CN112390728B - Method for continuously preparing cyano norbornene by using microchannel reactor - Google Patents
Method for continuously preparing cyano norbornene by using microchannel reactor Download PDFInfo
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- CN112390728B CN112390728B CN202011360136.5A CN202011360136A CN112390728B CN 112390728 B CN112390728 B CN 112390728B CN 202011360136 A CN202011360136 A CN 202011360136A CN 112390728 B CN112390728 B CN 112390728B
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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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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0093—Microreactors, e.g. miniaturised or microfabricated reactors
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00781—Aspects relating to microreactors
- B01J2219/0095—Control aspects
- B01J2219/00984—Residence time
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2602/00—Systems containing two condensed rings
- C07C2602/36—Systems containing two condensed rings the rings having more than two atoms in common
- C07C2602/42—Systems containing two condensed rings the rings having more than two atoms in common the bicyclo ring system containing seven carbon atoms
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Abstract
The invention provides a method for continuously preparing cyano norbornene by using a microchannel reactor, which comprises the following steps: reacting cyclopentadiene and acrylonitrile preheated to 40-55 ℃ in a microchannel reactor to obtain cyano norbornene; the reaction temperature is 25-40 ℃, the pressure is 0.1-0.4 MPa, and the retention time is 10-100 s. The method provided by the invention greatly shortens the reaction time, improves the reaction efficiency and ensures that the product has higher yield and purity by controlling the reaction temperature, pressure and time of the cyclopentadiene and the preheated acrylonitrile in the microchannel reactor. The method avoids the industrial synthesis at high temperature and high pressure, improves the safety in the reaction process, is simple and has extremely high social and economic benefits. The experimental results show that: the yield of the product prepared by the method is more than 95%, and the purity is more than 96%.
Description
Technical Field
The invention belongs to the technical field of preparation of cyano norbornene, and particularly relates to a method for continuously preparing cyano norbornene by using a microchannel reactor.
Background
2-cyano-5-norbornene, hetero-bicyclo [2.2.1]Hept-5-ene-2-carbonitrile, formula C 8 H 9 N。
At present, the cyano norbornene is mostly prepared by taking cyclopentadiene or dicyclopentadiene as a raw material; the method comprises the following steps: patent publication No. CN110944976A synthesizes cyano norbornene from a system of dicyclopentadiene, acrylonitrile and a methyl-bis-cyclononadiene.
The synthesis method has incomplete reaction and needs to recycle unreacted raw materials; the reaction temperature is high; the reaction time is long, and the efficiency is slow; the reaction pressure is high; the reaction yield is low. In addition, the above method has a problem of complicated operation.
Disclosure of Invention
In view of this, the present invention provides a method for continuously preparing cyanonorbornene by using a microchannel reactor, which has the advantages of high reaction rate, high product yield and high purity.
The invention provides a method for continuously preparing cyano norbornene by using a microchannel reactor, which comprises the following steps:
reacting cyclopentadiene and acrylonitrile preheated to 40-55 ℃ in a microchannel reactor to obtain cyano norbornene;
the reaction temperature is 25-40 ℃, the pressure is 0.1-0.4 MPa, and the retention time is 10-100 s.
Preferably, the reaction temperature is 30-40 ℃, the pressure is 0.12-0.3 MPa, and the retention time is 25-90 s.
Preferably, the cyclopentadiene and acrylonitrile are present in a molar ratio of 1:1 to 1.1.
Preferably, the preheated acrylonitrile is prepared according to the following method:
preheating acrylonitrile in a microchannel reactor to obtain preheated acrylonitrile;
the preheating time is 15-45 s.
Preferably, the cyclopentadiene and acrylonitrile are present in a molar ratio of 1: 1.02-1.08.
Preferably, the characteristic dimension of the channels of the microchannel reactor is 30 μm, with a volume of 3.7ml per plate.
The invention provides a method for continuously preparing cyano norbornene by using a microchannel reactor, which comprises the following steps: reacting cyclopentadiene and acrylonitrile preheated to 40-55 ℃ in a microchannel reactor to obtain cyano norbornene; the reaction temperature is 25-40 ℃, the pressure is 0.1-0.4 MPa, and the retention time is 10-100 s. The method provided by the invention greatly shortens the reaction time, improves the reaction efficiency and ensures that the product has higher yield and purity by controlling the reaction temperature, pressure and time of the cyclopentadiene and the preheated acrylonitrile in the microchannel reactor. The method avoids the industrial synthesis at high temperature and high pressure, improves the safety in the reaction process, is simple and has extremely high social and economic benefits. The experimental results show that: the yield of the product prepared by the method is more than 95%, and the purity is more than 96%.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of cyanonorbornene prepared in example 1 of the present invention.
