CN112341311A - Preparation method of 1,1, 2-trifluoro-2-chloroethylene - Google Patents
Preparation method of 1,1, 2-trifluoro-2-chloroethylene Download PDFInfo
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- CN112341311A CN112341311A CN202011229710.3A CN202011229710A CN112341311A CN 112341311 A CN112341311 A CN 112341311A CN 202011229710 A CN202011229710 A CN 202011229710A CN 112341311 A CN112341311 A CN 112341311A
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- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 127
- OHMHBGPWCHTMQE-UHFFFAOYSA-N 2,2-dichloro-1,1,1-trifluoroethane Chemical compound FC(F)(F)C(Cl)Cl OHMHBGPWCHTMQE-UHFFFAOYSA-N 0.000 claims abstract description 53
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 31
- 239000007789 gas Substances 0.000 claims abstract description 26
- 238000010438 heat treatment Methods 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims abstract description 16
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 15
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000460 chlorine Substances 0.000 claims abstract description 15
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 15
- 229950011008 tetrachloroethylene Drugs 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 13
- 239000003513 alkali Substances 0.000 claims abstract description 7
- 239000012267 brine Substances 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 238000005086 pumping Methods 0.000 claims abstract description 7
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims description 44
- 238000004821 distillation Methods 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 17
- 239000000498 cooling water Substances 0.000 claims description 12
- 238000010992 reflux Methods 0.000 claims description 6
- VMPVEPPRYRXYNP-UHFFFAOYSA-I antimony(5+);pentachloride Chemical compound Cl[Sb](Cl)(Cl)(Cl)Cl VMPVEPPRYRXYNP-UHFFFAOYSA-I 0.000 claims description 5
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- BOSAWIQFTJIYIS-UHFFFAOYSA-N 1,1,1-trichloro-2,2,2-trifluoroethane Chemical compound FC(F)(F)C(Cl)(Cl)Cl BOSAWIQFTJIYIS-UHFFFAOYSA-N 0.000 description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 238000006298 dechlorination reaction Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- UJPMYEOUBPIPHQ-UHFFFAOYSA-N 1,1,1-trifluoroethane Chemical compound CC(F)(F)F UJPMYEOUBPIPHQ-UHFFFAOYSA-N 0.000 description 1
- LGPPATCNSOSOQH-UHFFFAOYSA-N 1,1,2,3,4,4-hexafluorobuta-1,3-diene Chemical compound FC(F)=C(F)C(F)=C(F)F LGPPATCNSOSOQH-UHFFFAOYSA-N 0.000 description 1
- BOUGCJDAQLKBQH-UHFFFAOYSA-N 1-chloro-1,2,2,2-tetrafluoroethane Chemical compound FC(Cl)C(F)(F)F BOUGCJDAQLKBQH-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229920001973 fluoroelastomer Polymers 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- -1 trifluoroethylene, trifluorobromoethylene Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
- C07C17/21—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms with simultaneous increase of the number of halogen atoms
Abstract
The invention relates to the technical field of chemical synthesis, in particular to a preparation method of 1,1, 2-trifluoro-2-chloroethylene; adding a catalyst into a reaction kettle, continuously adding hydrogen fluoride, tetrachloroethylene and chlorine into the reaction kettle, controlling the temperature and pressure, after reaction, opening a water inlet valve of a condenser, starting a cryogenic system, cooling the vented tail gas, collecting the discharged tail gas, rectifying the collected crude HCFC-123 by a rectifying tower to remove alkali, washing and sending to a chlorotrifluoroethylene working section; adding potassium hydroxide solution into a chlorotrifluoroethylene reaction kettle, heating, stirring, continuously pumping an intermediate HCFC-123, opening a light component removal kettle feed valve and a western rectification kettle feed valve, simultaneously opening a light component removal tower condenser frozen brine inlet and outlet valve, and collecting the discharge of the reaction kettle.
Description
Technical Field
The invention relates to the technical field of chemical synthesis, in particular to a preparation method of 1,1, 2-trifluoro-2-chloroethylene.
Background
Chlorotrifluoroethylene, also known as chlorotrifluoroethylene, is a colorless, slightly ether-smelling gas. Melting point-158 deg.C, boiling point-28.4 deg.C, relative density (water 1)1.20, and critical pressure 4.05 MPa. Combustible gas, the combustion limit in air is 16% -34% (volume); dissolved in ether.
Chlorotrifluoroethylene has properties of fluoroolefin, is an important fluorine-containing polymerization monomer, can prepare fluorine coating, fluororesin, fluororubber, chlorofluoro lubricating oil and the like through homopolymerization or copolymerization, and the fluorine-containing materials have excellent chemical inertness and weather resistance and are widely applied to the aspects of advanced technology, military space navigation field, electronic industry and the like.
Chlorotrifluoroethylene is also an important fluorine-containing intermediate, and downstream products such as trifluoroethylene, trifluorobromoethylene, hexafluorobutadiene and the like can be prepared.
