CN107033030A - A kind of production technology of continuous aniline-acetonitrile - Google Patents
A kind of production technology of continuous aniline-acetonitrile Download PDFInfo
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- CN107033030A CN107033030A CN201710326008.0A CN201710326008A CN107033030A CN 107033030 A CN107033030 A CN 107033030A CN 201710326008 A CN201710326008 A CN 201710326008A CN 107033030 A CN107033030 A CN 107033030A
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- aniline
- hydroxyacetonitrile
- acetonitrile
- continuous production
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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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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/32—Separation; Purification; Stabilisation; Use of additives
- C07C253/34—Separation; Purification
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of method of continuous production aniline-acetonitrile, microfluidic channel reactor is continued through with aniline and hydroxyacetonitrile and reacted, with molar ratio computing, 1<Aniline:Hydroxyacetonitrile≤1.2；Reaction temperature is 170~220 DEG C；Reaction time is 10~50 seconds.Methods described is carried out under conditions of without catalyst.The present invention combines the advantage of microfluidic channel reactor, it is to avoid the corrosion of microreactor, also causes reaction cost reduction, simplifies operating procedure, in the absence of enlarge-effect so that the technique can realize that a set of equipment produces ton scale per year；In course of reaction hydroxyacetonitrile do not polymerize the aniline reclaimed in generation impurity, nonreactive mother liquor again can be with recovery；Improve aniline-acetonitrile mother liquid disposal and have the shortcomings that labor intensity is big, cost of labor is high, wastewater flow rate is big, produced secondary mother liquid can repeatedly recycled, reduction environmental pollution.
Description
Technical field
The present invention relates to a kind of production technology of continuous aniline-acetonitrile, specifically a kind of aniline-acetonitrile it is micro-
The amplification large-scale production of fluid and disposing mother liquor apply mechanically technique, belong to aniline-acetonitrile synthesis field.
Background technology
Aniline-acetonitrile is the indigo intermediate of production, is mainly used in cowboy's cloth dyeing, for dyestuff intermediate；Also it can use
In the synthesis of other fine chemicals, the use " aniline hydroxyacetonitrile method " of more prevalence domestic at present.
Patent CN101514170A discloses one kind, and to continue through duct type preheater, pipeline mixer, duct type anti-
The production method of device and reactor is answered, the hydroxyacetonitrile of 60%~99.5% concentration is used for raw material, reaction needs to add auxiliary agent,
The fast reaction stage is first carried out in pipeline reactor, slow reaction in being carried out subsequently into reactor, the reaction time is longer,
Complex operation energy consumption is higher simultaneously, and there is safety hazard using the hydroxyacetonitrile of high concentration.
Chinese invention patent prospectus CN104496848 discloses a kind of method for preparing aniline-acetonitrile, with benzene
Amine continues through micro passage reaction condensation reaction generation aniline-acetonitrile with hydroxyacetonitrile, and the invention is pre- using base catalyst
Hydroxyacetonitrile is handled, reaction raw materials aniline is 1 with hydroxyacetonitrile mol ratio:1~1.3, pressure is 0.3MPa, and flow is smaller.Should
Corrosion can be produced to microreactor, the meeting by the way of hydroxyacetonitrile is excessive under the high temperature conditions in invention using base catalyst
So that the cyano group value in mother liquor is higher, hydroxyacetonitrile can not be reclaimed also can have pollution to environment, while due to excess in the mother liquor
It can not also be recycled more than impurity caused by hydroxyacetonitrile.
Microreactor synthesizing anilino acetonitrile application in recent years increasingly attracts attention, and has also carried out many researchs, has used
The microreactor lab scale stage can reach product purity well and yield, but be reacted using catalyst, at high temperature
Catalyst has serious corrosion to microreactor pipeline, limits the application of microreactor, and this has serious amplification production and asked
Topic, is that this present invention makes research.
The content of the invention
In order to solve, the present invention provides a kind of corrosion in order to avoid catalyst to microreactor, while reaching certain life
Production scale so that enlarge-effect is not present in the reaction, and feeding intake for material is changed completely with reference to the advantage of microfluidic channel reactor
Ratio, is added without catalyst and is reacted, obtained mother liquor recoverable, environmental pollution is reduced, with excellent actual life
Produce effect.
