CN107935888B - Method for preparing 3-aminopropionitrile under supercritical condition - Google Patents
Method for preparing 3-aminopropionitrile under supercritical condition Download PDFInfo
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- CN107935888B CN107935888B CN201711431100.XA CN201711431100A CN107935888B CN 107935888 B CN107935888 B CN 107935888B CN 201711431100 A CN201711431100 A CN 201711431100A CN 107935888 B CN107935888 B CN 107935888B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/18—Preparation of carboxylic acid nitriles by reaction of ammonia or amines with compounds containing carbon-to-carbon multiple bonds other than in six-membered aromatic rings
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Abstract
The invention discloses a method for preparing 3-aminopropionitrile under a supercritical condition. Taking liquid ammonia and acrylonitrile as raw materials, and directly carrying out addition reaction in a pipeline type reactor under the condition of not adding a catalyst and a solvent to obtain the 3-aminopropionitrile. The reaction is carried out under the supercritical condition of liquid ammonia, the use of a catalyst and a solvent when the liquid ammonia is used in the past report is avoided, the product can be obtained by continuous rectification, the unreacted raw materials can be directly applied, the process is safe and environment-friendly, the substances of the unreacted raw materials are not introduced, and the green chemical concept is met. The conversion rate of the acrylonitrile can reach 99.5-100.0%, the selectivity can reach 85.5-95.8%, and the acrylonitrile has high industrial application value.
Description
Technical Field
The invention relates to the field of fine chemical engineering, in particular to a method for preparing 3-aminopropionitrile under a supercritical condition.
Background
3-aminopropionitrile, also known as β -aminopropionitrile (β -amino propionitrile, C)3H6N2Molecular weight: 70.11, CAS number: 151-18-8), colorless liquid, ammoniacal, is an intermediate for the synthesis of alanine and pantothenic acid; 1, 3-diaminopropane can be prepared by reduction; reacting with phosgene to obtain isocyanate, reacting with p-nitroaniline to obtain a sweetening agent, and using as medical intermediate.
The main synthetic method of the 3-aminopropionitrile is obtained by the addition reaction of acrylonitrile and ammonia, and the reaction formula is as follows:
CH2＝CHCN+NH3→NH2CH2CH2CN
the main by-product is 3-aminopropionitrile which is continuously reacted with acrylonitrile to obtain 3, 3-iminodipropionitrile, and the reaction formula is as follows:
NH2CH2CH2CN+CH2＝CHCN→NH(CH2CH2CN)2
the synthesis process of the 3-aminopropionitrile is mature, and related reports are more at home and abroad. In the traditional process, excessive concentrated ammonia water and acrylonitrile are stirred to react in a batch kettle type reactor, but the method generates a large amount of byproducts (mainly 3, 3-imido-dipropionitrile), the yield of the 3-aminopropionitrile is very low and is only 12-40%, the products need to remove a large amount of water, the energy consumption is high, and meanwhile, the aminopropionitrile can be obtained by a large amount of byproducts through subsequent treatment, so that the process is complex and the industrial production difficulty is high.
In order to improve the yield of the 3-aminopropionitrile and avoid using ammonia water for reaction, a large amount of energy consumption is needed for recycling water after treatment, and the 3-aminopropionitrile is obtained by reacting ammonia water with acrylonitrile instead of strong ammonia water.
US4967006 reports the addition of 408g (27.1 moles) of liquid ammonia to a 1 liter stainless steel autoclave heated to 50 ℃. 214.5g (4.04 moles) of acrylonitrile were continuously added to the autoclave over 1 hour. The reaction mixture was stirred at 50 ℃ for a further 1 hour. Unreacted ammonia was discharged after cooling. About 266g of a clear, colorless liquid were recovered, analyzed by gas chromatography as 39.1% by weight Aminopropionitrile (APN), 59.3% by weight Iminodipropionitrile (IBPN) and 1.6% by weight impurities.
US2401429A reports that 200g of acrylonitrile and liquid ammonia are reacted under reflux in a vacuum flask equipped with a dry ice condenser for 7 hours, after which the condenser is removed and the mixture is left to stand in the vacuum flask for 2 days to give 76% of bis (2-cyanoethyl) ether and 11% of 3-aminopropionitrile.
