CN109305929A - A kind of N- cyanoethyl aniline zero-discharge production process - Google Patents
A kind of N- cyanoethyl aniline zero-discharge production process Download PDFInfo
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- CN109305929A CN109305929A CN201710634120.0A CN201710634120A CN109305929A CN 109305929 A CN109305929 A CN 109305929A CN 201710634120 A CN201710634120 A CN 201710634120A CN 109305929 A CN109305929 A CN 109305929A
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- aniline
- catalyst
- water
- acrylonitrile
- hydroquinone
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
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- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of production technologies of N- cyanoethyl aniline zero-emission, this technique uses aniline, acrylonitrile for raw material, catalyst is added, hydroquinone synthesizes N- cyanoethyl aniline in water phase, normal pressure recycles excessive acrylonitrile after reaction, recycling finishes slow cooling to 25 °C hereinafter, filtering and product being washed with a small amount.Mother liquid coming and washing water are used as next secondary response bottom water after collecting, catalyst and hydroquinone are added according to the residual quantity of the catalyst of mixing bottom water and hydroquinone when next secondary response feeds intake, catalyst total amount is equal with first time inventory, the N- cyanoethyl aniline content San 98% being obtained by filtration, the bis- cyanoethyl aniline content San 1.5% of N, N-.The three-waste free discharge in production procedure, is truly realized technique of zero discharge.
Description
Technical field
The present invention relates to the production technologies of N- cyanoethyl aniline.
Background technique
N- cyanoethyl aniline belongs to a kind of important fine chemical material and intermediate, and it is fine to can be used for dyestuff, pesticide etc.
The synthesis of chemical intermediate, such as: N_ cyanoethyl-N- Acetoxyethyl aniline, N- cyanoethyl-Phenhenzamine, N- cyanoethyl-
The synthesis of the products such as N- benzoxy ethyl aniline, N- cyanoethyl-N-ethylaniline, is widely used in dyestuff and pesticide industry.
The production method of traditional N- cyanoethyl aniline is made using hydrochloric acid, acetic acid, sulfuric acid, zinc chloride or alchlor etc.
For catalyst, hydroquinone is used to be synthesized as polymerization inhibitor, the mother liquid coming and washing water after synthesis carry out sewage treatment
After discharge, using the aniline and N- cyanoethyl aniline in mother liquid coming, product yield is low, and sewage belongs to high C0D waste water, processing
Higher cost.Present domestic production producer mostly uses the improved method of water phase production method, and general addition zinc chloride, which is used as, to be helped
Catalyst needs steam distillation, layering, neutralization etc. to operate, and complicated for operation, operating procedure is more, and energy consumption is high, the N- cyanogen of production
The content of N in ethyl aniline, N- dicyanoethyl-aniline is high (generally more than 2%), has an impact to the quality of subsequent production kind.Example
Such as: Publication No.: CN201310511201, CN201410245940, CN201110119218 patent.
Summary of the invention
- kind of N- cyanoethyl aniline zero-discharge production process, it is characterized in that: it be in water phase, be added aniline, acrylonitrile,
Hydroquinone, catalyst, the mass ratio of aniline, acrylonitrile and water are 100:68-75:350-500;The quality of catalyst and aniline
Than for 0.01 0.05:1;The mass ratio of hydroquinone and aniline is 0.002 0.02:1, is warming up to 100 ll 〇 °C, is kept
After 18-22 hours, then air-distillation Propylene recovery nitrile is cooled to 25 °C hereinafter, precipitation N- cyanoethyl aniline, is used in combination after filtering
The 30%-70% water washing of aniline quality is added, obtains product N- cyanoethyl aniline；Mother liquid coming and washing water are as next group N- cyanogen
The production bottom water of ethyl aniline, analysis mother liquid coming and the content for washing the catalyst and hydroquinone in water mixed liquid, add and urge
To above-mentioned requirement, the raw material of the acrylonitrile of recycling as the production of next group N- cyanoethyl aniline adds for agent and hydroquinone
Enter acrylonitrile and aniline, carries out next batch production, reach zero-discharge production process.
Above-mentioned N- cyanoethyl aniline zero-discharge production process, it is characterized in that: the catalyst is zinc chloride, tri-chlorination
Aluminium, hydrochloric acid or sulfuric acid.