The production process of chlorotrifluoroethylene reported in the prior literature mainly comprises the following steps: 1. a trifluoro trichloroethane metal zinc powder reduction dechlorination method; 2. catalytic hydrogenation dechlorination of trifluorotrichloroethane; 3. a catalytic dechlorination method of trifluorotrichloroethane under the participation of ethylene and oxygen; 4. electrochemical reduction of trifluorotrichloroethane; 5. HCFC-124 cracking process; 6. trifluoroethane directly reacts with chlorine gas at different positions of a fixed bed reactor to prepare chlorotrifluoroethylene; 7. chlorotrifluoroethylene is prepared by direct hydrogenation of trifluorotrichloroethane. The above process also has the disadvantages that the reaction conditions are severe and the raw materials are limited in supply.
Disclosure of Invention
The purpose of the invention is: overcomes the defects in the prior art, and provides a preparation method of 1,1, 2-trifluoro-2-chloroethylene, which has mild reaction conditions, easily obtained raw materials and no supply limitation.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a process for the preparation of 1,1, 2-trifluoro-2-chloroethylene comprising the steps of:
1) adding a catalyst into a reaction kettle, heating the reaction kettle to 100 ℃ by using steam, continuously adding hydrogen fluoride, tetrachloroethylene and chlorine into the reaction kettle at a certain speed, controlling the pressure of the reaction kettle to be 0.4-0.45 Mpa and the reaction temperature to be 100-115 ℃, opening a valve to a gas buffer tank, and controlling the temperature of a reaction bubbler to be 65-85 ℃; starting a water inlet valve of a condenser, starting a cryogenic system, cooling the vented tail gas, collecting the collected crude HCFC-123, rectifying the crude HCFC-123 by a rectifying tower to remove alkali, washing the crude HCFC-123 by water, and sending the crude HCFC-123 to a chlorotrifluoroethylene working section;
2) adding a potassium hydroxide solution into a chlorotrifluoroethylene reaction kettle, opening a hot water valve on the reaction kettle for heating, starting the reaction kettle for stirring, continuously pumping an intermediate HCFC-123 into the reaction kettle through an HCFC-123 metering tank and a metering pump, and simultaneously starting a cooling water inlet and outlet valve of a fractionating tower;
3) when the pressure of the kettle rises to 0.5MPa, slowly opening a gas phase valve and a reflux valve, when the pressure of the fractionating tower rises to 0.8MPa, slowly opening a discharge valve, and normally opening a feed valve of the lightness removing kettle;
controlling the temperature of the reaction kettle to be 60 ℃ by adjusting a water inlet valve of the reaction kettle; by adjusting a discharge valve, the kettle pressure is kept at 0.5-0.55MPa, when the HCFC-123 metering tank shows that 1500kg is finished, an HCFC-123 metering pump is closed, an HCFC-123 feeding valve on the reaction kettle is closed, HCFC-123 feeding is stopped, stirring is continued, the kettle temperature is kept at 58-62 ℃ until the pressure of the reaction kettle is reduced to 0.1MPa, the discharge valve is closed, and materials in the reaction kettle are pressed into a distillation kettle for distillation;
4) opening a light component removal kettle feed valve and a west rectifying kettle feed valve, simultaneously opening a light component removal tower condenser frozen brine inlet and outlet valve, collecting the reaction kettle discharge, starting to slowly heat up after reaction material collection is finished, maintaining the light component removal kettle pressure, slightly opening a light component removal tower top discharge valve, taking a light component removal tower middle sample at fixed time, and sending the kettle material to an east rectifying tower to rectify qualified chlorotrifluoroethylene products after the kettle sample is qualified;
5) after materials in the reaction kettle are pressed into the distillation kettle, slowly opening a steam valve and a drain valve, stopping heating when the temperature of the distillation kettle is raised to 95 ℃, opening cooling water to reduce the temperature to 40 ℃, and sending the materials to a post-treatment working section; the distilled materials are layered, the lower layer materials are rectified in a light component removal tower, and the upper layer water is sent to prepare a potassium hydroxide solution.
Further, the adding speeds of the hydrogen fluoride, the tetrachloroethylene and the chlorine gas in the step 1) are respectively as follows: the hydrogen fluoride is less than 250L/h, the tetrachloroethylene is less than 180L/h, and the chlorine is 12-15 Kg/h.
Further, the catalyst in the step 1) is antimony pentachloride or titanium tetrachloride.
Further, the top temperature of the condenser in the step 1) is controlled to be 40-45 ℃.
Further, the concentration of the potassium hydroxide solution in the step 2) is 20%, and the addition amount of the potassium hydroxide aqueous solution is 1000 kg.
Further, the temperature of the reaction kettle in the step 2) is heated to 60 ℃.
Further, the kettle pressure of the light component removal kettle in the step 4) is kept at 0.75-0.80 MPa.
Further, the heating rate of the distillation kettle in the step 5) is 20 ℃ per hour.