The technical solution adopted by the present invention：A kind of method of continuous production aniline-acetonitrile, is connected with aniline and hydroxyacetonitrile
It is continuous to be reacted by microfluidic channel reactor, with molar ratio computing, 1<Aniline:Hydroxyacetonitrile≤1.2；Reaction temperature is 170
~220 DEG C；Reaction time is 10~50 seconds.It is preferred that CPMM or Starlam series of microflow reactor according.
As preferred technical scheme, the method for the invention is carried out under conditions of without catalyst.
As preferred technical scheme, the mass concentration of aniline of the present invention is 99.0-99.9%, the matter of hydroxyacetonitrile
Amount concentration is 30-60%.
As preferred technical scheme, the method for continuous production aniline-acetonitrile of the present invention comprises the following steps：
(1), by counterbalance valve back pressure, the pressure in microfluidic channel reactor assembly is reached 2~5MPa；It is heat exchanger, micro- mixed
Clutch, shell-and-tube reactor delay pipeline are heated to 170-220 DEG C by constant temperature bath respectively；
(2) aniline is fed by feed pump, and the feed rate of aniline is 1.1-12.1L/min, flows through heat exchanger and is preheated；
(3) hydroxyacetonitrile is fed by feed pump, and the feed rate of hydroxyacetonitrile is 2.12-12.9L/min；
(4) the aniline after preheating is mixed with hydroxyacetonitrile in micro-mixer, complete anti-through shell-and-tube reactor delay lie
Should；
(5) reaction solution enters cooling system, is down to 20~30 DEG C, adds water stirring and separates out crystal.
Preferably, the step (5) reclaimed water addition for the step (2) aniline and the step (3) hydroxyacetonitrile body
0.5-5 times of product total amount.
As preferred technical scheme, the step of methods described also includes following aniline recovery：
(6) after the crystal in separating the step (5), remaining liquid is a mother liquor；
(7) the mother liquor multi_layer extraction aniline, remaining liquid be secondary mother liquid or into a mother liquor plus
Enter aniline, extract unreacted excessive aniline, remaining liquid is secondary mother liquid.
As preferred technical scheme, the step (7) middle aniline addition for the step (2) middle aniline inlet amount
1-15%.
It is highly preferred that the step (7) middle aniline addition for the step (2) the inlet amount of middle aniline 10%.
Mother liquor, which is added, stirs a period of time after aniline, standing sedimentation, aniline can separate obvious liquid layer, you can separation
Go out aniline, this part aniline is circularly used for reaction raw materials.
When rate of charge aniline:Hydroxyacetonitrile is 1.2:When 1, aniline is excessive in reaction, and aniline can be not required to reaction liquid layer
Additionally to add aniline；When rate of charge aniline:Hydroxyacetonitrile is 1.01:When 1, the aniline for adding 1-15% is more conducive to layering, most
Excellent addition is 10%.
The step of being recycled as preferred technical scheme, in addition to the secondary mother liquid：(7) the step is obtained
Secondary mother liquid replace the water of the step (5).
Microfluidic channel reactor causes consersion unit to have great specific surface area because of its internal micro-structural, reachable to stir
Mix even thousands of times of the hundred times of kettle specific surface area.Microfluidic channel reactor has fabulous heat transfer and mass transfer ability, can be with
Realize moment uniformly mixing and the efficient heat transfer of material.Aniline and hydroxyacetonitrile mol ratio of the present invention is 1.01~1.2:1, knot
The advantage of microfluidic channel reactor is closed, while slight excess of aniline plays certain catalytic action reaction is accelerated, can
Reach more excellent effect：
1st, microfluidic channel reactor feed system is carried out by feed pump, without artificial batch charging, without interval
Operation, can continuously operate and obtain that the occupation area of equipment that finished product uses is small, production capacity is high, easy to operate；
2nd, catalyst need not be added, it is to avoid the corrosion of microreactor, also causes reaction cost reduction, simplify operative employee
Skill, in the absence of enlarge-effect so that the technique can realize that a set of equipment produces ton scale per year；
3rd, in course of reaction hydroxyacetonitrile do not polymerize the aniline that is reclaimed in generation impurity, nonreactive mother liquor again can be with
Recovery；Improve aniline-acetonitrile mother liquid disposal and have the shortcomings that labor intensity is big, cost of labor is high, wastewater flow rate is big, reduce
Environmental pollution.
