CN1331844C - Process for preparing iminodiacetonitrile - Google Patents
Process for preparing iminodiacetonitrile Download PDFInfo
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- CN1331844C CN1331844C CNB2006100541722A CN200610054172A CN1331844C CN 1331844 C CN1331844 C CN 1331844C CN B2006100541722 A CNB2006100541722 A CN B2006100541722A CN 200610054172 A CN200610054172 A CN 200610054172A CN 1331844 C CN1331844 C CN 1331844C
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- hydroxyacetonitrile
- iminodiacetonitrile
- preheating
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Abstract
The present invention discloses a process for preparing iminodiacetonitrile by using hydroxy acetonitrile and ammonia water as raw materials, which is characterized in that the hydroxy acetonitrile and the ammonia water which are used as the raw materials are mixed to react with each other after respectively preheated. The present invention adopts a series of process measures for the disadvantages of the prior art so that the yield of the iminodiacetonitrile as a product obtained according to the present invention is more than 90 %, the purity is improved to more than 98 %, and thereby, the quality of the product is also greatly improved.
Description
Technical field
The present invention relates to a kind of preparation technology of iminodiacetonitrile, specifically prepare the technology of iminodiacetonitrile with hydroxyacetonitrile and ammonia source.
Background technology
Iminodiacetonitrile (Iminodiacetonitrile), light brown to the canescence crystalline powder, 75～76 ℃ of fusing points are a kind of important fine-chemical intermediates, are widely used in agricultural chemicals, dyestuff, medicine, synthetic resins, water treatment, field such as electric.
United States Patent (USP) 5187301 discloses the method for preparing iminodiacetonitrile with hydroxyacetonitrile and ammonia source, and its principle is as follows:
Main reaction:
NH
3+2HOCH
2CNNH(CH
2CN)
2+2H
2O
Side reaction:
NH
3+HOCH
2CNNH
2CH
2CN+H
2O
NH
3+
3HOCH
2CNN(CH
2CN)
3+3H
2O
In the above-mentioned reaction, side reaction also comprise above product self dimer, tripolymer and polymer and mutually between polymer.This preparation method divides two kinds of interrupter method and continuous processings.But no matter be interrupter method or continuous processing production, because itself reaction product complexity, polymerization easily cause the product instability, although the conversion rate of products height, product yield is low, and product content is low, of poor quality etc.
Summary of the invention
The object of the present invention is to provide the preparation technology of the iminodiacetonitrile of a kind of high purity, high yield.
The object of the present invention is achieved like this: a kind of preparation technology of iminodiacetonitrile, its adopts hydroxyacetonitrile and ammoniacal liquor is raw material, it is characterized in that: raw material hydroxyacetonitrile and ammoniacal liquor respectively after the preheating remix react.Why the present invention reacts the raw material preheating remix earlier, mainly is in order to reduce the generation of side reaction in the temperature-rise period, to avoid mixing temperature to be the defective of temperature of reaction.
The above-mentioned raw materials hydroxyacetonitrile is preheated to 50～120 ℃ earlier, and above-mentioned raw materials ammoniacal liquor is preheated to 170～180 ℃, again both is mixed reaction.
For polymerization and the decomposition that suppresses product, before the preheating of above-mentioned raw materials hydroxyacetonitrile, add the stablizer alchlor, its add-on is 0.1～5% of a hydroxyacetonitrile total amount, by weight percentage.
The contriver is through experiment discovery repeatedly, the product iminodiacetonitrile is unsettled in alkalescence and neutral environment, self is polymerized to dimer and polymer easily, and under acidic conditions, be metastable, therefore the contriver thinks, add diluted acid such as sulfuric acid, phosphoric acid, hydrochloric acid, acetate or other organic acids etc. in reaction mixture, making its pH value is 3～5.
For the color and luster that further improves product yield and improve product, visual appearance, the mixed solution that the present invention finishes post-reactor outlet with described reaction is chilled to 45～100 ℃ and enters crystallizer, adding diluted acid control pH value is 3～5, add the oxidation inhibitor that accounts for hydroxyacetonitrile total amount 0.2～0.5% by weight percentage again, get the product iminodiacetonitrile behind crystallisation by cooling, the centrifugal drying.
After the mixed solution chilling of above-mentioned reactor outlet entered crystallizer, the diluted acid of adding was dilute sulphuric acid or dilute hydrochloric acid, and the oxidation inhibitor of adding is dihydroxy-benzene or naphthalenediol.