Detailed Description
The invention provides a method for continuously preparing cyano norbornene by using a microchannel reactor, which comprises the following steps:
reacting cyclopentadiene and acrylonitrile preheated to 40-55 ℃ in a microchannel reactor to obtain cyano norbornene;
the reaction temperature is 25-40 ℃, the pressure is 0.1-0.4 MPa, and the retention time is 10-100 s.
The method provided by the invention greatly shortens the reaction time, improves the reaction efficiency and ensures that the product has higher yield and purity by controlling the reaction temperature, pressure and time of the cyclopentadiene and the preheated acrylonitrile in the microchannel reactor.
In the present invention, the reaction temperature is preferably 30 to 40 ℃, the pressure is preferably 0.15 to 0.35MPa, and the residence time is preferably 40 to 90s. In a specific embodiment, the reaction temperature is 38 ℃, the reaction time is 80s, and the reaction pressure is 0.35MPa; or the reaction temperature is 25 ℃, the reaction time is 55s, and the reaction pressure is 0.2MPa; or the reaction temperature is 32 ℃, the reaction time is 25s, and the reaction pressure is 0.12MPa.
In the present invention, the preheated acrylonitrile is prepared according to the following method:
preheating acrylonitrile in a microchannel reactor to obtain preheated acrylonitrile;
the preheating time is 10-45 s.
The preheating temperature is preferably 45-55 ℃, and the time is preferably 15-40 s. In a specific embodiment, the preheating temperature is 55 ℃ and the preheating time is 40s; or preheating at 48 deg.C for 25s; or the preheating temperature is 40 ℃ and the preheating time is 15s.
In the present invention, the molar ratio of cyclopentadiene and acrylonitrile is preferably 1: 1.02-1.08. In specific examples, the molar ratio of cyclopentadiene to acrylonitrile is 1.08; or 1:1.05; or 1:1.02.
the source of the microchannel reactor adopted by the invention is not particularly limited, and the device can be prepared by the equipment well known by the technical personnel in the field; the invention adopts a corning G1 silicon carbide reactor. The characteristic dimension of the channel of the microchannel reactor was 30 μm, and the volume of each plate was 3.7ml.
To further illustrate the present invention, a method for continuously preparing cyanonorbornene using a microchannel reactor according to the present invention will be described in detail with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Preheating acrylonitrile in a first microchannel reactor, wherein the preheating temperature is 55 ℃, the retention time is 40s, feeding the preheated acrylonitrile into a second microchannel reactor, and then feeding cyclopentadiene, wherein the mol ratio of cyclopentadiene to acrylonitrile is 1:1.08, controlling the temperature of the second microchannel to be 38 ℃, the retention time to be 80s, the reaction pressure to be 0.35MPa, receiving a reaction material after the reaction is finished, namely the cyano norbornene,
the detection of the reacted product shows that the product content is 97.1 percent and the yield is 96.3 percent.
The nuclear magnetic hydrogen spectrum diagram obtained by detecting the obtained product with nuclear magnetism is shown in figure 1.
Example 2
Preheating acrylonitrile in a first microchannel reactor, wherein the preheating temperature is 48 ℃, the retention time is 25s, feeding the preheated acrylonitrile into a second microchannel reactor, and then feeding cyclopentadiene, wherein the mol ratio of cyclopentadiene to acrylonitrile is 1:1.05, controlling the temperature of the second microchannel to be 25 ℃, the retention time to be 55s, the reaction pressure to be 0.20MPa, receiving a reaction material after the reaction is finished, namely the cyano norbornene,
the invention detects the reacted product, and the detection shows that the product content is 98.5 percent and the yield is 98.2 percent.
Example 3
Preheating acrylonitrile in a first microchannel reactor, wherein the preheating temperature is 40 ℃, the retention time is 15s, feeding the preheated acrylonitrile into a second microchannel reactor, and then feeding cyclopentadiene, wherein the mol ratio of cyclopentadiene to acrylonitrile is 1:1.02, controlling the temperature of the second microchannel at 32 ℃, the residence time at 25s, the reaction pressure at 0.12MPa, receiving a reaction material after the reaction is finished, namely the cyano norbornene,
the invention detects the reacted product, and the detection shows that the product content is 96.1 percent and the yield is 95.8 percent.
Comparative example 1
Adding acrylonitrile and dicyclopentadiene into a mixing kettle, wherein the molar ratio of the acrylonitrile to the dicyclopentadiene is 2.5:1, continuously feeding materials into a reaction kettle by using a quantitative pump after the materials are mixed, maintaining the utilization rate of the reaction kettle at 70 percent, keeping the pressure of the reaction kettle at 8MPa and the reaction temperature at 190 ℃, introducing a reaction solution after reaction for 12 hours into a flash evaporator, and recovering a mixed solution of unreacted acrylonitrile and dicyclopentadiene from the top of the flash evaporator, wherein the operating condition of the flash evaporator is 160 ℃; and introducing the recovered reaction liquid into a rectifying tower to rectify the reaction liquid, wherein the rectifying tower is a packed tower, the packing is a 1-inch step ring, and the operation conditions are that the temperature of the bottom of the tower is 143 ℃, the pressure of the top of the tower is 17.4KPa and the temperature of the top of the tower is 58 ℃.
