CN114560751B - Method for producing cis-or trans-1, 3-dichloropropene - Google Patents
Method for producing cis-or trans-1, 3-dichloropropene Download PDFInfo
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- CN114560751B CN114560751B CN202210136390.XA CN202210136390A CN114560751B CN 114560751 B CN114560751 B CN 114560751B CN 202210136390 A CN202210136390 A CN 202210136390A CN 114560751 B CN114560751 B CN 114560751B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/35—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction
- C07C17/358—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction by isomerisation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- C07C17/00—Preparation of halogenated hydrocarbons
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- C07C17/383—Separation; Purification; Stabilisation; Use of additives by distillation
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- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
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- C07B2200/09—Geometrical isomers
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Abstract
The invention provides a method for producing cis-or trans-1, 3-dichloropropene, which can carry out mutual conversion of cis-1, 3-dichloropropene and trans-1, 3-dichloropropene under the condition of not requiring visible light or ultraviolet light by using a catalyst, can freely select the conversion direction according to the actual requirement, has simple equipment and no need of special design, can be used for preparing the trans-1, 3-dichloropropene from the cis-1, 3-dichloropropene and can also be operated reversely by the same equipment, and only needs to use a pipeline to control corresponding products to enter a product tank and a raw material tank.
Description
Technical Field
The invention relates to the field of chemical intermediate production, in particular to a method for producing trans-or cis-1, 3-dichloropropene.
Background
1, 3-dichloropropene is a by-product in the production of epoxy chloropropane, and contains cis-1, 3-dichloropropene and trans-1, 3-dichloropropene isomer mixture, and CN110078584A discloses a process for recovering dichloropropane and dichloropropene from DD mixed agent, wherein the DD mixed agent is used for removing carbon and tar in a de-heavy tower, the dichloropropane and the dichloropropene are pre-separated in a pre-fractionating tower, high-purity 1, 2-dichloropropane is separated in a low-boiling removal tower and a 1, 2-dichloropropane refining tower, and high-purity cis-dichloropropene and trans-dichloropropene are separated in a recovery tower, and the process achieves the aim of separating dichloropropane and dichloropropene.
The cis-1, 3-dichloropropene and the trans-1, 3-dichloropropene are used in different ways, and the price varies with the demand, CN109694308A describes a method for converting trans-1, 3-dichloropropene into cis-1, 3-dichloropropene, and CN111848334A discloses a method for converting cis-1, 3-dichloropropene into trans-1, 3-dichloropropene, but all the methods need to be reacted under visible light or ultraviolet light. The photocatalysis has the defects that ultraviolet light or visible light is generally required to irradiate the reactor, the reactor needs to be transparent or a light source is arranged inside the reactor, the design of the reactor is greatly limited, and the photocatalysis is difficult to apply to industrial production.
Disclosure of Invention
In order to solve the problems in the background art, the invention provides the following technical scheme:
a process for producing trans-1, 3-dichloropropene comprising the steps of:
s1: mixing cis-1, 3-dichloropropene and a catalyst in a proportioning kettle in proportion;
s2: continuously introducing the mixed raw materials into a kettle type reactor for reaction;
s3: extracting reaction liquid from the top of the kettle reactor through gas phase to a rectifying tower for negative pressure rectification, and supplying heat through a reboiler;
s4: the trans-1, 3-dichloropropene extracted from the side line is condensed by a condenser and enters a product tank, and the cis-1, 3-dichloropropene extracted from the top is condensed and enters a raw material tank;
in S1, the catalyst is C3-C6 alkyl bromide or C3-C6 olefin bromide.
Further, in S1, the catalyst is selected from one or more of 3-bromopropene, 1, 2-tribromopropane, 1-bromo-1, 5-hexadiene, 1-bromohexene and 1-bromo-4-methylpentene.
Furthermore, in S1, the weight ratio of the catalyst to the cis-1, 3-dichloropropene is 0.3-1.5%.
Further, in S2, the reaction conditions in the tank reactor are: the reaction temperature is 60-80 ℃, and the reaction residence time is 2-4 h; in S3, the temperature of the bottom of the rectifying tower is 82 ℃, the temperature of the top of the rectifying tower is 62 ℃, the vacuum degree of the bottom of the rectifying tower is-0.065 MPa, the vacuum degree of the top of the rectifying tower is-0.075 MPa, and the reflux ratio of the rectifying tower is 3-6; the feed rate in S2 corresponds to the withdrawal rate in S3.