Specifically, the present invention is such: in weight percent concentration is to add the aluminium sesquioxide that accounts for hydroxyacetonitrile total amount 0.1～5% by weight percentage in 20～80% the hydroxyacetonitrile, at room temperature mix, being acidified to pH value is 3～5, is preheating to 50～120 ℃ again; With weight percent concentration is that 25～28% ammoniacal liquor is preheating to 170～180 ℃; Then two kinds of raw materials of above-mentioned preheating are sent into the flow reactor hybrid reaction, temperature of reaction is 120～180 ℃, and reaction pressure is 0.4～1Mpa, and the reaction times is 0.5～3 minute; Afterwards, enter crystallizer after the reaction mixture of above-mentioned flow reactor outlet is quenched to 45～100 ℃, adding dilute sulphuric acid control pH value is 3～5, adds dihydroxy-benzene or the naphthalenediol that accounts for hydroxyacetonitrile total amount 0.2～0.5% again, gets the product iminodiacetonitrile behind crystallisation by cooling, the centrifugal drying.
The present invention enters hybrid reaction in the flow reactor after reactant feed is preheating to certain temperature respectively again, has avoided reaching long problem of temperature required time of reaction after reactant mixes in the prior art; And raw material is a progressive process from low temperature to high temperature after mixing in the prior art, in this process, there are many side reactions and by product to produce, the present invention is by difference preheating reactant feed, when reactant feed reaches us when temperature required, two kinds of reactants just mix reaction, avoid mixing temperature to be the defective of temperature of reaction, greatly reduced the generation of temperature-rise period side reaction.
The present invention also by add the stablizer aluminium sesquioxide of product iminodiacetonitrile in the raw material hydroxyacetonitrile, suppresses the polymerization and the decomposition of product iminodiacetonitrile; In addition by chilling to the reaction mixture that comes out from flow reactor, be about at high temperature unsettled product iminodiacetonitrile and be cooled to its equilibrium temperature rapidly, greatly reduce the degree of decomposition of product iminodiacetonitrile, guaranteed in high transformation efficiency, high yield is also arranged, solve transformation efficiency height in the prior art and the low problem of yield, also improved the purity of product iminodiacetonitrile simultaneously greatly.
Because the raw material, intermediate, product and the byproduct that relate among the present invention all are the unstable material, the oxidation of easy in process of production oxidized property material causes the reactant color burn, causes reactant to handle when serious, the finished product content is low, and color and luster is undesirable.The present invention also helps the raising of quality product by add oxidation inhibitor dihydroxy-benzene or naphthalenediol etc. in the crystallisation by cooling process.
In addition, the contriver is finding in the experiment repeatedly, the product iminodiacetonitrile is unsettled in alkalescence and neutral environment, self is polymerized to dimer and polymer easily, and under acidic conditions, be metastable, therefore the present invention adds diluted acid as stablizer in reaction mixture and in the crystallizer of reaction after finishing, and the yield and the quality of product all had tangible raising effect.
In a word, the present invention is directed to the defective of prior art, take above-mentioned series of process measure, the feasible product iminodiacetonitrile that obtains according to the present invention, its yield improves greatly, all more than 90%, purity is brought up to more than 98%, thereby quality product also improves greatly.
Embodiment
Below by embodiment the present invention is described, but the present invention is not limited to these embodiment.
Embodiment 1: under preheating condition not, be that 40% hydroxyacetonitrile and weight percent concentration are 26.5% ammoniacal liquor with weight percent concentration, enter flow reactor with volume pump respectively by theoretical proportioning then, the hydroxyacetonitrile flow is 2m
3/ hour, temperature of reaction is controlled to be 165 ℃～180 ℃, reaction pressure is 0.4Mpa, material residence time in reactor is 1 minute, the high-efficient liquid spectrum analysis of reactor outlet mixed solution, transformation efficiency are 78.7%, and successive reaction obtained 9680 kilograms of black solid iminodiacetonitrile products in 24 hours, content 88.1%, yield 53.4%.
Embodiment 2: be respectively that 40% hydroxyacetonitrile is preheating to 80 ℃ with weight percent concentration, weight percent concentration is that 26.5% ammoniacal liquor is preheating to 175 ℃, enters flow reactor with volume pump respectively by theoretical proportioning then, and the hydroxyacetonitrile flow is 2m
3/ hour, temperature of reaction is controlled to be 165 ℃～170 ℃, reaction pressure is 0.7Mpa, material residence time in reactor is 1 minute, the high-efficient liquid spectrum analysis of reactor outlet mixed solution, transformation efficiency are 95.7%, and successive reaction obtained 13356 kilograms of black solid iminodiacetonitrile products in 24 hours, content 92.6%, yield 77.3%.
