CN108675912B - Method for preparing 1, 3-dichloropropene by chlorination of 1-chloropropene - Google Patents
Method for preparing 1, 3-dichloropropene by chlorination of 1-chloropropene Download PDFInfo
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- CN108675912B CN108675912B CN201810384846.8A CN201810384846A CN108675912B CN 108675912 B CN108675912 B CN 108675912B CN 201810384846 A CN201810384846 A CN 201810384846A CN 108675912 B CN108675912 B CN 108675912B
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/10—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms
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Abstract
The invention provides a method for preparing 1, 3-dichloropropene by chlorination of 1-chloropropene, which comprises the following steps: continuously introducing nitrogen into the fixed bed reactor according to a preset airspeed; after 1-chloropropene is vaporized, placing the vaporized 1-chloropropene in a fixed bed reactor at a preset feeding speed; heating the fixed bed reactor to be stable at a preset temperature; chlorine is introduced into the fixed bed reactor, and the 1-chloropropene and the chlorine are subjected to chlorination reaction to generate the 1, 3-dichloropropene. The technical scheme of the invention has the advantages of high safety performance, simple process, high purity and yield of the generated 1, 3-dichloropropene, high conversion rate and high selectivity, and is suitable for popularization, production and application.
Description
Technical Field
The invention relates to the technical field of chemical product preparation, and particularly relates to a method for preparing 1, 3-dichloropropene by chlorination of 1-chloropropene.
Background
The 1, 3-dichloropropene can be mixed with chloropicrin to be used as a soil fumigant, can also be used as a chemical reagent and a solvent, can be used for treating soil before crop planting, can be used for controlling root-knot nematodes, pratylenchus praecox, cyst nematode lampwick and underground pests of various crops, can also be used for organic synthesis, and can be used as a mildew preventive and a medical intermediate.
However, in the related art, the chloropropene is generally prepared by separating a byproduct of the high-temperature chlorination of propylene to prepare chloropropene, or by dehydrochlorination of 1, 2, 3-trichloropropane under the action of alkali, so that the purity and the yield are low, and the process is complicated.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art or the related art.
Therefore, the invention aims to provide a method for preparing 1, 3-dichloropropene by chlorination of 1-chloropropene, which has the advantages of simple process, high conversion rate, high selectivity and high yield.
In order to achieve the purpose, the technical scheme of the invention provides a method for preparing 1, 3-dichloropropene by chlorination of 1-chloropropene, which comprises the following steps: continuously introducing nitrogen into the fixed bed reactor according to a preset airspeed; after 1-chloropropene is vaporized, placing the vaporized 1-chloropropene in a fixed bed reactor at a preset feeding speed; heating the fixed bed reactor to be stable at a preset temperature; chlorine is introduced into the fixed bed reactor, and the 1-chloropropene and the chlorine are subjected to chlorination reaction to generate the 1, 3-dichloropropene.
According to the technical scheme, nitrogen is continuously introduced into the fixed bed reactor according to a preset airspeed, then 1-chloropropene is vaporized and then is placed into the fixed bed reactor according to a preset feeding speed, then the fixed bed reactor is heated and stabilized at a preset temperature, so that the high-efficiency reaction can be carried out without a catalyst, the conversion rate and the selectivity of the 1, 3-dichloropropene are high, the 1, 3-dichloropropene with high purity and yield can be obtained, and the chlorine is introduced into the fixed bed reactor, so that the 1-chloropropene and the chlorine are subjected to chlorination reaction to generate the 1, 3-dichloropropene, the safety performance is high, the process is simple, and the purity and the yield of the generated 1, 3-dichloropropene are high.
In the above technical solution, preferably, the value range of the preset airspeed is 500h-1～2000h-1。
In the technical scheme, the value range of the preset airspeed is 500h-1～2000h-1On one hand, the phenomenon of energy waste caused by overhigh nitrogen gas introduction speed is reduced, and on the other hand, the phenomena of poor protection and anti-oxidation effect caused by overlow nitrogen gas introduction speed and the like are reduced.
In any of the above technical solutions, preferably, the preset temperature is in a range of 300 ℃ to 400 ℃.