The invention also provides a method for producing cis-1, 3-dichloropropene, which comprises the following steps:
s1: mixing trans-1, 3-dichloropropene and a catalyst in a batching kettle according to a proportion;
s2: continuously introducing the mixed raw materials into a kettle type reactor for reaction;
s3: extracting reaction liquid from the top of the kettle reactor through gas phase to a rectifying tower for negative pressure rectification, and supplying heat through a reboiler;
s4: the trans-1, 3-dichloropropene extracted from the side line is condensed by a condenser and enters a raw material tank, and the cis-1, 3-dichloropropene extracted from the top is condensed and enters a product tank;
in S1, the catalyst is C3-C6 alkyl bromide or C3-C6 olefin bromide.
Further, in S1, the catalyst is selected from one or more of 3-bromopropene, 1, 2-tribromopropane, 1-bromo-1, 5-hexadiene, 1-bromohexene and 1-bromo-4-methylpentene.
Furthermore, in S1, the weight ratio of the catalyst to the trans-1, 3-dichloropropene is 0.3-1.5%.
Further, in S2, the reaction conditions in the tank reactor are: the reaction temperature is 60-80 ℃, and the reaction residence time is 2-4 h; in S3, the temperature of the bottom of the rectifying tower is 82 ℃, the temperature of the top of the rectifying tower is 62 ℃, the vacuum degree of the bottom of the rectifying tower is-0.065 MPa, the vacuum degree of the top of the rectifying tower is-0.075 MPa, and the reflux ratio of the rectifying tower is 3-6; the feed rate in S2 corresponds to the withdrawal rate in S3.
The beneficial effects of the invention are as follows:
the invention provides a method for producing cis-or trans-1, 3-dichloropropene, which can carry out interconversion of cis-1, 3-dichloropropene and trans-1, 3-dichloropropene by using a catalyst under the condition of not needing visible light or ultraviolet light, can freely select the conversion direction according to actual requirements, has simple equipment without special design, even the same set of equipment can be used for preparing the trans-1, 3-dichloropropene from the cis-1, 3-dichloropropene and also can be used for preparing the cis-1, 3-dichloropropene from the trans-1, 3-dichloropropene, and only needs to use a pipeline to control corresponding products to enter a product tank and a raw material tank.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
Example 1
A process for producing trans-1, 3-dichloropropene comprising the steps of:
s1: raw material cis-1, 3-dichloropropene (with the content of 98%) and catalyst 3-bromopropene are mixed in a blending kettle according to the weight ratio of 1: mixing at a ratio of 0.3%;
s2: the mixed raw materials are continuously fed into a 500L kettle-type reactor at a feeding speed of 75L/h for reaction, the reaction temperature is 60 ℃, and the reaction residence time is 4h (calculated by a feeding coefficient of 0.6);
s3: extracting reaction liquid into a rectifying tower through a gas phase at the top of a tank reactor, wherein the operating conditions of the rectifying tower are that the temperature of the tower bottom is 82 ℃, the temperature of the tower top is 62 ℃, the vacuum degree of the tower bottom is-0.065 MPa, the vacuum degree of the tower top is-0.075 MPa, and heat is supplied through a reboiler, and the reflux ratio of the rectifying tower is 6;
s4: the trans-1, 3-dichloropropene with the content of 99.1 percent is extracted from the side line and condensed by a condenser, the extracted amount is 21.4L/h and enters a product tank, the cis-1, 3-dichloropropene with the content of 98.4 percent is extracted from the top and enters a raw material tank with the extracted amount of 53.6L/h after being condensed.
Example 2
A process for producing trans-1, 3-dichloropropene comprising the steps of:
s1: raw material cis-1, 3-dichloropropene (with the content of 98%) and catalyst 1-bromo-1, 5-hexadiene are added into a blending kettle according to the weight ratio of 1: mixing at a ratio of 0.6%;
s2: the mixed raw materials are continuously fed into a 500L kettle-type reactor at a feeding speed of 100L/h for reaction, the reaction temperature is 65 ℃, and the reaction residence time is 3h (calculated by a feeding coefficient of 0.6);
s3: extracting reaction liquid into a rectifying tower through a gas phase at the top of a tank reactor, wherein the operating conditions of the rectifying tower are that the temperature of the tower bottom is 82 ℃, the temperature of the tower top is 62 ℃, the vacuum degree of the tower bottom is-0.065 MPa, the vacuum degree of the tower top is-0.075 MPa, and heat is supplied through a reboiler, and the reflux ratio of the rectifying tower is 4;
s4: the trans-1, 3-dichloropropene with the content of 99.2 percent is extracted from the side line and condensed by a condenser, the extracted amount is 39.8L/h and enters a product tank, the cis-1, 3-dichloropropene with the content of 98.1 percent is condensed and then the extracted amount is 60.2L/h and enters a raw material tank.