4th, produced secondary mother liquid can multiple recycled, separate out product for decrease temperature crystalline.Inside secondary mother liquid
Hydroxyacetonitrile reaction is very complete, has seldom impurity in mother liquor, in order to reduce the three wastes, secondary mother liquid can be recycled completely,
I.e. reaction completion cooling, which is quenched after reaction, adds secondary mother liquid, and dilution is beneficial to stirring, while product precipitation.
Brief description of the drawings
The width of accompanying drawing 1 of the present invention,
Fig. 1, present invention process flow chart；
In figure, u micro-mixers, P pumps, V chargings/receiving tank, F filters, PT pressure transmitters, PSV safety valves, TE temperature
Meter, BPV counterbalance valves, PG pressure gauges, CV check valves, PIA pressure sensors, TI temperature sensors, E heat exchangers.
Embodiment
Following non-limiting examples can make one of ordinary skill in the art be more fully understood the present invention, but not with
Any mode limits the present invention.Reagent and material described in following embodiments, unless otherwise specified, are commercially obtained
, the present invention can reach that a set of equipment produces the scale of ton, but provide different flow data in example explanation.
Following examples are carried out under conditions of without catalyst using Starlam series of microfluidic channels reactor.
Embodiment 1
1) by reacting system pressure, 3MPa is reached by counterbalance valve, heat exchanger and micro-mixer are heated to 170 by constant temperature bath
℃；Shell-and-tube reactor delay pipeline is heated to 170 DEG C by constant temperature bath；
2) mass concentration is fed for 99.5% aniline with volume flow 1.10L/min by pump P-01, flows through heat exchanger
Preheated；
3) mass concentration is fed for 30.0% hydroxyacetonitrile with volume flow 2.12L/min by pump P-02；
4) aniline is mixed with hydroxyacetonitrile in micro-mixer U；Mixed liquor flows through shell-and-tube reactor delay pipeline and completes contracting
Reaction is closed, the time is 30 seconds；
5) mixed liquor export liquid flows into cooling kettle V-03, and cooling is quenched, and equipment is run 30 minutes, adds water or two
Secondary mother liquor insulation separates out product at 30 DEG C, and yield is 99.90%, and purity is 98.9%；
6) separating step 5) in crystal after remaining liquid be mother liquor；
7) mother liquor multi_layer extraction aniline, remaining liquid is secondary mother liquid or added into a mother liquor
Aniline, extracts unreacted excessive aniline (being circularly used for reaction raw materials), and remaining liquid is secondary mother liquid.
8) secondary mother liquid is recycling in step 5) separate out crystal.
Embodiment 2
1) by reacting system pressure, pressure 3MPa is reached by counterbalance valve, heat exchanger and micro-mixer are heated to by constant temperature bath
170℃；Shell-and-tube reactor delay pipeline is heated to 180 DEG C by constant temperature bath；
2) mass concentration is fed for 99.9% aniline with volume flow 2.19L/min by pump P-01, flows through heat exchanger
Preheated；
3) mass concentration is fed for 50.0% hydroxyacetonitrile with volume flow 2.54L/min by pump P-02；
4) aniline is mixed with hydroxyacetonitrile in micro-mixer U；Mixed liquor flows through shell-and-tube reactor delay pipeline and completes contracting
Reaction is closed, the time is 20 seconds；
5) mixed liquor export liquid flows into cooling kettle V-03, and cooling is quenched, and equipment is run 45 minutes, adds water or two
Secondary mother liquor insulation separates out product at 30 DEG C, and yield is 99.92%, and purity is 99%；
6) separating step 5) in crystal after remaining liquid be mother liquor；
7) mother liquor multi_layer extraction aniline, remaining liquid is secondary mother liquid or added into a mother liquor
Aniline, extracts unreacted excessive aniline (being circularly used for reaction raw materials), and remaining liquid is secondary mother liquid；
8) secondary mother liquid is recycling in step 5) separate out crystal.