In the technical scheme, the value range of the preset temperature is 300-400 ℃, which is determined by a large amount of experimental researches, and under the preset temperature in the range, the side reaction products can be reduced, and the selectivity and the conversion rate of the 1, 3-dichloropropene can be improved.
In any of the above embodiments, preferably, the preset feed rate is 1.5 ml/min; the rate of chlorine gas introduction was 1.5 ml/min.
In the technical scheme, the feeding speed is preset to be 1.5ml/min and the introduction speed of the chlorine gas is 1.5ml/min, so that the full reaction is favorably ensured, and the selectivity and the conversion rate of the 1, 3-dichloropropene are further improved.
In any of the above technical solutions, preferably, the preset temperature is 350 ℃ and the preset space velocity is 1200h-1。
In the technical scheme, the preset temperature is 350 ℃, and the preset airspeed is 1200h-1The reaction product is detected on a gas chromatograph, the conversion rate can reach 87.0 percent, and the selectivity is 99.5 percent.
In any of the above technical solutions, preferably, the preset temperature is 350 ℃ and the preset space velocity is 1000h-1。
In the technical scheme, the preset temperature is 350 ℃, and the preset airspeed is 1000h-1The reaction product was detected on a gas chromatograph with a conversion of 86.5% and a selectivity of 99.2%.
In any one of the above technical schemes, the preset temperature is 320 ℃, and the preset airspeed is 1000h-1。
In the technical scheme, the preset temperature is 320 ℃, and the preset airspeed is 1000h-1The reaction product was detected on a gas chromatograph with a conversion of 85.7% and a selectivity of 99.6%.
In any one of the above technical schemes, the preset temperature is 350 ℃, and the preset airspeed is 800h-1。
In the technical scheme, the preset temperature is 350 ℃, and the preset airspeed is 800h-1The reaction product was detected on a gas chromatograph with a conversion of 90.6% and a selectivity of 99.2%.
By the technical scheme, the method is carried out for 500h-1～2000h-1The nitrogen is continuously introduced at the airspeed, the vaporized 1-chloropropene reacts with chlorine at the reaction temperature of 300-400 ℃, the 1, 3-dichloropropene can be generated without adding a catalyst, the safety performance is higher, the process is simple, and the purity and the yield of the generated 1, 3-dichloropropene are higher.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Detailed Description
The invention discloses a method for preparing 1, 3-dichloropropene by chlorination of 1-chloropropene, and a person skilled in the art can appropriately improve process parameters by referring to the content. It is expressly intended that all such similar substitutes and modifications which would be obvious to one skilled in the art are deemed to be included in the invention. While the methods and applications of this invention have been described in terms of preferred embodiments, it will be apparent to those of ordinary skill in the art that variations and modifications in the methods and applications described herein, as well as other suitable variations and combinations, may be made to implement and use the techniques of this invention without departing from the spirit and scope of the invention.
The invention is further illustrated by the following examples:
example 1
According to 1200h-1Continuously introducing nitrogen into the fixed bed reactor at the airspeed of the nitrogen; after vaporizing the 1-chloropropene, placing the vaporized 1-chloropropene in a fixed bed reactor at the speed of 1.5 ml/min; the heating fixed bed reactor is stabilized at 350 ℃; chlorine is introduced into the fixed bed reactor, 1-chloropropene and chlorine are subjected to chlorination reaction to generate 1, 3-dichloropropene, and the reaction product is detected on a gas chromatography, so that the conversion rate can reach 87.0 percent, and the selectivity is 99.5 percent.
Example 2
According to 1000h-1Continuously introducing nitrogen into the fixed bed reactor at the airspeed of the nitrogen; after vaporizing the 1-chloropropene, placing the vaporized 1-chloropropene in a fixed bed reactor at the speed of 1.5 ml/min; the heating fixed bed reactor is stabilized at 350 ℃; chlorine gas is introduced into the fixed bed reactor, 1-chloropropene and chlorine gas are subjected to chlorination reaction to generate 1, 3-dichloropropene, and the reaction product is detected on a gas chromatography, wherein the conversion rate is 86.5%, and the selectivity is 99.2%.