Although liquid ammonia is directly reacted with acrylonitrile to avoid adding water, a large amount of iminodiacetonitrile is generated as a byproduct, and the yield of the 3-aminopropionitrile is not remarkably improved. In order to improve the yield, the person skilled in the art can improve the product selectivity by adding a solvent or a catalyst into the system, or continuously react the iminodiacetonitrile with ammonia to generate the 3-aminopropionitrile in a continuous reaction mode, so as to improve the product yield.
The document Przemysl Chemiczny, 44, 2(1965) reports the preparation of 3-aminopropionitrile by reaction of acrylonitrile and ammonia in methanol at 118 ℃ and 1.2MP for 10 minutes with a yield of 81%. Patent JP07017935A reports the reaction of acrylonitrile with ammonia in an alcoholic solvent (e.g. isopropanol, 2-butanol, 2-pentanol, 2-methyl-3-pentanol, 2-hexanol, etc.), the conversion of acrylonitrile being 100% and the selectivity of 3-aminopropionitrile in the product being 75% when isopropanol is used as solvent.
U.S. Pat. No. 3,162,14280 reports the reaction of acrylonitrile with 25% ammonia in an autoclave, rectification under reduced pressure at a temperature below 60 ℃ to remove the ammonia and simultaneously separate 3-aminopropionitrile, the addition of the by-product iminodipropionitrile to the ammonia, and a cyclic reaction at 150 ℃ for 2 hours, and found that 63% of the iminodipropionitrile was converted to 3-aminopropionitrile, leaving only 7% of iminodipropionitrile and a yield of 3-aminopropionitrile of 84%.
U.S. Pat. No. 5,5247120 reports the conversion of acrylonitrile to 100% and the content of 3-aminopropionitrile to 90.6% in a tubular reactor in which acrylonitrile is reacted with liquid ammonia at 90 ℃ and 180bar in the presence of a ZSM-11 molecular sieve having a silica/alumina ratio of 2:8 as catalyst.
Patent CN 10139266 reports that a reaction-rectification coupling device is used for preparing 3-aminopropionitrile, the reaction temperature is 70-180 ℃, the pressure is 0.3-2 MPa, the reaction time is 0.5-2 hours, and the molar ratio of liquid ammonia to acrylonitrile is 1-10: 1, taking tert-butyl alcohol as a solvent, wherein the selectivity of the 3-aminopropionitrile is 62-80%.
Patent CN101817752 reports that 3-aminopropionitrile is prepared by using a fixed bed reactor, Dut-0 is used as a catalyst, the reaction temperature is 110 ℃, the pressure is 9.0MPa, and the molar ratio of liquid ammonia to acrylonitrile is 20: 1, volume space velocity of 0.8h-1The conversion of acrylonitrile was 100%, and the content of 3-aminopropionitrile was 87.9%.
Patent US5434291 reports the continuous reaction of liquid ammonia with acrylonitrile in a tubular reactor with Fe2O3The catalyst is used, the reaction temperature is 50 ℃, the pressure is 150bar, the acrylonitrile conversion rate is 90 percent and the content of the 3-aminopropionitrile is 57.6 percent after 22 hours of continuous reaction. When the acid ion exchanger Amberlyst 15 is used as a catalyst, the conversion rate of acrylonitrile is 99.4 percent and the content of 3-aminopropionitrile is 81.0 percent after 20 hours of continuous reaction. When the basic ion exchanger (Lewatit MP-600) is used as a catalyst, the reaction temperature is increased to 180 ℃, and after 20 hours of continuous reaction, the conversion rate of acrylonitrile is 99.4 percent, and the content of 3-aminopropionitrile is 77.8 percent.
Patent CN102827031 reports a process for continuously producing 3-aminopropionitrile, which comprises the steps of taking a mixture of isopropanol and n-propanol as a phase transfer catalyst, reacting ammonia water and acrylonitrile at the reaction temperature of 100-150 ℃ and the pressure of 0.05-1 MPa, then carrying out reduced pressure ammonia removal, water removal and solvent removal treatment, and finally carrying out distillation to obtain the 3-aminopropionitrile.
