CN111548248B - Method for producing 1,3,3, 3-tetrachloropropene - Google Patents
Method for producing 1,3,3, 3-tetrachloropropene Download PDFInfo
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- CN111548248B CN111548248B CN202010424459.XA CN202010424459A CN111548248B CN 111548248 B CN111548248 B CN 111548248B CN 202010424459 A CN202010424459 A CN 202010424459A CN 111548248 B CN111548248 B CN 111548248B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
- C07C17/272—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions
- C07C17/275—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions of hydrocarbons and halogenated hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/38—Separation; Purification; Stabilisation; Use of additives
- C07C17/383—Separation; Purification; Stabilisation; Use of additives by distillation
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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
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Abstract
The invention discloses a method for producing 1,3,3, 3-tetrachloropropene, which adopts a reactive distillation integrated device mainly comprising a rectifying tower and side reactors which are coupled, takes carbon tetrachloride and acetylene as raw materials, the carbon tetrachloride with a dissolved catalyst is introduced into a first side reactor coupled with the rectifying tower through an absorption tower, the acetylene is continuously introduced into each side reactor connected with the rectifying tower, in the side reactors, addition reaction is carried out under the action of light and the catalyst, liquid phase materials obtained by the reaction enter the rectifying tower, and required products are extracted from a first plate at the upper part of a rectifying tower kettle; or when the number of the side reactors is more than two, extracting the liquid phase material of the rectifying tower, then feeding the extracted liquid phase material into the next-stage side reactor for continuous reaction, returning the extracted liquid phase material to the next extracted tower plate, and extracting the required product from the first plate on the upper part of the rectifying tower kettle. The invention has the advantage of producing the 1,3,3, 3-tetrachloropropene with high conversion rate and selectivity.
Description
Technical Field
The invention relates to the field of preparation of intermediates, in particular to a method for producing 1,3,3, 3-tetrachloropropene.
Background
1,3,3, 3-tetrachloropropene is an important organic intermediate and can be used for preparing various fluorocarbons, such as 1,3,3, 3-tetrachloropropene, and can be used for synthesizing 1-chloro-3, 3, 3-trifluoropropene and 1,3,3, 3-tetrafluoropropene by reacting with hydrogen fluoride. Among them, in the fluorine refrigeration industry, 1,3,3, 3-tetrafluoropropene has low Ozone Depletion Potential (ODP) and low-temperature room effect potential (GWP), and is considered to be a 3 rd generation refrigerant replacing high GWP such as 1,1,1, 2-tetrafluoroethane (HFC-134 a), l,1,1,2, 2-pentafluoroethane (HFC-125), and has a wide application value. Therefore, the synthesis of the 1,3,3, 3-tetrachloropropene has certain research value. At present, the synthesis of 1,3,3, 3-tetrachloropropene by catalyzing carbon tetrachloride and acetylene to react in an autoclave by mercury chloride or palladium chloride is reported in documents, the mercury chloride catalyst used in the method has high toxicity and the palladium chloride catalyst has high cost, and 1,3,3, 3-tetrachloropropene is easy to thermally decompose at high temperature, so that the selectivity of a target product is low.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for producing 1,3,3, 3-tetrachloropropene with high conversion rate and selectivity, 1,3,3, 3-tetrachloropropene is prepared at normal pressure by adopting a rectification coupling technology, 1,3,3, 3-tetrachloropropene decomposition and coking are avoided by adopting a low-temperature reaction mode and a mode of controlling the low conversion rate and the low residence time of a single kettle, and in order to make up for the insufficient capacity of a single reactor, a method of coupling a plurality of side reactors is adopted, so that the reaction process and the separation process are effectively combined, and the production capacity is improved.
The technical purpose of the invention is realized by the following technical scheme:
a method for producing 1,3,3, 3-tetrachloropropene, characterized by, said method adopts the integrated device of reactive distillation mainly formed by coupling of rectifying column and side reactor, regard carbon tetrachloride and acetylene as raw materials, introduce the carbon tetrachloride of the dissolved catalyst into the first side reactor coupled with rectifying column through the absorption column, acetylene is introduced into each side reactor connected with rectifying column continuously, in the side reactor, take place the addition reaction under the effect of light and catalyst, the liquid phase supplies got in the reaction enter the rectifying column, the products needed are extracted from the first slab of the upper portion of the rectifying column kettle; or when the number of the side reactors is more than two, extracting the liquid phase material of the rectifying tower, then feeding the extracted liquid phase material into the next-stage side reactor for continuous reaction, returning the extracted liquid phase material to the next extracted tower plate, and extracting the required product from the first plate on the upper part of the rectifying tower kettle.