Example 3
A process for producing trans-1, 3-dichloropropene comprising the steps of:
s1: mixing a raw material cis-1, 3-dichloropropene (with the content of 98%) and a catalyst 1-bromo-1, 5-hexadiene and 1-bromohexene in a blending kettle according to the weight ratio of 1: mixing at a ratio of 1.5%;
s2: the mixed raw materials are continuously fed into a 500L kettle-type reactor at a feeding speed of 150L/h for reaction, the reaction temperature is 80 ℃, and the reaction residence time is 2h (calculated by a feeding coefficient of 0.6);
s3: extracting reaction liquid into a rectifying tower through a gas phase at the top of a kettle type reactor, wherein the operating conditions of the rectifying tower are that the tower bottom temperature is 82 ℃, the tower top temperature is 62 ℃, the tower bottom vacuum degree is-0.065 MPa, the tower top vacuum degree is-0.075 MPa, heat is supplied through a reboiler, and the reflux ratio of the rectifying tower is 3;
s4: the trans-1, 3-dichloropropene with the content of 99.0 percent is extracted from the side line and condensed by a condenser, the extracted amount is 68.1L/h and enters a product tank, the cis-1, 3-dichloropropene with the content of 97.8 percent is condensed and then the extracted amount is 81.8L/h and enters a raw material tank.
Example 4
A process for producing cis-1, 3-dichloropropene comprising the steps of:
s1: raw material trans-1, 3-dichloropropene (content is 96.7%) and catalyst 1, 2-tribromopropane are added into a blending kettle according to the weight ratio of 1: mixing at a ratio of 0.9%;
s2: the mixed raw materials are continuously introduced into a 500L kettle-type reactor at a feeding speed of 120L/h for reaction, the reaction temperature is 70 ℃, and the reaction residence time is 2.5h (calculated by a feeding coefficient of 0.6);
s3: extracting reaction liquid into a rectifying tower through a gas phase at the top of a kettle type reactor, wherein the operating conditions of the rectifying tower are that the tower bottom temperature is 82 ℃, the tower top temperature is 62 ℃, the tower bottom vacuum degree is-0.065 MPa, the tower top vacuum degree is-0.075 MPa, and heat is supplied through a reboiler, and the reflux ratio of the rectifying tower is 4;
s4: the trans-1, 3-dichloropropene with the content of 97.3 percent is extracted from the side line and condensed by a condenser, the extracted amount is 48.1L/h and enters a raw material tank, the cis-1, 3-dichloropropene with the content of 98.6 percent is extracted from the top and enters a product tank after being condensed with the extracted amount of 71.9L/h.
Example 5
A process for producing cis-1, 3-dichloropropene comprising the steps of:
s1: raw material trans-1, 3-dichloropropene (content: 96.7%) and catalyst 1-bromo-4-methylpentene are added into a blending kettle according to the weight ratio of 1: mixing at a ratio of 1.2%;
s2: the mixed raw materials are continuously fed into a 500L kettle-type reactor at a feeding speed of 86L/h for reaction, the reaction temperature is 75 ℃, and the reaction residence time is 3.5h (calculated by a feeding coefficient of 0.6);
s3: extracting reaction liquid into a rectifying tower through a gas phase at the top of a kettle type reactor, wherein the operating conditions of the rectifying tower are that the tower bottom temperature is 82 ℃, the tower top temperature is 62 ℃, the tower bottom vacuum degree is-0.065 MPa, the tower top vacuum degree is-0.075 MPa, heat is supplied through a reboiler, and the reflux ratio of the rectifying tower is 5;
s4: the trans-1, 3-dichloropropene with the content of 98.0 percent is extracted from the side line and condensed by a condenser, the extracted amount is 28.7L/h and enters a raw material tank, the cis-1, 3-dichloropropene with the content of 99.0 percent is condensed and then the extracted amount is 57.3L/h and enters a product tank.
Finally, it should be noted that the above-mentioned contents are only used for illustrating the technical solutions of the present invention, and not for limiting the protection scope of the present invention, and that the simple modifications or equivalent substitutions of the technical solutions of the present invention by those of ordinary skill in the art can be made without departing from the spirit and scope of the technical solutions of the present invention.
Claims (8)
1. A method for producing trans-1, 3-dichloropropene is characterized by comprising the following steps: the method comprises the following steps:
s1: mixing cis-1, 3-dichloropropene and a catalyst in a proportioning kettle in proportion;
s2: continuously introducing the mixed raw materials into a kettle type reactor for reaction;
s3: extracting reaction liquid from the top of the kettle reactor through gas phase to a rectifying tower for negative pressure rectification, and supplying heat through a reboiler;
s4: the trans-1, 3-dichloropropene extracted from the side line is condensed by a condenser and enters a product tank, and the cis-1, 3-dichloropropene extracted from the top is condensed and enters a raw material tank;
in S1, the catalyst is C3-C6 alkyl bromide or C3-C6 olefin bromide.
