CN107935888A - A kind of method for preparing 3 aminopropionitriles at supercritical conditions - Google Patents
A kind of method for preparing 3 aminopropionitriles at supercritical conditions Download PDFInfo
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- CN107935888A CN107935888A CN201711431100.XA CN201711431100A CN107935888A CN 107935888 A CN107935888 A CN 107935888A CN 201711431100 A CN201711431100 A CN 201711431100A CN 107935888 A CN107935888 A CN 107935888A
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- reaction
- aminopropionitriles
- acrylonitrile
- liquefied ammonia
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
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- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a kind of method for preparing 3 aminopropionitriles at supercritical conditions.Using liquefied ammonia and acrylonitrile as raw material, under conditions of catalysts and solvents are not added with, direct addition reaction obtains 3 aminopropionitriles in pipeline reactor.Present invention reaction carries out under the super critical condition of liquefied ammonia, avoid the previously reported middle use with catalysts and solvents during liquefied ammonia, pass through continuous rectification, it can obtain product, unreacting material can be applied mechanically directly, the environmental protection of this process safety, is not introduced into the material of non-reaction raw materials, meets green chemical concept.Up to 99.5 100.0%, selectivity up to 85.5 95.8% there are the conversion ratio of acrylonitrile of the present invention higher industrial applications to be worth.
Description
Technical field
The present invention relates to field of fine chemical, a kind of 3- aminopropionitriles that prepare at supercritical conditions are related in particular to
Method.
Background technology
3- aminopropionitriles, also referred to as β-aminopropionitrile (β-amino propionitrile, C3H6N2, molecular weight：70.11,
No. CAS：151-18-8), colourless liquid, there is ammonia odor, is the intermediate for synthesizing alanine and pantothenic acid；1,3- can be made through reduction
Diaminopropanes；Isocyanates can be made with phosgene reaction, a kind of sweetener can be made with paranitroanilinum reaction, also serve as doctor
Medicine intermediate.
The primary synthetic methods of 3- aminopropionitriles obtain for acrylonitrile with ammonia addition reaction, and reaction equation is as follows：
CH2=CHCN+NH3→NH2CH2CH2CN
Main By product continues to obtain 3,3- iminobis-propanenitriles with acrylonitrile reactor for 3- aminopropionitriles, and reaction equation is such as
Under：
NH2CH2CH2CN+CH2=CHCN → NH (CH2CH2CN)2
The synthesis technique comparative maturity of 3- aminopropionitriles, domestic and international relevant report are more.Traditional handicraft is in batch tank
Excessive concentrated ammonia and acrylonitrile stirring are reacted in reactor, but the substantial amounts of accessory substance of this method generation (mainly 3,
3- iminodipropioditriles), the yield of 3- aminopropionitriles is very low, and only 12~40%, product needs to remove substantial amounts of water, energy consumption
Greatly, while substantial amounts of accessory substance needs that by subsequent treatment aminopropionitrile could be obtained, and makes complex process, industrialized production difficulty
Greatly.
To improve the yield of 3- aminopropionitriles, while avoid being reacted using ammonium hydroxide, post processing recycle-water needs a large amount of
Energy consumption, it will usually instead of concentrated ammonia liquor with liquefied ammonia, 3- aminopropionitriles obtained with acrylonitrile reactor.
US4967006 reports addition 408g (27.1 moles) liquefied ammonia into 1 liter of stainless steel autoclave, is heated to 50 DEG C.1
214.5g (4.04 moles) acrylonitrile is added continuously in autoclave in hour.Reaction mixture is stirred for 1 at 50 DEG C
Hour.Unreacted ammonia is discharged after cooling.The colourless liquid of about 266g clarifications has been recycled, has been by gas chromatography analysis
The impurity of the aminopropionitrile (APN) of 39.1% (weight), 59.3% (weight) iminobis-propanenitrile (IBPN) and 1.6 weight %.
US2401429A reports 200g acrylonitrile and liquefied ammonia back flow reaction 7 in the Dewar bottle equipped with dry-ice condenser
Hour, condenser is then removed, mixture stands 2 days in Dewar bottle, and obtaining must outside 76% double (2- cyano ethyls) ethers
To 11% 3- aminopropionitriles.