Embodiment 3: in weight percent concentration is to add the stablizer alchlor in 20% the hydroxyacetonitrile, and its add-on is 0.1% of a hydroxyacetonitrile weight, at room temperature mixes, and is preheating to 60 ℃; With weight percent concentration is that 25% ammoniacal liquor is preheating to 170 ℃; Enter flow reactor with volume pump respectively, temperature of reaction is controlled to be 120 ℃～140 ℃, and reaction pressure is 0.5Mpa, and material residence time in reactor is 3 minutes; The high-efficient liquid spectrum analysis of reactor outlet mixed solution, transformation efficiency is 94.9%, obtains 7122 kilograms of brownish black solid iminodiacetonitrile products, content 94.8%, yield 84.4%.
Embodiment 4: add aluminium sesquioxide in weight percent concentration is 80% hydroxyacetonitrile, its add-on is 5% of a hydroxyacetonitrile weight, and at room temperature mixing the back, to be acidified to pH value with dilute sulphuric acid be 4, is preheating to 120 ℃; With weight percent concentration is that 28% ammoniacal liquor is preheating to 180 ℃; Enter flow reactor with volume pump respectively, the hydroxyacetonitrile flow is 2m
3/ hour, temperature of reaction is controlled to be 160 ℃～180 ℃, and reaction pressure is 0.6Mpa, and material residence time in reactor is 2 minutes; Afterwards, enter crystallizer after the reaction mixture of above-mentioned flow reactor outlet is quenched to 75～100 ℃, add the antioxidant Resorcinol that accounts for hydroxyacetonitrile weight 0.2%, adding dilute sulphuric acid again, to make pH value be 5, collect 24 hours reaction mixture continuously, obtain 29424 kilograms of light brown solid iminodiacetonitrile products, content 98.2%, yield 90.3%.
Embodiment 5: add aluminium sesquioxide in weight percent concentration is 60% hydroxyacetonitrile, its add-on is 3% of a hydroxyacetonitrile weight, and at room temperature mixing the back, to be acidified to pH value with dilute sulphuric acid be 5, is preheating to 50 ℃; With weight percent concentration is that 25% ammoniacal liquor is preheating to 170 ℃; Enter flow reactor with volume pump respectively, the hydroxyacetonitrile flow is 2m
3/ hour, temperature of reaction is controlled to be 120 ℃～130 ℃ ℃, and reaction pressure is 0.5Mpa, and material residence time in reactor is 0.5 minute; Afterwards, enter crystallizer after the reaction mixture of above-mentioned flow reactor outlet is quenched to 70 ℃, add the antioxidant pyrocatechol that accounts for hydroxyacetonitrile weight 0.3%, adding dilute sulphuric acid again, to make pH value be 3, transformation efficiency is 94.9%, obtain 21949 kilograms of light brown solid iminodiacetonitrile products, content 98.4%, yield 90.0%.
Embodiment 6: weight percent concentration is that the aluminium sesquioxide that adds in 55% hydroxyacetonitrile is 0.5%, be preheating to 100 ℃, ammoniacal liquor is preheating to 170 ℃, the reactor outlet reaction mixture is chilled to 100 ℃, adds the antioxidant naphthalenediol that accounts for hydroxyacetonitrile weight 0.5%, and all the other are with embodiment 5, transformation efficiency is 94.7%, obtain 20428 kilograms of light brown solid iminodiacetonitrile products, content 98.1%, yield 91.1%.
Embodiment 7: weight percent concentration is the aluminium sesquioxide of adding 3% in 75% hydroxyacetonitrile, be preheating to 110 ℃, weight percent concentration is that 26.0% ammoniacal liquor is preheating to 180 ℃, and the reactor outlet reaction mixture is chilled to 65 ℃, adds the antioxidant naphthalenediol that accounts for hydroxyacetonitrile weight 0.4%, making the system pH value with phosphoric acid is 5, all the other are with embodiment 4, and transformation efficiency is 94.9%, obtain 28052 kilograms of light brown solid iminodiacetonitrile products, content 97.1%, yield 90.8%.
Embodiment 8: weight percent concentration is the aluminium sesquioxide of adding 2% in 30% hydroxyacetonitrile, be preheating to 60 ℃, ammoniacal liquor is preheating to 180 ℃, the reactor outlet reaction mixture is chilled to 50 ℃, adds the antioxidant Resorcinol that accounts for hydroxyacetonitrile weight 0.3%, and making the system pH value with dilute hydrochloric acid is 3, transformation efficiency is 92.9%, obtain 11049 kilograms of light brown solid iminodiacetonitrile products, content 98.5%, yield 90.7%.