The invention detects the distilled product, and the purity of the product is 97.3 percent and the yield is 90 percent.
Comparative example 2
Preheating acrylonitrile in a first microchannel reactor, wherein the preheating temperature is 30 ℃, the retention time is 15s, feeding the preheated acrylonitrile into a second microchannel reactor, and then feeding cyclopentadiene, wherein the mol ratio of cyclopentadiene to acrylonitrile is 1:1.05, controlling the temperature of the second micro-channel to be 25 ℃, the retention time to be 50s, the reaction pressure to be 0.30MPa, receiving out a reaction material after the reaction is finished, namely the cyano norbornene,
the detection of the product after the reaction shows that the product content is 82.3 percent and the yield is 72.4 percent.
Comparative example 3
Precooling acrylonitrile in a first microchannel reactor, wherein the precooling temperature is 10 ℃, the retention time is 20s, sending the preheated acrylonitrile into a second microchannel reactor, and then feeding cyclopentadiene, wherein the mol ratio of cyclopentadiene to acrylonitrile is 1:1.05, controlling the temperature of the second microchannel to be 15 ℃, the retention time to be 50s, the reaction pressure to be 0.30MPa, receiving a reaction material after the reaction is finished, namely the cyano norbornene,
the invention detects the reacted product, and the detection shows that the product content is 74.6 percent and the yield is 68.4 percent.
Comparative example 4
Preheating acrylonitrile in a first microchannel reactor, wherein the preheating temperature is 70 ℃, the retention time is 20s, feeding the preheated acrylonitrile into a second microchannel reactor, and then feeding cyclopentadiene, wherein the mol ratio of cyclopentadiene to acrylonitrile is 1:1.05, controlling the temperature of the second microchannel to be 50 ℃, the retention time to be 30s, the reaction pressure to be 0.45MPa, receiving a reaction material after the reaction is finished, namely the cyano norbornene,
the invention detects the reacted product, and the detection shows that the product content is 85.8 percent and the yield is 80.1 percent.
Comparative example 5
Preheating acrylonitrile in a first microchannel reactor, wherein the preheating temperature is 85 ℃, the retention time is 20s, feeding the preheated acrylonitrile into a second microchannel reactor, and then feeding cyclopentadiene, wherein the mol ratio of cyclopentadiene to acrylonitrile is 1:1.05, controlling the temperature of the second microchannel to be 70 ℃, the retention time to be 30s, the reaction pressure to be 0.60MPa, receiving a reaction material after the reaction is finished, namely the cyano norbornene,
the invention detects the reacted product, and the detection shows that the product content is 81.4 percent and the yield is 76.9 percent.
As can be seen from the above examples, the present invention provides a method for continuously preparing cyanonorbornene using a microchannel reactor, comprising the steps of: reacting cyclopentadiene and acrylonitrile preheated to 40-55 ℃ in a microchannel reactor to obtain cyano norbornene; the reaction temperature is 25-40 ℃, the pressure is 0.1-0.4 MPa, and the retention time is 10-100 s. The method provided by the invention greatly shortens the reaction time, improves the reaction efficiency and ensures that the product has higher yield and purity by controlling the reaction temperature, pressure and time of the cyclopentadiene and the preheated acrylonitrile in the microchannel reactor. The method avoids the industrial synthesis at high temperature and high pressure, improves the safety in the reaction process, is simple and has extremely high social and economic benefits. The experimental results show that: the yield of the product prepared by the method is more than 95%, and the purity is more than 96%.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (1)
1. A method for continuously preparing cyano norbornene by using a microchannel reactor, comprising the steps of:
reacting cyclopentadiene and acrylonitrile preheated to 48 ℃ in a microchannel reactor to obtain cyano norbornene;
the preheated acrylonitrile is prepared according to the following method:
preheating acrylonitrile in a microchannel reactor to obtain preheated acrylonitrile; the preheating time is 25s;
the reaction temperature is 25 ℃, the pressure is 0.20MPa, and the retention time is 55s; the characteristic dimension of the channel of the microchannel reactor is 30 μm, and the volume of each plate is 3.7ml;
the molar ratio of the cyclopentadiene to the acrylonitrile is 1.05;
the microchannel reactor is a corning G1 silicon carbide reactor.
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| JP2002348271A (en) * | 2001-05-25 | 2002-12-04 | Mitsui Chemicals Inc | Method for producing cyanonorbornene |
| CN105924337B (en) * | 2016-04-27 | 2018-11-13 | 南京工业大学 | A method of preparing 5- norbornene -2- formaldehyde in micro-structured reactor |
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