanically after concentrating cooling filtering ammonium chloride.
Embodiment 2
In 1000 milliliters reaction flask, add hydroxyacetonitrile (50%) 500 gram (4.39mol), stir and add ammonium chloride 38.5 grams (0.72mol) down, heat to system then, when being heated to 110 ℃, begin to add ammoniacal liquor, the rate of addition of control ammoniacal liquor, between 5～8, the temperature of controlling reaction system simultaneously is between 110～130 ℃ with the pH value that guarantees reaction solution.After adding ammoniacal liquor (25%) 158 gram (2.3mol), can stop to drip, continue 110-130 ℃ of insulation 2 hours, reaction solution is transferred in 2000 milliliters the reaction flask.
Add 865 grams (8.53mol) by 36% formulated concentrated hydrochloric acid of last batch mother liquor and water blended absorbent hydrogen chloride gas, after hydrochloric acid adds, 80～150 ℃ of following insulation reaction 4 hours, cool then, when temperature drops to 10 ℃, suction filtration obtains mixture 568.8 grams of Iminodiacetate hydrochlorate and ammonium chloride, and folding hundred yields in kind are 88%.Reaction mother liquor is applied mechanically, and crude product is made with extra care.
The gained crude product is with 570 gram water recrystallizations, obtains content and be 98% pure product 111.9 grams (0.65mol) of Iminodiacetate hydrochlorate, and yield is 29.5%.Mother liquid obtainedly transfer pH value to 2 with ammonia, separate out solid, stirring suction filtration after 0.5 hour, to obtain content be that 98.4% iminodiethanoic acid 169 restrains (1.25mol), and yield is 57%, and then total yield is 86.5%.Crystalline mother solution is waited until down to criticize and is applied mechanically after concentrating cooling filtering ammonium chloride.
Embodiment 3
In 1000 milliliters reaction flask, add hydroxyacetonitrile (50%) 500 gram (4.39mol), stir and add ammonium chloride 38.5 grams (0.72mol) down, heat to system then, when being heated to 110 ℃, begin to add ammoniacal liquor, the rate of addition of control ammoniacal liquor, between 5～8, the temperature of controlling reaction system simultaneously is between 110～130 ℃ with the pH value that guarantees reaction solution.After adding ammoniacal liquor (25%) 158 gram (2.3mol), can stop to drip, continue 110-130 ℃ of insulation 2 hours, reaction solution is transferred in 2000 milliliters the reaction flask.
Add 865 grams (8.53mol) by 36% formulated concentrated hydrochloric acid of last batch mother liquor and water blended absorbent hydrogen chloride gas, after hydrochloric acid adds, 80～150 ℃ of following insulation reaction 4 hours, cool then, when temperature drops to 10 ℃, suction filtration obtains mixture 568.8 grams of Iminodiacetate hydrochlorate and ammonium chloride, and folding hundred yields in kind are 88%.Reaction mother liquor is applied mechanically, and crude product is made with extra care.
The gained crude product is with 500 gram water dissolution, and feeding ammonia or ammoniacal liquor, to transfer pH be 2, separates out solid, and stirring suction filtration after 0.5 hour, to obtain content be that 98.4% iminodiethanoic acid 252 restrains (1.25mol), and yield is 85%.Crystalline mother solution is waited until down to criticize and is applied mechanically after concentrating cooling filtering ammonium chloride.
The comparative example 1
In 500 milliliters reaction flask, add hydroxyacetonitrile (50%) 250 gram (2.2mol), begin heating, when being heated to 110 ℃, begin to add ammoniacal liquor, the rate of addition of control ammoniacal liquor, between 5～8, after adding ammoniacal liquor (25%) 80 gram (1.18mol), stop dropping with the pH value that guarantees reaction solution, continuation was 110-130 ℃ of insulation 2 hours, cool, suction filtration separates that to obtain content be 95% iminodiacetonitrile 76.76 grams (0.77mol), and yield is 70%.
The iminodiacetonitrile of gained is mixed with 230 gram water, stir and drip (30%) 205 gram (1.54mol) white liquor down, controlled temperature is at 50-60 ℃ in the process, after dropwising, it is 50% Iminodiacetic acid sodium salt salt 174.68 grams (0.49mol) that 50-60 ℃ of insulation 4 little (time the ammonia that produces of vacuum removal alkaline hydrolysis) simultaneously, crystallisation by cooling, suction filtration obtain content, the mother liquor decompression dehydration obtains content and is 35% Iminodiacetic acid sodium salt salt 83.18 grams (0.16mol).
The two batches of solids of above gained are merged with 200 gram water dissolution, use hydrochloric acid adjust pH to 2 then, have iminodiethanoic acid to separate out, it is that 98% iminodiethanoic acid 74.4 restrains (0.55mol) that suction filtration obtains content.After mother liquor removes sodium-chlor, obtain iminodiethanoic acid 7.68 grams (0.05mol) once more, content is 95%, and then iminodiethanoic acid is 55% with respect to total yield of hydroxyacetonitrile.
Claims (10)
1, a kind of is the method for raw material production iminodiethanoic acid with the hydroxyacetonitrile, and this method comprises the steps:
1) to hydroxyacetonitrile solution, perhaps dropping ammonia or feed ammonia in hydroxyacetonitrile and the ammonium salt in catalysis agent composition, reaction obtains ammonification liquid;
2) directly drip excessive mineral acid to ammonification liquid, reaction obtains acid hydrolysis solution;
3) acid hydrolysis solution is carried out aftertreatment, obtain the inorganic acid salt of iminodiethanoic acid, perhaps iminodiethanoic acid.