Example 3
According to 1000h-1Continuously introducing nitrogen into the fixed bed reactor at the airspeed of the nitrogen; after vaporizing the 1-chloropropene, placing the vaporized 1-chloropropene in a fixed bed reactor at the speed of 1.5 ml/min; the heating fixed bed reactor is stabilized at 320 ℃; chlorine is introduced into the fixed bed reactor, 1-chloropropene and chlorine are subjected to chlorination reaction to generate 1, 3-dichloropropene, and the reaction product is detected on a gas chromatography, wherein the conversion rate is 85.7 percent, and the selectivity is 99.6 percent.
Example 4
According to 800h-1Continuously introducing nitrogen into the fixed bed reactor at a space velocity ofGas; after vaporizing the 1-chloropropene, placing the vaporized 1-chloropropene in a fixed bed reactor at the speed of 1.5 ml/min; the heating fixed bed reactor is stabilized at 350 ℃; chlorine is introduced into the fixed bed reactor, 1-chloropropene and chlorine are subjected to chlorination reaction to generate 1, 3-dichloropropene, and the reaction product is detected on a gas chromatography, wherein the conversion rate is 90.6%, and the selectivity is 99.2%.
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 (5)
1. A method for preparing 1, 3-dichloropropene by chlorination of 1-chloropropene is characterized by comprising the following steps:
continuously introducing nitrogen into the fixed bed reactor according to a preset airspeed, wherein the value range of the preset airspeed is 500h-1～2000h-1；
After 1-chloropropene is vaporized, placing the vaporized 1-chloropropene in the fixed bed reactor at a preset feeding speed of 1.5 ml/min; heating the fixed bed reactor to be stable at a preset temperature, wherein the value range of the preset temperature is 300-400 ℃;
and introducing chlorine into the fixed bed reactor, wherein the introducing speed of the chlorine is 1.5ml/min, and the 1-chloropropene and the chlorine are subjected to chlorination reaction to generate 1, 3-dichloropropene.
2. The process for the preparation of 1, 3-dichloropropene according to claim 1, which comprises chlorinating 1-chloropropene,
the preset temperature is 350 ℃, and the preset airspeed is 1200h-1。
3. The process for the preparation of 1, 3-dichloropropene according to claim 1, which comprises chlorinating 1-chloropropene,
the preset temperature is 350 ℃, and the preset airspeed is 1000h-1。
4. The process for the preparation of 1, 3-dichloropropene according to claim 1, which comprises chlorinating 1-chloropropene,
the preset temperature is 320 ℃, and the preset airspeed is 1000h-1。
5. The process for the preparation of 1, 3-dichloropropene according to claim 1, which comprises chlorinating 1-chloropropene,
the preset temperature is 350 ℃, and the preset airspeed is 800h-1。
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| CN201810384846.8A CN108675912B (en) | 2018-04-26 | 2018-04-26 | Method for preparing 1, 3-dichloropropene by chlorination of 1-chloropropene |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB968931A (en) * | 1962-06-01 | 1964-09-09 | Richard Klar | Improvements relating to the chlorination of olefines |
| JPS5479208A (en) * | 1977-12-05 | 1979-06-25 | Showa Denko Kk | Preparation of 1,3-dichloropropene |
| CN103724155A (en) * | 2013-12-19 | 2014-04-16 | 山东海益化工科技有限公司 | Chloropropene production process |
| CN103724157A (en) * | 2013-12-19 | 2014-04-16 | 山东海益化工科技有限公司 | Chlorination process in chloropropene production |
-
2018
- 2018-04-26 CN CN201810384846.8A patent/CN108675912B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB968931A (en) * | 1962-06-01 | 1964-09-09 | Richard Klar | Improvements relating to the chlorination of olefines |
| JPS5479208A (en) * | 1977-12-05 | 1979-06-25 | Showa Denko Kk | Preparation of 1,3-dichloropropene |
| CN103724155A (en) * | 2013-12-19 | 2014-04-16 | 山东海益化工科技有限公司 | Chloropropene production process |
| CN103724157A (en) * | 2013-12-19 | 2014-04-16 | 山东海益化工科技有限公司 | Chlorination process in chloropropene production |
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