Preferably, the rectifying tower is divided into a reaction rectifying area and a stripping area from top to bottom, and the reaction rectifying area is connected and coupled with each side reactor through a material inlet pipeline and a material outlet pipeline.
Preferably, the operation pressure in the rectifying tower is 3 kPa-6 kPa.
Preferably, the catalyst is Cu-EDTA, and the mass concentration of the catalyst in carbon tetrachloride for dissolving the catalyst is 0.1%.
Preferably, the reaction temperature in the side reactor is 35-70 ℃, the reaction pressure is normal pressure, and the reaction residence time is controlled to be 0.5-6 h.
Preferably, the number of the tower plates in the stripping area is 5-50, the number of the tower plates in the reaction rectifying area is 1-20, and the number of the tower plates in the reaction rectifying area spaced between adjacent side reactors is 1-5.
Preferably, the number of the side reactors is 1-5.
Preferably, a light source with a bias ultraviolet wavelength is arranged in the side reactor.
Preferably, the molar ratio of the total introduction of carbon tetrachloride to the feed of acetylene is 1: 1.
In conclusion, the invention has the following beneficial effects:
1. the method for synthesizing the 1,3,3, 3-tetrachloropropene at normal pressure and low temperature is provided, the coking of high-temperature and high-pressure reaction products is avoided, unreacted acetylene is absorbed by carbon tetrachloride and then added into a coupling side reactor for recycling, and the utilization rate of raw materials is improved.
2. By adopting a reactive distillation process and controlling the low conversion rate and the residence time of a single kettle, the 1,3,3, 3-decomposition product can be reduced, and the selectivity of the 1,3,3, 3-tetrachloropropene can be improved.
3. The advantages of the reactive distillation integration technology can be kept, and the operating conditions of the reactor and the rectifying tower can be kept independent.
4. The number of the reactors and the reaction amount can be freely adjusted, the optimal matching of the reaction capacity and the separation capacity is realized, and the large-scale industrial production is favorably realized.
5. The reaction process route is simple, highly polluted carbon tetrachloride can be converted into 1,3,3, 3-tetrachloropropene with high added value, and the process is green and environment-friendly.
Drawings
FIG. 1 is a schematic process flow diagram of the present invention;
the reference numbers in fig. 1 are: 1-a rectifying tower reaction rectifying area, 2-a rectifying tower stripping area, 3-a rectifying tower top vapor phase pipeline, 4-a rectifying tower top condenser, 5-a gas-liquid separator, 6-a tail gas discharging pipeline, 7-a feeding pipeline from the condenser to the gas-liquid separator, 8-a final product output pipeline, 9-a liquid phase pipeline from the gas-liquid separator to the 1 st platform side reactor, 10-an acetylene feeding pipeline of each side reactor, 11-a gas phase feeding pipeline from the gas-liquid separator to an absorption tower, 12-a carbon tetrachloride liquid phase feeding pipeline of a dissolved catalyst of the absorption tower, 13-a liquid phase pipeline from the absorption tower to the 1 st platform side reactor, 14-the absorption tower, 15-the 1 st platform side reactor, 16-a gas phase discharging pipeline from the 1 st platform side reactor to the rectifying tower, 17-a liquid phase discharge pipeline from the rectifying tower to the 2 nd side reactor, 18-a liquid phase feed pipeline returning to the rectifying tower from the 2 nd side reactor, 19-a liquid phase discharge pipeline from the rectifying tower to the nth side reactor, 20-the 2 nd side reactor, 21-a rectifying tower kettle reboiler vapor phase circulation pipeline, 22-a rectifying tower kettle reboiler, 23-a rectifying tower kettle reboiler liquid phase circulation pipeline, 24-a rectifying tower kettle product extraction pipeline, 25-a liquid phase feed pipeline returning to the rectifying tower from the nth side reactor, and 26-the nth side reactor.