2, according to the method for claim 1, this method comprises the steps:
1) under heating condition, to hydroxyacetonitrile solution, perhaps in hydroxyacetonitrile and the ammonium salt in catalysis agent composition, dropping ammonia or feed ammonia, reaction obtains ammonification liquid;
2) directly drip excessive mineral acid to ammonification liquid,, obtain acid hydrolysis solution 60-150 ℃ of reaction down without crystallisation by cooling;
3) in the presence of excess acid, acid hydrolysis solution is carried out aftertreatment, obtain the inorganic acid salt of iminodiethanoic acid, perhaps iminodiethanoic acid.
3, according to the method for claim 2, this method comprises the steps:
1) under 60-180 ℃, in hydroxyacetonitrile and the ammonium salt in catalysis agent composition, dropping ammonia or feeding ammonia, reaction obtains ammonification liquid;
2) directly drip excessive mineral acid to ammonification liquid,, obtain acid hydrolysis solution 60-150 ℃ of reaction down without crystallisation by cooling;
3) in the presence of excess acid, with acid hydrolysis solution cool off, crystallization, separation, obtain the inorganic acid salt and the ammonium salt mixture crude product of iminodiethanoic acid, obtain the pure product of iminodiethanoic acid inorganic acid salt through recrystallization, perhaps adopt ammoniacal liquor to regulate about pH value to 2 acid hydrolysis solution or above-mentioned crude product, obtain the pure product of iminodiethanoic acid.
4, according to the arbitrary described method of claim 1-3, wherein, the mol ratio of hydroxyacetonitrile and ammonia is 1: 0.1～1 in the step 1), is preferably 0.3-0.8.
5, the mol ratio of hydroxyacetonitrile and mineral acid is 1: 1～2.5 according to the arbitrary described method of claim 1-4, wherein, step 2), is preferably 1: 1.4-2.
6, according to the arbitrary described method of claim 1-5, wherein, the mol ratio of hydroxyacetonitrile and ammonium salt in catalysis agent is 1: 0.01～0.5 in the step 1), is preferably 1: 0.1-0.4.
7, according to the arbitrary described method of claim 1-6, wherein, the pH value in reaction in the step 1) is controlled at 5-8.
8, according to the arbitrary described method of claim 1-7, wherein, the ammonium salt in catalysis agent is the inorganic acid ammonium salt that is selected from ammonium sulfate, ammonium chloride, volatile salt, ammonium nitrate or ammonium phosphate, or is selected from the organic acid ammonium salt of ammonium acetate or ammonium formiate, is preferably ammonium chloride.
9, according to the arbitrary described method of claim 1-8, wherein, mineral acid is to be selected from sulfuric acid, hydrochloric acid, nitric acid or phosphoric acid, is preferably hydrochloric acid.
10, according to the arbitrary described method of claim 1-9, wherein, the ammonification liquid of step 1) can adopt iminodiacetonitrile solution, and perhaps the mixed solution of iminodiacetonitrile and its synthesis mother liquid substitutes.
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|---|---|---|---|
| CNB200610090115XA CN100558699C (en) | 2006-06-23 | 2006-06-23 | A kind of is the method for feedstock production iminodiethanoic acid with the hydroxyacetonitrile |
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| CNB200610090115XA CN100558699C (en) | 2006-06-23 | 2006-06-23 | A kind of is the method for feedstock production iminodiethanoic acid with the hydroxyacetonitrile |
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| CN100558699C CN100558699C (en) | 2009-11-11 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009079861A1 (en) * | 2007-12-25 | 2009-07-02 | Beijing Unis Insight Chemical Technology Co., Ltd. | Method for preparing iminodiacetic acid by using raw material of hydroxy acetonitrile |
| CN101445464B (en) * | 2008-12-25 | 2012-09-05 | 广西壮族自治区化工研究院 | Method for preparing iminodiacetic acid from iminodiacetic acid disodium salt |
| CN103012473A (en) * | 2012-12-21 | 2013-04-03 | 山东潍坊润丰化工有限公司 | Synthesis method of N-(Phosphonomethyl) iminodiacetic acid |
| CN103232355A (en) * | 2013-04-25 | 2013-08-07 | 重庆紫光化工股份有限公司 | Environmentally-friendly clean production method of iminodiacetic acid |
| CN103265443A (en) * | 2013-06-05 | 2013-08-28 | 重庆紫光化工股份有限公司 | Industrial production method of high-purity iminodiacetic acid |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5187301A (en) * | 1989-10-26 | 1993-02-16 | W. R. Grace & Co.-Conn. | Preparation of iminodiacetonitrile from glycolonitrile |
-
2006
- 2006-06-23 CN CNB200610090115XA patent/CN100558699C/en active Active
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009079861A1 (en) * | 2007-12-25 | 2009-07-02 | Beijing Unis Insight Chemical Technology Co., Ltd. | Method for preparing iminodiacetic acid by using raw material of hydroxy acetonitrile |
| CN101445464B (en) * | 2008-12-25 | 2012-09-05 | 广西壮族自治区化工研究院 | Method for preparing iminodiacetic acid from iminodiacetic acid disodium salt |
| CN103012473A (en) * | 2012-12-21 | 2013-04-03 | 山东潍坊润丰化工有限公司 | Synthesis method of N-(Phosphonomethyl) iminodiacetic acid |
| CN103012473B (en) * | 2012-12-21 | 2016-03-02 | 山东潍坊润丰化工股份有限公司 | A kind of synthetic method of pmida98 |
| CN103232355A (en) * | 2013-04-25 | 2013-08-07 | 重庆紫光化工股份有限公司 | Environmentally-friendly clean production method of iminodiacetic acid |
| CN103265443A (en) * | 2013-06-05 | 2013-08-28 | 重庆紫光化工股份有限公司 | Industrial production method of high-purity iminodiacetic acid |
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| CN100558699C (en) | 2009-11-11 |
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