CN107033030B - 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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- CN107033030B CN107033030B CN201710326008.0A CN201710326008A CN107033030B CN 107033030 B CN107033030 B CN 107033030B CN 201710326008 A CN201710326008 A CN 201710326008A CN 107033030 B CN107033030 B CN 107033030B
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- aniline
- hydroxyacetonitrile
- continuous production
- reaction
- acetonitrile
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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
Abstract
The invention discloses a kind of methods of continuous production aniline-acetonitrile, continue through microfluidic channel reactor with aniline and hydroxyacetonitrile and are reacted, with molar ratio computing, 1 < aniline: hydroxyacetonitrile≤1.2；Reaction temperature is 170~220 DEG C；Reaction time is 10~50 seconds.The method carries out under conditions of not adding catalyst.The advantages of present invention combination microfluidic channel reactor, the corrosion of microreactor is avoided, but also reaction cost reduces, simplify operating procedure, enlarge-effect is not present, so that the technique can realize that a set of equipment produces 10,000 tons scale per year；Hydroxyacetonitrile does not polymerize generation impurity in reaction process, and the aniline recycled in nonreactive mother liquor again can be with recovery；Improve aniline-acetonitrile mother liquid disposal have the shortcomings that large labor intensity, high labor cost, wastewater flow rate are big, generated secondary mother liquid can multiple recycled, reduce 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 technique, belong to aniline-acetonitrile synthesis field.
Background technique
Aniline-acetonitrile is the indigo intermediate of production, is mainly used for cowboy's cloth dyeing, is used for dyestuff intermediate；Also it can be used
In the synthesis of other fine chemicals, more popular use " aniline hydroxyacetonitrile method " domestic at present.
Patent CN101514170A discloses one kind, and to continue through duct type preheater, pipeline mixer, duct type anti-
The production method for answering device and reaction kettle uses the hydroxyacetonitrile of 60%~99.5% concentration for raw material, and reaction needs that auxiliary agent is added,
The fast reaction stage is first carried out in pipeline reactor, subsequently into slow reaction in reaction kettle progress, the reaction time is longer,
Energy consumption complicated for operation is higher simultaneously, and there are safety hazards using the hydroxyacetonitrile of high concentration.
Chinese invention patent prospectus CN104496848 discloses a kind of method for preparing aniline-acetonitrile, with benzene
Amine and hydroxyacetonitrile continue through micro passage reaction condensation reaction and generate aniline-acetonitrile, and the invention is pre- using basic catalyst
Handle hydroxyacetonitrile, reaction raw materials aniline and hydroxyacetonitrile molar ratio are 1:1~1.3, pressure 0.3MPa, and flow is smaller.It should
Corrosion can be generated to microreactor under the high temperature conditions using basic catalyst in invention, using the excessive mode meeting of hydroxyacetonitrile
So that the cyano value in mother liquor is higher, hydroxyacetonitrile can not recycle can also pollution to environment, while due to excess in the mother liquor
Impurity caused by hydroxyacetonitrile mostly can not also recycle.
Microreactor synthesizing anilino acetonitrile is using more and more attention has been paid to also carried out many researchs, used in recent years
The microreactor lab scale stage can achieve 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 there are serious amplification productions to ask for this
Topic, the present invention makes research thus.
Summary 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 changes feeding intake for material in conjunction with the advantages of microfluidic channel reactor so that enlarge-effect is not present in the reaction completely
Ratio is added without catalyst and is reacted, and obtained mother liquor recoverable reduces environmental pollution, and has excellent practical 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.
The method of the invention carries out under conditions of not adding catalyst as a preferred technical solution,.
The mass concentration of aniline of the present invention is 99.0-99.9%, the matter of hydroxyacetonitrile as a preferred technical solution,
Amount concentration is 30-60%.
The method of continuous production aniline-acetonitrile of the present invention as a preferred technical solution, comprising the following steps:
(1), by counterbalance valve back pressure, the pressure in microfluidic channel reactor assembly is made to reach 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, is flowed 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 mixes in micro-mixer with hydroxyacetonitrile, it is completed through shell-and-tube reactor delay lie anti-
It answers；
(5) reaction solution enters cooling system, is down to 20~30 DEG C, and water stirring is added and precipitates crystal.
Preferably, the step (5) in water additional amount be the step (2) aniline and the step (3) hydroxyacetonitrile body
0.5-5 times of product total amount.