Detailed Description
The following further describes the embodiments of the present invention with reference to the drawings, and the present embodiment is not to be construed as limiting the invention.
As shown in fig. 1, the specific process flow of the present invention is as follows:
adding a carbon tetrachloride material dissolved with a catalyst into a system through an acetylene carbon tetrachloride absorption tower 14, enabling the material to flow into a first side reactor 15 coupled with a rectifying tower, enabling the material to have a normal-pressure photocatalytic reaction with introduced acetylene in the first side reactor 15, enabling a product to flow into a rectifying tower reaction rectifying area 1, enabling an unreacted part of substances to flow into a gas-liquid separator 5 after being condensed by a rectifying tower top condenser 4, enabling a condensate to be added into the first side reactor 15 coupled with the rectifying tower for continuous reaction, introducing a noncondensable gas containing a small amount of acetylene into the acetylene carbon tetrachloride absorption tower 14, and discharging a tail gas after the absorption of the carbon tetrachloride material to enter subsequent tail gas treatment. When the number of the side reactors is two or more, liquid-phase materials on the tower plates connected with the 2 nd side reactor 20 in the reaction rectification area 1 of the rectification tower are extracted, and respectively undergo photocatalytic reaction with acetylene in the corresponding 2 nd side reactor 20, the reaction liquid returns to the next tower plate of the extracted tower plate in the reaction rectification area, the reaction steps are continuously repeated to the nth side reactor 26, the reaction product is extracted in the rectification area 2 of the rectification tower, the obtained reaction product is extracted from the first plate on the upper part of the rectification tower kettle, and high-boiling water is discharged from the tower kettle.
The following is a further description of the specific embodiments of the present invention by means of specific examples, which are not intended to limit the invention.
Example 1
In a rectifying tower with the diameter of 0.8m and the number of 15 trays (the number of the trays in a reaction rectifying area is 1, the number of the trays in a stripping area is 14), and 1 rectifying tower with the volume of 5m3The reactor is connected, wherein the carbon tetrachloride condensate at the top of the tower and the carbon tetrachloride imbibition of acetylene all enter the 1 st side reactor, the material at the outlet of the side reactor returns to the 1 st tower plate (the number of the tower plates is counted from top to bottom) of the rectifying tower, and the material between the rectifying tower and the side reactor is conveyed by a pump.
The side reactor is internally provided with a light source with a partial ultraviolet wavelength and carbon tetrachloride, and the content of the catalyst Cu-EDTA is 0.1 percent. The feed flow rate of carbon tetrachloride containing 0.1% of catalyst to the side reactor was 4.0kmol/h, the feed flow rate of acetylene to the side reactor was 4.0kmol/h, the reaction temperature was 50 ℃, the liquid phase flow rate from the side reactor back to the rectification column was 65kmol/h, and the mole fractions of the components were: carbon tetrachloride 0.956, 1,3,3, 3-tetrachloropropene 0.044. The operating pressure of the rectifying tower is 4.5kPa, and the extraction amount at the bottom of the tower is 4.0 kmol/h. The temperature of the tower bottom of the rectifying tower is 60.1 ℃. The mole fraction of 1,3,3, 3-tetrachloropropene in the bottom product is 0.997, and the mole fraction of carbon tetrachloride is 0.003 respectively.
Example 2
In a rectifying tower with the diameter of 0.8m and 15 tower plates (the number of the tower plates in a reaction rectifying area is 7, the number of the tower plates in a stripping area is 8) and 2 rectifying towers with the volume of 3m3The kettle type side reactors are connected with each other,the number of the tower plates at intervals between the reactors is 5, wherein the condensed liquid of the vapor phase material at the top of the tower and the carbon tetrachloride absorption liquid of the non-condensable gas all enter the 1 st side reactor, and the material at the outlet of the side reactor returns to the 1 st tower plate of the rectifying tower (the number of the tower plates is counted from top to bottom); the material from the 6 th rectifying tower plate enters the 2 nd reactor, the material from the outlet of the side reactor returns to the 7 th tower plate of the rectifying tower, and the material between the rectifying tower and the side reactor is conveyed by a pump.