Present invention process applies mother liquor and washing water production, and the mass ratio for controlling catalyst and aniline is 0.01 0.05:
1, catalytic amount in reaction system is effectively controlled, so that reaction is gone on smoothly, and the content of N, N_ dicyanoethyl-aniline reaches
It is required that.To the analysis of the catalyst content of mother liquor and washing water it is recognised that a batch production synthesizes and band in product is precipitated after filtering
The catalyst walked is seldom, and most catalyst of reaction system are present in mother liquor and washing water, if not controlling catalyst
Additional amount can make the catalyst increase in reaction system that subsequent mother liquor be caused to apply N in the product of production, N- dicyanoethyl-aniline
Content increases, in actual production since the catalyst in mother liquor will appear operation fluctuation, it is therefore desirable to catalyst amounts
It is adjusted within the scope of total amount.
Present invention process, hydroquinone are as the polymerization inhibitor for preventing acrylonitrile polymerization, due to benzene in the reaction system
Diphenol is dissolved in water and chemical property is relatively stable, therefore after applying mother liquor and washing water completely, the dosage of hydroquinone
Greatly reduce, therefore is also required to be adjusted hydroquinone dosage within the scope of total amount.
Present invention process, in production, washing water are controlled, and when washing water is more, wash water jacket is endless,
It is few to wash water, next batch synthesis is need to add clear water to will lead to catalyst content in system relatively low, cause reaction conversion ratio to reduce,
Therefore washing water need to be controlled, washs water and mother liquor water total amount equal to bottom water volume needed for primary production.
By analysis, reacts remaining aniline and a small amount of product is dissolved in mother liquid coming, by mother liquor and wash water jacket,
The chemical substance being effectively utilized in mother liquor and washing water so that the product yield for applying batch improves 5% or so, and eliminates
The wastewater treatment process of high C0D mother liquor.
In short, controlling catalyst content in reaction system using the present invention, being obtained by simple mother liquor and wash water jacket
Qualified products have been arrived, and have solved the environmental issue of mother liquid coming and washing water discharge in original technique, embodying the present invention has
Higher economic benefit and social benefit.
The present invention is reducing catalyst and hydroquinone dosage on the basis of has been truly realized following for mother liquor and washing water
Ring set is used, and the N- cyanoethyl aniline of synthesis is through HPLC analysis content in 98% or more, N, and N- dicyanoethyl-aniline content is on 1.5% left side
The right side, aniline residue amount is less than 0.5%.Production technology has accomplished wastewater zero discharge, easy to operate, and required equipment is less, and cost reduces
Obviously.
Specific embodiment
Comparative example 1
In 1000ml autoclave, successively plus water 550ml, 30% hydrochloric acid 3g, hydroquinone lg, aniline 140g, acrylonitrile 95g, slowly
Slowly after being warming up to 110 °C of holdings 20 hours, the excessive acrylonitrile of air-distillation, the acrylonitrile of recycling is layered to obtain acrylonitrile 15g,
Water 20g.Reaction mass is slowly cooled to 25 °C, and vacuum filter simultaneously is washed with a small amount to obtain product 198.8g (folding hundred), mother liquor
Water 471ml, washing water 50ml.Product yield 92.3%, N, N- dicyanoethyl-aniline 1.35%.
Embodiment 1
In 1000ml autoclave, the mother liquid coming and washing water, zinc chloride 0.2g, hydroquinone 0.lg, aniline of comparative example 1 is added
The acrylonitrile (including water phase) of 140g, acrylonitrile 80g and the recycling in comparative example 1.110 °C of holdings 20 hours are warming up to, often
Pressure distills excessive acrylonitrile, and Propylene recovery nitrile is layered 14.8g, water 21g.Reaction mass is slowly cooled to 25 °C, vacuum filter
And it is washed with a small amount to obtain product 211g (folding hundred), mother liquid coming 475ml, washing water 60ml.Product yield 97%, N, N- dicyan
Ethyl aniline 1.4%.Mother liquid coming makees test next time and repeats to apply operation.