The step of the method also includes following aniline recoveries as a preferred technical solution:
(6) separate the step (5) in crystal after, remaining liquid be a mother liquor；
(7) the mother liquor multi_layer extraction aniline, remaining liquid are secondary mother liquid or add into a mother liquor
Enter aniline, extract unreacted excessive aniline, remaining liquid is secondary mother liquid.
As a preferred technical solution, the step (7) in aniline additional amount be the step (2) in aniline inlet amount
1-15%.
It is highly preferred that the step (7) in aniline additional amount be the step (2) in aniline inlet amount 10%.
Mother liquor stirs a period of time after aniline is added, and standing sedimentation, aniline can separate apparent liquid layer, i.e., separable
Aniline out, this part aniline are circularly used for reaction raw materials.
When feed ratio aniline: when hydroxyacetonitrile is 1.2:1, aniline is excessive in reaction, and aniline can be not required to reaction liquid layer
Aniline is additionally added；When feed ratio aniline: when hydroxyacetonitrile is 1.01:1, the aniline that 1-15% is added is more conducive to be layered, most
Excellent additional amount is 10%.
Further include the steps that the secondary mother liquid recycles as a preferred technical solution: (7) the step is obtained
Secondary mother liquid replace the water of the step (5).
Microfluidic channel reactor is reachable to stir because its internal micro-structure makes consersion unit have great specific surface area
Even thousands of times of hundred times for mixing kettle specific surface area.Microfluidic channel reactor has fabulous heat transfer and mass transfer ability, can be with
Realize that the moment of material uniformly mixes and efficiently conducts heat.Aniline and hydroxyacetonitrile molar ratio of the present invention is 1.01~1.2:1, knot
The advantages of closing microfluidic channel reactor, while slight excess of aniline plays certain catalytic action and reaction is accelerated, it can
Reach more preferably effect:
1, microfluidic channel reactor feed system is carried out by feed pump, is not necessarily to artificial batch charging, does not have to interval
Operation, can continuously operate to obtain that the occupation area of equipment that finished product uses is small, production capacity is high, easy to operate；
2, it does not need that catalyst is added, avoids the corrosion of microreactor, but also reaction cost reduces, simplify operative employee
Enlarge-effect is not present in skill, so that the technique can realize that a set of equipment produces 10,000 tons scale per year；
3, hydroxyacetonitrile does not polymerize generation impurity in reaction process, and the aniline recycled in nonreactive mother liquor again can be with
Recovery；Improve aniline-acetonitrile mother liquid disposal and have the shortcomings that large labor intensity, high labor cost, wastewater flow rate are big, reduces
Environmental pollution.
4, generated secondary mother liquid can multiple recycled, for decrease temperature crystalline be precipitated product.Inside secondary mother liquid
Hydroxyacetonitrile reaction is very complete, there is seldom impurity in mother liquor, and in order to reduce the three wastes, secondary mother liquid can recycle completely,
I.e. secondary mother liquid is added after completing cooling quenching reaction in reaction, and dilution is conducive to stirring, while product is precipitated.
Detailed description of the invention
1 width of attached drawing of the present invention,
Fig. 1, process flow chart of the invention；
In figure, u micro-mixer, P pump, V charging/receiving tank, F filter, PT pressure transmitter, PSV safety valve, TE temperature
Meter, BPV counterbalance valve, PG pressure gauge, CV check valve, PIA pressure sensor, TI temperature sensor, E heat exchanger.
Specific embodiment
Following non-limiting embodiments can with a person of ordinary skill in the art will more fully understand the present invention, but not with
Any mode limits the present invention.Reagent described in following embodiments and material commercially obtain unless otherwise specified
, the present invention can achieve the scale of a set of equipment production 10,000 tons, but provide different flow data in example explanation.