Claims (7)
1, a kind of preparation technology of iminodiacetonitrile, its adopts hydroxyacetonitrile and ammoniacal liquor is raw material, it is characterized in that: raw material hydroxyacetonitrile and ammoniacal liquor respectively after the preheating remix react; Wherein the raw material hydroxyacetonitrile is preheated to 50～120 ℃ earlier, raw material ammonia water is preheated to 170～180 ℃.
2, the preparation technology of iminodiacetonitrile as claimed in claim 1 is characterized in that: add the stablizer alchlor before the preheating of described raw material hydroxyacetonitrile, its add-on is a hydroxyacetonitrile total amount 0.1～5%, by weight percentage.
3, the preparation technology of iminodiacetonitrile as claimed in claim 1 or 2 is characterized in that: adding diluted acid control pH value before the preheating of described raw material hydroxyacetonitrile is 3～5.
4, the preparation technology of iminodiacetonitrile as claimed in claim 3 is characterized in that: adding diluted acid before the preheating of described raw material hydroxyacetonitrile is sulfuric acid or phosphoric acid or hydrochloric acid or acetate.
5, the preparation technology of iminodiacetonitrile as claimed in claim 1 or 2, it is characterized in that: the mixed solution that post-reactor outlet is finished in described reaction is chilled to 45～100 ℃ and enters crystallizer, adding diluted acid control pH value is 3～5, add the oxidation inhibitor that accounts for hydroxyacetonitrile total amount 0.2～0.5% by weight percentage again, get the product iminodiacetonitrile behind crystallisation by cooling, the centrifugal drying.
6, the preparation technology of iminodiacetonitrile as claimed in claim 5 is characterized in that: after the mixed solution chilling of described reactor outlet entered crystallizer, the diluted acid of adding was dilute sulphuric acid, dilute hydrochloric acid or dilute phosphoric acid, and the oxidation inhibitor of adding is dihydroxy-benzene or naphthalenediol.
7, the preparation technology of iminodiacetonitrile as claimed in claim 5, it is characterized in that: in weight percent concentration is to add the stablizer alchlor in 20～80% the hydroxyacetonitrile, its add-on is a hydroxyacetonitrile total amount 0.1～5%, by weight percentage, at room temperature mix, being acidified to pH value with diluted acid again is 3～5, is preheating to 50～120 ℃; With weight percent concentration is that 25～28% ammoniacal liquor is preheating to 170～180 ℃; Then two kinds of raw materials of described preheating are sent into the flow reactor hybrid reaction, temperature of reaction is 120～180 ℃, and reaction pressure is 0.4～1Mpa, and the reaction times is 0.5～3 minute; Afterwards, enter crystallizer after the reaction mixture of described flow reactor outlet is quenched to 45～100 ℃, adding diluted acid control pH value is 3～5, add Resorcinol or the naphthalenediol that accounts for hydroxyacetonitrile total amount 0.2～0.5% by weight percentage again, get the product iminodiacetonitrile behind crystallisation by cooling, the centrifugal drying.
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|---|---|---|---|
| CNB2006100541722A CN1331844C (en) | 2006-03-30 | 2006-03-30 | Process for preparing iminodiacetonitrile |
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|---|---|---|---|
| CNB2006100541722A CN1331844C (en) | 2006-03-30 | 2006-03-30 | Process for preparing iminodiacetonitrile |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100422144C (en) * | 2007-05-15 | 2008-10-01 | 四川省天然气化工研究院 | Method for preparing diethylacetonitrile in imino group |
| CN101671362B (en) * | 2009-09-28 | 2012-12-12 | 安徽国星生物化学有限公司 | Process for preparing N-(phosphonomethyl) iminodiacetic acid by hydroxyacetonitrile continuous method |
| CN103787919B (en) * | 2012-12-27 | 2016-06-29 | 三达膜科技（厦门）有限公司 | A kind of discoloration method of Iminodiacetonitrile 1,1'-Imidodiacetonitrile |
| CN103910651B (en) * | 2014-03-10 | 2016-01-20 | 河北诺达化工设备有限公司 | Iminodiacetonitrile continuous crystallisation technique |
Citations (2)
| 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 |
| CN1187187A (en) * | 1995-06-06 | 1998-07-08 | 汉普郡化学公司 | Nitrile stabilization |
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2006
- 2006-03-30 CN CNB2006100541722A patent/CN1331844C/en active Active
Patent Citations (2)
| 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 |
| CN1187187A (en) * | 1995-06-06 | 1998-07-08 | 汉普郡化学公司 | Nitrile stabilization |
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Address after: No. 426, Chemical Road, Yongchuan District, Chongqing Patentee after: Chongqing Unisplendour Chemical Co., Ltd. Address before: No. 426, Chemical Road, Yongchuan, Chongqing Patentee before: Congqing Ziguang Chemical Industry Co., Ltd. |