Patent CN105884649 reports a recovery process of 3-aminopropionitrile, a certain amount of 35% ammonia water is added into distillation waste liquid of 3-aminopropionitrile (the content of 3, 3-imido-dipropionitrile is 80%), the pressure is controlled at 4MPa and the temperature is 120 ℃ in a high-pressure kettle, the reaction is carried out for 2 hours, the ammonia water is recovered after cooling, and the 3-aminopropionitrile is obtained by distillation, wherein the yield is 61.7% -69.4%.
In the above reports, the use of alcohol as solvent in the synthesis of 3-aminopropionitrile has the advantages of reducing the amount of ammonia, increasing the reaction speed, improving the selectivity of the main product, etc., but the separation of the solvent required in the reaction is required, and the separation of the produced alkoxypropionitrile from the product is difficult, thereby limiting the development of the method in industry. The catalyst can effectively improve the product yield, but also increases the cost, and the invalid catalyst needs to be replaced in the production process, so that the operation is complicated. The continuous reaction is carried out in a fixed bed tubular reactor to produce the 3-aminopropionitrile, the by-product iminodiacetonitrile needs to be recycled and further reacts with ammonia to generate a product, so that the process is complex and the energy consumption is high.
Disclosure of Invention
In order to solve the problems in the prior art, the present invention provides a method for preparing 3-aminopropionitrile under supercritical conditions.
A process for preparing 3-aminopropionitrile under supercritical conditions, comprising:
reacting liquid ammonia with acrylonitrile under the supercritical condition that the temperature is 135-250 ℃ and the pressure is 13-20 MPa to obtain the 3-aminopropionitrile.
In the invention, reactants are put under a specific supercritical condition for reaction, 3-aminopropionitrile can be obtained with higher efficiency without adding catalysts and solvents in the prior art, the conversion rate of acrylonitrile can reach 99.5-100.0%, the selectivity can reach 85.5-95.8%, and the method has higher industrial application value.
Preferably, the reaction does not require the addition of a catalyst and a solvent. Because no other additional reagent is added, after the reaction is finished, the post-treatment process of the reaction liquid is simpler, and the industrial operation is facilitated.
Preferably, the pressure under the supercritical condition is 13MPa to 18 MPa.
More preferably, the temperature of the supercritical condition is 150 to 200 ℃. At this temperature and pressure, the conversion and selectivity of the reaction can be further increased.
In the invention, the reaction is carried out in a pipeline reactor;
during the reaction, the flow of the acrylonitrile is controlled by a metering pump, the acrylonitrile enters a vaporization chamber to be vaporized and then enters a pipeline reactor, and meanwhile, the flow of the liquid ammonia is controlled by the metering pump to directly enter the pipeline reactor to carry out the reaction.
In the invention, the molar ratio of the liquid ammonia to the acrylonitrile is 8-20: 1. further preferably, the molar ratio of the liquid ammonia to the acrylonitrile is 10-15: 1. in the reaction process, liquid ammonia is used as an excessive reagent, so that the generation of 3, 3-imido-dipropionitrile can be effectively prevented, and the liquid ammonia can be recovered and reused more conveniently after the reaction is finished.
In the invention, in the pipeline type reactor, the retention time is too long, side reactions are possibly caused, the reaction is insufficient when the retention time is too short, and the reaction retention time is generally 5-30 min. Preferably, the reaction residence time is 10 to 20 min.
In the invention, after the reaction is finished, the post-treatment process is as follows: collecting reaction liquid, separating an organic layer, and purifying (such as rectifying) to obtain the 3-aminopropionitrile, wherein unreacted raw materials can be conveniently recycled and reused.
Compared with the prior art, the invention has the beneficial effects that:
(1) the ammonia water is replaced by the liquid ammonia in the reaction process, so that the introduction of water in the system is avoided, on one hand, the energy consumption of subsequent distilled water recovery is reduced, on the other hand, the generation of a byproduct, namely hydroxypropionitrile (an addition product of acrylonitrile and water) is reduced, and the yield is improved.