Embodiment 3
1) by reacting system pressure, pressure 3MPa is reached by counterbalance valve, heat exchanger and micro-mixer are heated to by constant temperature bath
180℃；Shell-and-tube reactor delay pipeline is heated to 200 DEG C by constant temperature bath；
2) mass concentration is fed for 99.0% aniline with volume flow 5.5L/min by pump P-01, flows through heat exchanger and enter
Row preheating；
3) mass concentration is fed for 40.0% hydroxyacetonitrile with volume flow 7.3L/min by pump P-02；
4) aniline is mixed with hydroxyacetonitrile in micro-mixer U；Mixed liquor flows through shell-and-tube reactor delay pipeline and completes contracting
Reaction is closed, the time is 15 seconds；
5) mixed liquor export liquid flows into cooling kettle V-03, and cooling is quenched, and equipment is run 2 hours, adds water or two
Secondary mother liquor insulation separates out product at 20 DEG C, and yield is 99.94%, and purity is 99.0%；
6) separating step 5) in crystal after remaining liquid be mother liquor；
7) mother liquor multi_layer extraction aniline, remaining liquid is secondary mother liquid or added into a mother liquor
Aniline, extracts unreacted excessive aniline, is circularly used for reaction raw materials, and remaining liquid is secondary mother liquid；
8) secondary mother liquid is recycling in step 5) separate out crystal.
Embodiment 4
1) by reacting system pressure, pressure 5MPa is reached by counterbalance valve, heat exchanger and micro-mixer are heated to by constant temperature bath
200℃；Shell-and-tube reactor delay pipeline is heated to 220 DEG C by constant temperature bath；
2) mass concentration is fed for 99.0% aniline with volume flow 12.1L/min by pump P-01, flows through heat exchanger
Preheated；
3) mass concentration is fed for 50.0% hydroxyacetonitrile with volume flow 12.9L/min by pump P-02；
4) aniline is mixed with hydroxyacetonitrile in micro-mixer U；Mixed liquor flows through shell-and-tube reactor delay pipeline and completes contracting
Reaction is closed, the time is 10 seconds；
5) mixed liquor export liquid flows into cooling kettle V-03, and cooling is quenched, and equipment is run 12 hours, adds water or two
Secondary mother liquor insulation separates out product at 20 DEG C, and yield is 99.93%, and purity is 99.1%；
6) separating step 5) in crystal after remaining liquid be mother liquor；
7) mother liquor multi_layer extraction aniline, remaining liquid is secondary mother liquid or added into a mother liquor
Aniline, extracts unreacted excessive aniline (being circularly used for reaction raw materials), and remaining liquid is secondary mother liquid；Recyclable profit
For step 5) separate out crystal.
Run 8000 hours with aniline volume flow 12.1L/min, hydroxyacetonitrile volume flow 12.9L/min, annual production
Up to 7500 tons.
Claims (9)
1. a kind of method of continuous production aniline-acetonitrile, continues through microfluidic channel reactor with aniline and hydroxyacetonitrile and enters
Row reaction, with molar ratio computing, 1<Aniline:Hydroxyacetonitrile≤1.2；Reaction temperature is 170~220 DEG C；Reaction time is 10~50
Second.
2. the method for continuous production aniline-acetonitrile according to claim 1, it is characterized in that, methods described is without urging
Carried out under conditions of agent.
3. the method for continuous production aniline-acetonitrile according to claim 1, it is characterized in that, the mass concentration of the aniline
For 99.0-99.9%, the mass concentration of hydroxyacetonitrile is 30-60%.