Following embodiment is carried out under conditions of not adding 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) aniline that mass concentration is 99.5% is fed with volume flow 1.10L/min by pump P-01, flows through heat exchanger
It is preheated；
3) hydroxyacetonitrile that mass concentration is 30.0% is fed with volume flow 2.12L/min by pump P-02；
4) aniline mixes in micro-mixer U with hydroxyacetonitrile；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 stream enters to cool down kettle V-03, and cooling is quenched, and equipment is run 30 minutes, and water or two is added
Secondary mother liquor heat preservation is in 30 DEG C of precipitation products, yield 99.90%, purity 98.9%；
6) separating step 5) in crystal after remaining liquid be a mother liquor；
7) mother liquor multi_layer extraction aniline, remaining liquid are secondary mother liquid or are 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) and precipitates 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) aniline that mass concentration is 99.9% is fed with volume flow 2.19L/min by pump P-01, flows through heat exchanger
It is preheated；
3) hydroxyacetonitrile that mass concentration is 50.0% is fed with volume flow 2.54L/min by pump P-02；
4) aniline mixes in micro-mixer U with hydroxyacetonitrile；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 stream enters to cool down kettle V-03, and cooling is quenched, and equipment is run 45 minutes, and water or two is added
Secondary mother liquor heat preservation is in 30 DEG C of precipitation products, yield 99.92%, purity 99%；
6) separating step 5) in crystal after remaining liquid be a mother liquor；
7) mother liquor multi_layer extraction aniline, remaining liquid are secondary mother liquid or are 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) and precipitates 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) by mass concentration be 99.0% aniline with volume flow 5.5L/min by pump P-01 charging, flow through heat exchanger into
Row preheating；
3) hydroxyacetonitrile that mass concentration is 40.0% is fed with volume flow 7.3L/min by pump P-02；
4) aniline mixes in micro-mixer U with hydroxyacetonitrile；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 stream enters to cool down kettle V-03, and cooling is quenched, and equipment is run 2 hours, and water or two is added
Secondary mother liquor heat preservation is in 20 DEG C of precipitation products, yield 99.94%, purity 99.0%；
6) separating step 5) in crystal after remaining liquid be a mother liquor；
7) mother liquor multi_layer extraction aniline, remaining liquid are secondary mother liquid or are 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) and precipitates 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) aniline that mass concentration is 99.0% is fed with volume flow 12.1L/min by pump P-01, flows through heat exchanger
It is preheated；
3) hydroxyacetonitrile that mass concentration is 50.0% is fed with volume flow 12.9L/min by pump P-02；
4) aniline mixes in micro-mixer U with hydroxyacetonitrile；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 stream enters to cool down kettle V-03, and cooling is quenched, and equipment is run 12 hours, and water or two is added
Secondary mother liquor heat preservation is in 20 DEG C of precipitation products, yield 99.93%, purity 99.1%；
6) separating step 5) in crystal after remaining liquid be a mother liquor；
7) mother liquor multi_layer extraction aniline, remaining liquid are secondary mother liquid or are 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 benefit
It is precipitated crystal for step 5).
It is run 8000 hours with aniline volume flow 12.1L/min, hydroxyacetonitrile volume flow 12.9L/min, annual output
Up to 7500 tons.
Claims (8)
1. a kind of method of continuous production aniline-acetonitrile, with aniline and hydroxyacetonitrile continue through microfluidic channel reactor into
Row reaction, with molar ratio computing, 1 < aniline: hydroxyacetonitrile≤1.2；Reaction temperature is 170~220 DEG C；Reaction time is 10~50
Second；The method carries out under conditions of not adding catalyst.
2. the method for continuous production aniline-acetonitrile according to claim 1, characterized in that the mass concentration of the aniline
For 99.0-99.9%, the mass concentration of hydroxyacetonitrile is 30-60%.
3. the method for continuous production aniline-acetonitrile according to claim 1, characterized in that the following steps are included:
(1), by counterbalance valve back pressure, the pressure in microfluidic channel reactor assembly is made to reach 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, is flowed 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 mixes in micro-mixer with hydroxyacetonitrile, completes to react through shell-and-tube reactor delay lie；
(5) reaction solution enters cooling system, is down to 20~30 DEG C, and water stirring is added and precipitates crystal.
4. the method for continuous production aniline-acetonitrile according to claim 3, characterized in that the step (5) in water plus
Enter 0.5-5 times that amount is the step (2) aniline and the step (3) volume total amount of hydroxyacetonitrile.
5. the method for continuous production aniline-acetonitrile according to claim 3, characterized in that further include following aniline recovery
The step of:
(6) separate the step (5) in crystal after, remaining liquid be a mother liquor；
(7) the mother liquor multi_layer extraction aniline, remaining liquid are secondary mother liquid or benzene are added into a mother liquor
Amine, extracts unreacted excessive aniline, and remaining liquid is secondary mother liquid.
6. the method for continuous production aniline-acetonitrile according to claim 5, characterized in that the step (7) in aniline
Additional amount be the step (2) in aniline inlet amount 1-15%.
7. the method for continuous production aniline-acetonitrile according to claim 6, characterized in that the step (7) in aniline
Additional amount be the step (2) in aniline inlet amount 10%.
8. the method for continuous production aniline-acetonitrile according to claim 5, characterized in that further include the secondary mother liquid
The step of recycling: (7) secondary mother liquid that the step is obtained replaces the water of the step (5).
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| 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 |
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 |
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- 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 |
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