Each side reactor is internally provided with a light source with a partial ultraviolet wavelength and carbon tetrachloride, and the content of a catalyst Cu-EDTA is 0.1 percent. The feed flow rate of carbon tetrachloride containing 0.1% of the catalyst to the side reactor was 4.0kmol/h, and the feed flow rates of acetylene to the 1 st and 2 nd side reactors were 2.4 and 1.6kmol/h, respectively. The reaction temperature was 67 ℃ and the liquid phase flow rate and composition from the side reactor back to the rectification column are given in Table 1. The operating pressure of the rectifying tower is 6kPa, the extraction amount at the bottom of the tower is 4.0kmol/h, and the liquid phase material of the tower plate is fully extracted and enters a side reactor connected with the tower plate. The temperature of the rectifying tower still is 66.5 ℃. The mole fraction of 1,3,3, 3-tetrachloropropene in the product extracted from the tower bottom is 0.998, and the mole fraction of carbon tetrachloride is 0.002 respectively.
TABLE 1 side reactor outlet liquid phase flow Rate and composition
While the invention has been described with reference to a preferred embodiment, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the spirit and scope of the invention.
Claims (9)
1. A method for producing 1,3,3, 3-tetrachloropropene, characterized by, said method adopts the integrated device of reactive distillation mainly formed by coupling of rectifying column and side reactor, regard carbon tetrachloride and acetylene as raw materials, introduce the carbon tetrachloride of the dissolved catalyst into the first side reactor coupled with rectifying column through the absorption column, acetylene is introduced into each side reactor connected with rectifying column continuously, in the side reactor, take place the addition reaction under the effect of light and catalyst, the liquid phase supplies got in the reaction enter the rectifying column, the products needed are extracted from the first slab of the upper portion of the rectifying column kettle; or when the number of the side reactors is more than two, extracting the liquid phase material of the rectifying tower, then feeding the extracted liquid phase material into the next-stage side reactor for continuous reaction, returning the extracted liquid phase material to the next extracted tower plate, and extracting the required product from the first plate on the upper part of the rectifying tower kettle.
2. The process for producing 1,3,3, 3-tetrachloropropene according to claim 1, wherein: the rectifying tower is divided into a reaction rectifying area and a stripping area from top to bottom, and the reaction rectifying area is connected and coupled with each side reactor through a material inlet pipeline and a material outlet pipeline.
3. The process for producing 1,3,3, 3-tetrachloropropene according to claim 1, wherein: the operating pressure in the rectifying tower is 3-6 kPa.
4. The process for producing 1,3,3, 3-tetrachloropropene according to claim 1, wherein: the catalyst is Cu-EDTA, and the mass concentration of the catalyst in carbon tetrachloride dissolving the catalyst is 0.1%.
5. The process for producing 1,3,3, 3-tetrachloropropene according to claim 1, wherein: the reaction temperature in the side reactor is 35-70 ℃, the reaction pressure is normal pressure, and the reaction residence time is controlled to be 0.5-6 h.
6. A process for producing 1,3,3, 3-tetrachloropropene according to claim 2, wherein: the number of the tower plates in the stripping area is 5-50, the number of the tower plates in the reaction rectifying area is 1-20, and the number of the tower plates in the reaction rectifying area spaced between adjacent side reactors is 1-5.
7. The process for producing 1,3,3, 3-tetrachloropropene according to claim 1, wherein: the number of the side reactors is 1-5.
8. The process for producing 1,3,3, 3-tetrachloropropene according to claim 1, wherein: and a light source with a bias ultraviolet wavelength is arranged in the side reactor.
9. The process for producing 1,3,3, 3-tetrachloropropene according to claim 1, wherein: the molar ratio of the total introduced carbon tetrachloride to the feeding amount of acetylene is 1: 1.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1181873A (en) * | 1966-05-18 | 1970-02-18 | Aquitaine Petrole | A process for the production of Halo-Alkenes |
| WO2013074394A1 (en) * | 2011-11-18 | 2013-05-23 | Dow Global Technologies, Llc | Process for the production of chlorinated propanes and/or propenes |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1181873A (en) * | 1966-05-18 | 1970-02-18 | Aquitaine Petrole | A process for the production of Halo-Alkenes |
| WO2013074394A1 (en) * | 2011-11-18 | 2013-05-23 | Dow Global Technologies, Llc | Process for the production of chlorinated propanes and/or propenes |
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