4. the method for continuous production aniline-acetonitrile according to claim 1, it is characterized in that, comprise the following steps：
(1), by counterbalance valve back pressure, the pressure in microfluidic channel reactor assembly is reached 2~5MPa；Heat exchanger, micro-mixer,
Shell-and-tube reactor delay pipeline is heated to 170-220 DEG C by constant temperature bath respectively；
(2) aniline is fed by feed pump, and the feed rate of aniline is 1.1-12.1L/min, flows through heat exchanger and is preheated；
(3) hydroxyacetonitrile is fed by feed pump, and the feed rate of hydroxyacetonitrile is 2.12-12.9L/min；
(4) the aniline after preheating is mixed with hydroxyacetonitrile in micro-mixer, completes to react through shell-and-tube reactor delay lie；
(5) reaction solution enters cooling system, is down to 20~30 DEG C, adds water stirring and separates out crystal.
5. it is according to claim 4 it is continuous production aniline-acetonitrile method, it is characterized in that, the step (5) reclaimed water plus
Enter amount for 0.5-5 times of the step (2) aniline and the step (3) volume total amount of hydroxyacetonitrile.
6. the method for continuous production aniline-acetonitrile according to claim 4, it is characterized in that, in addition to following aniline recovery
The step of：
(6) after the crystal in separating the step (5), remaining liquid is a mother liquor；
(7) the mother liquor multi_layer extraction aniline, remaining liquid is secondary mother liquid or adds benzene into a mother liquor
Amine, extracts unreacted excessive aniline, and remaining liquid is secondary mother liquid.
7. the method for continuous production aniline-acetonitrile according to claim 6, it is characterized in that, the step (7) middle aniline
Addition is the 1-15% of the step (2) inlet amount of middle aniline.
8. the method for continuous production aniline-acetonitrile according to claim 7, it is characterized in that, the step (7) middle aniline
Addition be the step (2) the inlet amount of middle aniline 10%.
9. the method for continuous production aniline-acetonitrile according to claim 6, it is characterized in that, in addition to the secondary mother liquid
The step of recycling：The secondary mother liquid that (7) step is obtained replaces the water of the step (5).
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110732298A (en) * | 2019-11-21 | 2020-01-31 | 温州国仕邦高分子材料有限公司 | Microwave radiation continuous water-based resin synthesis pipeline reactor |
| CN114716348A (en) * | 2022-03-02 | 2022-07-08 | 重庆东庚工程技术有限公司 | Production method and production system of anilinoacetonitrile |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101514170A (en) * | 2009-04-03 | 2009-08-26 | 重庆紫光化工股份有限公司 | Method for preparing n-phenylglycinonitrile |
| CN104496848A (en) * | 2015-01-15 | 2015-04-08 | 河北诚信有限责任公司 | Method for preparing n-phenylglycinenitrile |
| CN104628601A (en) * | 2015-01-30 | 2015-05-20 | 广安诚信化工有限责任公司 | Preparation method of efficient environmental-friendly aniline acetonitrile |
| CN104788340A (en) * | 2015-03-20 | 2015-07-22 | 重庆紫光化工股份有限公司 | Method for preparing n-phenylglycinenitrile |
-
2017
- 2017-05-10 CN CN201710326008.0A patent/CN107033030B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101514170A (en) * | 2009-04-03 | 2009-08-26 | 重庆紫光化工股份有限公司 | Method for preparing n-phenylglycinonitrile |
| CN104496848A (en) * | 2015-01-15 | 2015-04-08 | 河北诚信有限责任公司 | Method for preparing n-phenylglycinenitrile |
| CN104628601A (en) * | 2015-01-30 | 2015-05-20 | 广安诚信化工有限责任公司 | Preparation method of efficient environmental-friendly aniline acetonitrile |
| CN104788340A (en) * | 2015-03-20 | 2015-07-22 | 重庆紫光化工股份有限公司 | Method for preparing n-phenylglycinenitrile |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110732298A (en) * | 2019-11-21 | 2020-01-31 | 温州国仕邦高分子材料有限公司 | Microwave radiation continuous water-based resin synthesis pipeline reactor |
| CN110732298B (en) * | 2019-11-21 | 2024-02-23 | 温州国仕邦高分子材料有限公司 | Microwave radiation continuous water resin synthesis pipeline reactor |
| CN114716348A (en) * | 2022-03-02 | 2022-07-08 | 重庆东庚工程技术有限公司 | Production method and production system of anilinoacetonitrile |
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