Although avoiding the addition of water using the directly reaction of liquefied ammonia and acrylonitrile, but still there is substantial amounts of accessory substance imino-diacetic
Propionitrile generates, and the yield of 3- aminopropionitriles does not increase significantly.In order to improve yield, those skilled in the art pass through in system
Add solvent or catalyst improves product selectivity, or make iminobis-propanenitrile continuation anti-with ammonia by the way of successive reaction
3- aminopropionitriles should be generated, to improve product yield.
Document Przemysl Chemiczny, 44,2 (1965) are reported at 118 DEG C, under 1.2MP, acrylonitrile and ammonia is molten
Reaction prepares 3- aminopropionitriles in methanol, and in 10 minutes reaction time, yield is up to 81%.Patent JP07017935A is reported
The reaction of acrylonitrile and ammonia, is adopted in alcoholic solvent (such as isopropanol, 2- butanol, 2- amylalcohols, 2- methyl -3- amylalcohols, 2- hexanols etc.)
When with isopropanol being solvent, the conversion ratio of acrylonitrile is up to 100%, and the selectivity of 3- aminopropionitriles is 75% in product.
United States Patent (USP) US3914280 is reported reacts acrylonitrile and 25% ammonium hydroxide in autoclave, is less than in temperature
Rectification under vacuum removes ammonium hydroxide at 60 DEG C, while isolates 3- aminopropionitriles, and accessory substance iminobis-propanenitrile is rejoined ammonia
In water, when circular response 2 is small at 150 DEG C, it is found that 63% iminobis-propanenitrile is converted into 3- aminopropionitriles, only remaining 7%
Iminobis-propanenitrile, 3- aminopropionitriles yield be 84%.
United States Patent (USP) US5247120 is reported using silica alumina ratio as 2:8 ZSM-11 molecular sieves are catalyst, in pipe reaction
The reaction of acrylonitrile and liquefied ammonia in device, at 90 DEG C, under conditions of 180bar, acrylonitrile conversion rate is up to 100%, 3- aminopropionitriles
Content is 90.6%.
Patent CN101397266 reports a kind of reaction rectification coupling device and prepares 3- aminopropionitriles, reaction temperature 70
DEG C~180 DEG C, 0.3~2MPa of pressure, when the reaction time 0.5~2 is small, the molar ratio of liquefied ammonia and acrylonitrile is 1~10：1, with uncle
Butanol is solvent, and the selectivity of 3- aminopropionitriles is 62%~80%.
Patent CN101817752 is reported prepares 3- aminopropionitriles using fixed bed reactors, using Dut-0 as catalyst,
Reaction temperature is 110 DEG C, pressure 9.0MPa, and the molar ratio of liquefied ammonia and acrylonitrile is 20：1, volume space velocity 0.8h-1, acrylonitrile turn
Rate 100%, 3- aminopropionitriles content are 87.9%.
Patent US5434291 is reported in tubular reactor, liquefied ammonia and acrylonitrile successive reaction, with Fe2O3For catalysis
Agent, 50 DEG C, pressure 150bar of reaction temperature, after 22h successive reactions, acrylonitrile conversion rate is 90%, 3- aminopropionitriles
Content is 57.6%.When with acid ion exchangers Amberlyst 15 being catalyst, after 20h successive reactions, acrylonitrile turns
Rate is that the content of 99.4%, 3- aminopropionitriles is 81.0%.Alkaline ion exchanger (Lewatit MP-600) is catalyst
When, reaction temperature brings up to 180 DEG C, and after 20h successive reactions, acrylonitrile conversion rate contains for 99.4%, 3- aminopropionitriles
Measure as 77.8%.
Patent CN102827031 reports a kind of technique of continuous production 3- aminopropionitriles, with isopropanol and normal propyl alcohol
Mixture is reacted as phase transfer catalyst, ammonium hydroxide with acrylonitrile, 100 DEG C~150 DEG C of reaction temperature, and pressure 0.05~
1MPa, then carries out decompression and drives ammonia, water removal and except solvent processing, finally distilled to obtain 3- aminopropionitriles.
Patent CN105884649 reports a kind of recovery process of 3- aminopropionitriles, in the slops of 3- aminopropionitriles
(3,3- iminodipropioditrile contents add a certain amount of 35% ammonium hydroxide to be 80%) middle, and pressure is controlled in 4MPa in autoclave,
120 DEG C of temperature, when reaction 2 is small, recycles ammonium hydroxide, distillation obtains 3- aminopropionitriles, and yield is 61.7%~69.4% after cooling.