(2) The reaction is carried out under the supercritical condition of liquid ammonia, the feeding proportion of the liquid ammonia is increased, the reaction time can be effectively shortened, the use of a catalyst and a solvent when the liquid ammonia is used in the previous report is avoided, the reactant is the solvent, the separation difficulty of the solvent is avoided in the post-treatment, the product can be obtained by continuous rectification, the unreacted raw materials can be directly used, and the generation of the by-product iminodipropionitrile is reduced.
(3) The process is safe and environment-friendly, does not introduce substances of non-reaction raw materials, and accords with the green chemical concept.
Drawings
FIG. 1 is a flow diagram of a supercritical tubular reaction of the present invention.
Detailed Description
The invention is described in detail below with reference to the drawings and the detailed description.
Example 1
As shown in a reaction flow chart shown in figure 1, a metering pump 1 is started, acrylonitrile is pumped in at a constant rate of 2ml/min, the temperature of a vaporizer is set to be 90 ℃, a liquid ammonia metering pump 2 is started, liquid ammonia is pumped in at a constant rate of 9ml/min, the temperature of a supercritical pipeline reactor is set to be 160 ℃, a high-precision reverse pressure controller behind a condenser is adjusted, the pressure is controlled to be 15 +/-1 MPa, and the reaction residence time is 20 min. After the completion of the reaction, the reaction liquid was collected, the organic layer was separated, and the conversion of acrylonitrile was calculated to be 100% and the selectivity of 3-aminopropionitrile was calculated to be 90.2% by gas chromatography.
Examples 2 to 22
According to the operating method of example 1, the reaction conditions were varied: liquid ammonia flow, reactor temperature, reaction pressure, residence time, reaction conditions and reaction results are shown in table 1.
TABLE 1 reaction conditions and reaction results of examples 2 to 22
From the results in table 2, it can be seen that under the supercritical conditions of the present invention, better conversion and selectivity can be obtained without adding additional catalyst and solvent.
Claims (9)
1. A process for preparing 3-aminopropionitrile under supercritical conditions, comprising:
under the supercritical conditions that the temperature is 150-200 ℃ and the pressure is 13-20 MPa, liquid ammonia and acrylonitrile react to obtain the 3-aminopropionitrile.
2. The method of claim 1, wherein the reaction does not require the addition of a catalyst and a solvent.
3. The method of claim 1, wherein the supercritical conditions are at a pressure of 13MPa to 18 MPa.
4. A process according to any one of claims 1 to 3, wherein the reaction is carried out in a pipeline reactor;
during the reaction, the flow of the acrylonitrile is controlled by a metering pump, the acrylonitrile enters a vaporization chamber to be vaporized and then enters a pipeline reactor, and meanwhile, the flow of the liquid ammonia is controlled by the metering pump to directly enter the pipeline reactor to carry out the reaction.
5. The method according to claim 4, wherein the molar ratio of the liquid ammonia to the acrylonitrile is 8-20: 1.
6. the method according to claim 5, wherein the molar ratio of the liquid ammonia to the acrylonitrile is 10-15: 1.
7. the method according to claim 4, wherein the reaction residence time is 5 to 30min in the pipe reactor.
8. The method according to claim 7, wherein the reaction residence time is 10-20 min in the pipeline reactor.
9. The method according to claim 1, wherein the 3-aminopropionitrile is obtained by collecting a reaction solution after completion of the reaction, separating an organic layer, and purifying the organic layer.
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| CN107935888B (en) * | 2017-12-26 | 2020-04-07 | 浙江新和成股份有限公司 | Method for preparing 3-aminopropionitrile under supercritical condition |
| CN112279783B (en) * | 2020-09-27 | 2022-09-02 | 山东新和成精化科技有限公司 | Method for preparing 3-hydroxypropionitrile under supercritical condition |
| CN116162043A (en) * | 2022-12-23 | 2023-05-26 | 大连理工大学 | Continuous preparation method of 3-hydroxy propionitrile |
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