2. A process for producing trans-1, 3-dichloropropene according to claim 1 which comprises: in S1, the catalyst is selected from one or more of 3-bromopropene, 1, 2-tribromopropane, 1-bromo-1, 5-hexadiene, 1-bromohexene and 1-bromo-4-methylpentene.
3. A process for producing trans-1, 3-dichloropropene according to claim 1 or 2, wherein: in S1, the weight ratio of the catalyst to the cis-1, 3-dichloropropene is 0.3-1.5%.
4. A process for producing trans-1, 3-dichloropropene according to claim 3 which comprises: in S2, the reaction conditions in the kettle type reactor are as follows: the reaction temperature is 60-80 ℃, and the reaction residence time is 2-4 h; in S3, the temperature of the bottom of the rectifying tower is 82 ℃, the temperature of the top of the rectifying tower is 62 ℃, the vacuum degree of the bottom of the rectifying tower is-0.065 MPa, the vacuum degree of the top of the rectifying tower is-0.075 MPa, and the reflux ratio of the rectifying tower is 3-6; the feed rate in S2 corresponds to the withdrawal rate in S3.
5. A method for producing cis-1, 3-dichloropropene is characterized by comprising the following steps: the method comprises the following steps:
s1: mixing trans-1, 3-dichloropropene and a catalyst in a proportioning kettle in proportion;
s2: continuously introducing the mixed raw materials into a kettle type reactor for reaction;
s3: extracting reaction liquid from the top of the kettle reactor through gas phase to a rectifying tower for negative pressure rectification, and supplying heat through a reboiler;
s4: the trans-1, 3-dichloropropene extracted from the side line is condensed by a condenser and enters a raw material tank, and the cis-1, 3-dichloropropene extracted from the top is condensed and enters a product tank;
in S1, the catalyst is C3-C6 alkyl bromide or C3-C6 olefin bromide.
6. The process according to claim 5, wherein: in S1, the catalyst is selected from one or more of 3-bromopropene, 1, 2-tribromopropane, 1-bromo-1, 5-hexadiene, 1-bromohexene and 1-bromo-4-methylpentene.
7. The process according to claim 5 or 6 for the production of cis-1, 3-dichloropropene, characterized in that: in S1, the weight ratio of the catalyst to the trans-1, 3-dichloropropene is 0.3-1.5%.
8. The process according to claim 7 for producing cis-1, 3-dichloropropene, which comprises: in S2, the reaction conditions in the kettle type reactor are as follows: the reaction temperature is 60-80 ℃, and the reaction residence time is 2-4 h; in S3, the temperature of the bottom of the rectifying tower is 82 ℃, the temperature of the top of the rectifying tower is 62 ℃, the vacuum degree of the bottom of the rectifying tower is-0.065 MPa, the vacuum degree of the top of the rectifying tower is-0.075 MPa, and the reflux ratio of the rectifying tower is 3-6; the feed rate in S2 corresponds to the withdrawal rate in S3.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1376809A (en) * | 1963-10-11 | 1964-10-31 | Showa Denko Kk | Process for the production of 1, 3-dichloro-olefins |
| US3914167A (en) * | 1974-08-26 | 1975-10-21 | Dow Chemical Co | Process for making cis-1,3-dichloropropene |
| JP5790438B2 (en) * | 2011-11-21 | 2015-10-07 | セントラル硝子株式会社 | Process for producing trans-1-chloro-3,3,3-trifluoropropene |
| US9162947B2 (en) * | 2013-03-15 | 2015-10-20 | Honeywell International Inc. | High temperature isomerization of (E)-1-chloro-3,3,3-trifluoropropene to (Z)-1-chloro-3,3,3-trifluoropropene |
| CN109694308B (en) * | 2018-08-27 | 2021-09-24 | 浙江大学宁波理工学院 | Method for obtaining cis-1, 3-dichloropropene by in-situ reversion of trans-1, 3-dichloropropene |
| CN111848334A (en) * | 2020-07-30 | 2020-10-30 | 江苏扬农化工集团有限公司 | Method for treating by-products in process of preparing chloropropene by chlorination of propylene |
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Non-Patent Citations (1)
| Title |
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| 张建伟.《化工单元操作实验与设计》.天津大学出版社,2012,(第1版),第193-194页. * |
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