In above-mentioned report, the dosage of ammonia can be reduced when synthesizing 3- aminopropionitriles using alcohol as solvent, accelerates reaction speed,
The advantages that principal product is selective, but required solvent in reaction to be separated are improved, while the alkoxypropionitrile generated is difficult to from product
Middle separation, thus limit its development in the industry.Product yield can be effectively improved using catalyst, but is also increased at the same time
Cost, the catalyst of failure is needed replacing in production process, is made complicated.Carried out in fixed-bed tube reactor continuous
Change reaction production 3- aminopropionitriles, it is necessary to which accessory substance iminobis-propanenitrile is recycled, generation product further reacted with ammonia,
Make complex process, energy consumption is big.
The content of the invention
In order to solve above-mentioned problems of the prior art, the present invention provides one kind to prepare 3- at supercritical conditions
The method of aminopropionitrile.
A kind of method for preparing 3- aminopropionitriles at supercritical conditions, including：
It it is 135 DEG C~250 DEG C in temperature, pressure is under the super critical condition of 13MPa~20MPa, and liquefied ammonia is sent out with acrylonitrile
Raw reaction, obtains the 3- aminopropionitriles.
In the present invention, reactant is placed under specific super critical condition and is reacted, be added without urging for the prior art
When agent and solvent, 3- aminopropionitriles can be also obtained with higher efficiency, the conversion ratio of acrylonitrile is up to 99.5-100.0%, choosing
Selecting property up to 85.5-95.8% there are higher industrial applications to be worth.
Preferably, the reaction need not add catalysts and solvents.Due to being added without other additional agents, reaction
After the completion of, the last handling process of reaction solution is simpler, easy to industrial operation.
Preferably, the pressure of the super critical condition is 13MPa~18MPa.
As further preferably, the temperature of the super critical condition is 150 DEG C~200 DEG C.At this temperature and pressure,
The conversion ratio and selectivity of reaction can be further improved.
In the present invention, the reaction carries out in pipeline reactor；
The flow of acrylonitrile is controlled during reaction by metering pump, duct type reaction is entered back into after being introduced into vaporizer vaporization
Device, while liquefied ammonia is directly entered in pipeline reactor by metering pump control flow and is reacted.
In the present invention, the molar ratio of the liquefied ammonia and acrylonitrile is 8~20：1.As further preferred, the liquefied ammonia
Molar ratio with acrylonitrile is 10~15：1.In reaction process, using liquefied ammonia as excessive reagent, on the one hand can effectively it prevent
The generation of 3,3- iminodipropioditriles, on the other hand, after liquefied ammonia reaction is completed, can be more convenient to carry out recovery.
In the present invention, in pipeline reactor, the residence time is long, it is possible to can cause the generation of side reaction, stop
Time is too short, then reacts insufficient, reaction time is generally 5~30min.Preferably, reaction time for 10~
20min。
In the present invention, after reaction, last handling process is as follows：Reaction solution is collected, separates organic layer, by purifying (example
Such as rectifying) obtain as described in 3- aminopropionitriles, unreacted raw material can easily carry out recovery.
Compared with the existing technology, beneficial effects of the present invention are embodied in：
(1) reaction process substitutes ammonium hydroxide with liquefied ammonia, avoids and water is introduced in system, on the one hand reduces subsequent recovery steaming
The energy consumption of water, on the other hand reduces the generation of accessory substance hydroxypropionitrile (acrylonitrile and water addition compound product), improves yield.
(2) reaction carries out under the super critical condition of liquefied ammonia, and increases the ingredient proportion of liquefied ammonia, can effectively shorten reaction
Time, avoids the previously reported middle use with catalysts and solvents during liquefied ammonia, and reactant is solvent in itself, is kept away in post processing
It is difficult to have exempted from the separation of solvent, has passed through continuous rectification, you can obtain product, unreacting material can directly be applied mechanically, reduced at the same time
The generation of accessory substance iminobis-propanenitrile.
(3) this process safety environmental protection, is not introduced into the material of non-reaction raw materials, meets green chemical concept.
Brief description of the drawings
Fig. 1 is the flow chart of the overcritical pipe reaction of the present invention.
Embodiment
Below in conjunction with specification drawings and specific embodiments, the present invention is described in detail.