Embodiment 2
In 1000ml autoclave, the mother liquid coming of embodiment 1 and washing water, zinc chloride 0.05g, alchlor 0.lg, right is added
Benzenediol 0.lg, aniline 140g, acrylonitrile 80g and the acrylonitrile of the recycling in embodiment 1 (including water phase).It is warming up to 110 °
C is kept for 20 hours, the excessive acrylonitrile of air-distillation, and Propylene recovery nitrile is layered 15.lg, water 20.5g.Reaction mass slowly cools down
To 25 °C, vacuum filter simultaneously is washed with a small amount to obtain product 213g (folding hundred), mother liquid coming 472ml, washing water 55ml.Product is received
Rate 97.9%, N, N- dicyanoethyl-aniline 1.2%.Mother liquid coming makees test next time and repeats to apply operation.
Embodiment 3
In 1000ml autoclave, the mother liquid coming and washing water, hydrochloric acid 0.2g, hydroquinone 0.lg, aniline of embodiment 2 is added
The acrylonitrile (including water phase) of 140g, acrylonitrile 80g and the recycling in embodiment 2.110 °C of holdings 20 hours are warming up to, often
Pressure distills excessive acrylonitrile, and Propylene recovery nitrile is layered 15g, water 19g.Reaction mass is slowly cooled to 25 °C, and vacuum filter is simultaneously
It is washed with a small amount to obtain product 212g (folding hundred), mother liquid coming 470ml, washing water 60ml.Product yield 97.4%, N, N- dicyan
Ethyl aniline 1.4%.Mother liquid coming makees test next time and repeats to apply operation.
Embodiment 4
In 1000ml autoclave, be added embodiment 3 mother liquid coming and washing water, sulfuric acid 0.2g, hydroquinone 0.lg,
The acrylonitrile (including water phase) of aniline 140g, acrylonitrile 80g and the recycling in embodiment 3.It is warming up to 110 °C and keeps 20
Hour, the excessive acrylonitrile of air-distillation, Propylene recovery nitrile is layered 14.8g, water 21g.Reaction mass is slowly cooled to 25 °C, very
Sky filters and is washed with a small amount to obtain product 213.2g (folding hundred), mother liquid coming 475ml, washing water 60ml.Product yield
97.98%, N, N- dicyanoethyl-aniline 1.5%.Mother liquid coming makees test next time and repeats to apply operation.
Claims (1)
1. a kind of N- cyanoethyl aniline zero-discharge production process, it is characterized in that: it is that aniline, acrylonitrile, right is added in water phase
Benzenediol, catalyst, the mass ratio of aniline, acrylonitrile and water are 100:68-75:350-500;The mass ratio of catalyst and aniline
For 0.01 0.05:1;The mass ratio of hydroquinone and aniline is 0.002 0.02:1, is warming up to 100 ll0 °C, keeps 18-
After 22 hours, air-distillation Propylene recovery nitrile, be then cooled to 25 °C hereinafter, be precipitated N- cyanoethyl aniline, after filtering and with add
The 30%-70% water washing for entering aniline weight obtains product N- cyanoethyl aniline；Mother liquid coming and washing water are as next group N- cyanogen second
The production bottom water of base aniline analyzes the content of catalyst and hydroquinone in the mixed liquor of mother liquid coming and washing water, adds catalysis
To above-mentioned requirement, the raw material of the acrylonitrile of recycling as the production of next group N- cyanoethyl aniline is added for agent and hydroquinone
Acrylonitrile and aniline carry out next batch production.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710634120.0A CN109305929A (en) | 2017-07-29 | 2017-07-29 | A kind of N- cyanoethyl aniline zero-discharge production process |
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| CN201710634120.0A CN109305929A (en) | 2017-07-29 | 2017-07-29 | A kind of N- cyanoethyl aniline zero-discharge production process |
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| CN109305929A true CN109305929A (en) | 2019-02-05 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113956178A (en) * | 2021-09-23 | 2022-01-21 | 万华化学集团股份有限公司 | N, N' -dicyanoethyl-diaminodiphenylmethane and preparation method thereof |
-
2017
- 2017-07-29 CN CN201710634120.0A patent/CN109305929A/en not_active Withdrawn
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113956178A (en) * | 2021-09-23 | 2022-01-21 | 万华化学集团股份有限公司 | N, N' -dicyanoethyl-diaminodiphenylmethane and preparation method thereof |
| CN113956178B (en) * | 2021-09-23 | 2023-08-11 | 万华化学集团股份有限公司 | N, N' -dicyanoethyl-diamino diphenyl methane and preparation method thereof |
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Application publication date: 20190205 |
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| WW01 | Invention patent application withdrawn after publication |