Embodiment 1
As shown in reacting flow chart as shown in Figure 1, metering pump 1 is opened, acrylonitrile, vapour are pumped into 2ml/min constant rate of speed
The temperature setting for changing device is 90 DEG C, drives metering of liquid ammonia pump 2, liquefied ammonia, overcritical pipeline reactor are pumped into 9ml/min constant rate of speed
Temperature is set as 160 DEG C, adjusts the high-precision buffer brake controller after condenser, and pressure control stops in 15 ± 1MPa, reaction
It is 20min to stay the time.After the completion of reaction, reaction solution is collected, separates organic layer, and with gas chromatographic analysis, calculate acrylonitrile
Conversion ratio be that the selectivity of 100%, 3- aminopropionitriles is 90.2%.
Embodiment 2-22
According to the operating method of embodiment 1, change reaction condition：Liquefied ammonia flow, temperature of reactor, reaction pressure, stop
Time, obtains reaction solution, its reaction condition and reaction result are as shown in table 1.
The reaction condition and reaction result of 1 embodiment 2~22 of table
As shown in Table 2, under the super critical condition of the present invention, extra catalysts and solvents are added without, are reacted
Also preferable conversion ratio and selectivity can be obtained.
Claims (10)
- A kind of 1. method for preparing 3- aminopropionitriles at supercritical conditions, it is characterised in that including：It it is 135 DEG C~250 DEG C in temperature, pressure is under the super critical condition of 13MPa~20MPa, and liquefied ammonia occurs anti-with acrylonitrile Should, obtain the 3- aminopropionitriles.
- 2. according to the method described in claim 1, it is characterized in that, the reaction need not add catalysts and solvents.
- 3. according to the method described in claim 1, it is characterized in that, the pressure of the super critical condition is 13MPa~18MPa.
- 4. according to the method described in claim 1, it is characterized in that, the temperature of the super critical condition is 150 DEG C~200 DEG C.
- 5. according to Claims 1 to 4 any one of them method, it is characterised in that the reaction is in pipeline reactor Carry out；The flow of acrylonitrile is controlled during reaction by metering pump, enters back into pipeline reactor after being introduced into vaporizer vaporization, together When liquefied ammonia be directly entered in pipeline reactor and reacted by metering pump control flow.
- 6. according to the method described in claim 5, it is characterized in that, the molar ratio of the liquefied ammonia and acrylonitrile is 8~20：1.
- 7. according to the method described in claim 6, it is characterized in that, the molar ratio of the liquefied ammonia and acrylonitrile is 10~15：1.
- 8. according to the method described in claim 5, it is characterized in that, in pipeline reactor, reaction time for 5~ 30min。
- 9. according to the method described in claim 8, it is characterized in that, in pipeline reactor, reaction time for 10~ 20min。
- 10. according to the method described in claim 1, it is characterized in that, after reaction, collection reaction solution, separates organic layer, passes through Cross purifying and obtain the 3- aminopropionitriles.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN112279783A (en) * | 2020-09-27 | 2021-01-29 | 山东新和成精化科技有限公司 | Method for preparing 3-hydroxypropionitrile under supercritical condition |
| CN116655496A (en) * | 2022-12-23 | 2023-08-29 | 大连理工大学 | Continuous preparation method of 3-hydroxy propionitrile |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN112279783A (en) * | 2020-09-27 | 2021-01-29 | 山东新和成精化科技有限公司 | Method for preparing 3-hydroxypropionitrile under supercritical condition |
| CN116655496A (en) * | 2022-12-23 | 2023-08-29 | 大连理工大学 | Continuous preparation method of 3-hydroxy propionitrile |
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Effective date of registration: 20200604 Address after: 312500, No. 418, West Avenue, Qixing street, Xinchang County, Shaoxing, Zhejiang Co-patentee after: SHANDONG XINHECHENG AMINO ACID Co.,Ltd. Patentee after: ZHEJIANG NHU Co.,Ltd. Co-patentee after: SHANDONG NHU VITAMIN Co.,Ltd. Co-patentee after: SHANDONG XINHECHENG FINE CHEMICAL TECHNOLOGY Co.,Ltd. Address before: 312500, No. 418, West Avenue, Qixing street, Xinchang County, Shaoxing, Zhejiang Co-patentee before: SHANDONG XINHECHENG AMINO ACID Co.,Ltd. Patentee before: ZHEJIANG NHU Co.,Ltd. Co-patentee before: SHANDONG NHU VITAMIN Co.,Ltd. |
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