The technical scheme adopted by the invention has the beneficial effects that:
in the invention, potassium hydroxide solution is used for alkaline hydrolysis of HCFC-123 to produce chlorotrifluoroethylene, and DCS automatic control reaction is adopted, so that artificial operation fluctuation in the reaction process is avoided, the reaction is more stable, the production safety is greatly improved, the product quality is improved, and the production cost is reduced.
The invention takes trichloroethylene as raw material to react with hydrogen fluoride and chlorine to prepare HCFC-123, HCFC-123 is alkaline hydrolyzed by potassium hydroxide solution to obtain chlorotrifluoroethylene, so that the conversion rate of the chlorotrifluoroethylene reaches 65 percent, the selectivity of the chlorotrifluoroethylene reaches 99 percent, the product content reaches more than 99.8 percent, and the moisture is less than 10 ppm.
Detailed Description
The present invention will now be described in further detail with reference to specific examples. The following examples are intended to provide those skilled in the art with a more complete understanding of the present invention, and are not intended to limit the scope of the present invention.
The catalyst is used in an excessive amount, about 10 tons of catalyst is added into a 10 cubic reaction kettle once, the catalyst can be recycled for many times after being added once, and the catalyst is far more than materials for reaction.
Example 1
A method for preparing 1,1, 2-trifluoro-2-chloroethylene, comprising the following steps:
1) adding a catalyst into a reaction kettle, wherein the catalyst is antimony pentachloride, continuously adding hydrogen fluoride, tetrachloroethylene and chlorine into the reaction kettle at the speed of hydrogen fluoride being less than 250L/h, tetrachloroethylene being less than 180L/h and chlorine being 15Kg/h when the temperature of the reaction kettle is heated to 100 ℃ by steam, controlling the pressure of the reaction kettle to be 0.4-0.45 Mpa and the reaction temperature to be 110-115 ℃, opening a valve of a gas buffer tank, and controlling the temperature of a reaction bubbler to be 80-85 ℃; opening a water inlet valve of a condenser, and controlling the top temperature of the condenser to be 40-45 ℃; starting a cryogenic system, cooling the vented tail gas, collecting the vented tail gas, rectifying the collected crude HCFC-123 by a rectifying tower to remove alkali, washing by water, and then sending to a chlorotrifluoroethylene working section;
2) adding a potassium hydroxide solution into a chlorotrifluoroethylene reaction kettle, wherein the concentration of the potassium hydroxide solution is 20 percent, and the addition amount of the potassium hydroxide solution is 1000 kg; opening a hot water valve on the reaction kettle and heating to 60 ℃; starting the reaction kettle for stirring, continuously pumping the intermediate HCFC-123 into the reaction kettle through an HCFC-123 metering tank and a metering pump, and simultaneously starting a cooling water inlet and outlet valve of a fractionating tower;
3) when the pressure of the kettle rises to 0.5MPa, slowly opening a gas phase valve and a reflux valve, when the pressure of the fractionating tower rises to 0.8MPa, slowly opening a discharge valve, and normally opening a feed valve of the lightness removing kettle;
controlling the temperature of the reaction kettle to be 60 ℃ by adjusting a water inlet valve of the reaction kettle; by adjusting a discharge valve, the kettle pressure is kept at 0.5-0.55MPa, when the HCFC-123 metering tank shows that 1500kg is finished, an HCFC-123 metering pump is closed, an HCFC-123 feeding valve on the reaction kettle is closed, HCFC-123 feeding is stopped, stirring is continued, the kettle temperature is kept at 58-62 ℃ until the pressure of the reaction kettle is reduced to 0.1MPa, the discharge valve is closed, and materials in the reaction kettle are pressed into a distillation kettle for distillation;
4) opening a light component removal kettle feed valve and a west rectifying kettle feed valve, simultaneously opening a light component removal tower condenser frozen brine inlet and outlet valve, collecting the discharged material of the reaction kettle, starting to slowly heat up after the reaction material collection is finished, maintaining the pressure of the light component removal kettle at 0.75-0.80 Mpa, slightly opening a light component removal tower top discharge valve, taking a light component removal tower middle sample at regular time, and sending the kettle material into an east rectifying tower to rectify qualified chlorotrifluoroethylene products after the kettle sample is qualified;
5) after materials in the reaction kettle are pressed into the distillation kettle, slowly opening a steam valve and a drain valve, stopping heating when the temperature of the distillation kettle is raised to 95 ℃, starting cooling water to cool to 40 ℃ at the heating rate of 20 ℃ per hour, and sending to a post-treatment working section; the distilled materials are layered, the lower layer materials are rectified in a light component removal tower, and the upper layer water is sent to prepare a potassium hydroxide solution.
The product content in the embodiment reaches more than 99.8 percent, the moisture is less than 10ppm, the conversion rate of the chlorotrifluoroethylene reaches 65 percent, and the selectivity of the chlorotrifluoroethylene reaches 99 percent.
Example 2
A method for preparing 1,1, 2-trifluoro-2-chloroethylene, comprising the following steps:
1) adding a catalyst into a reaction kettle, wherein the catalyst is antimony pentachloride, continuously adding hydrogen fluoride, tetrachloroethylene and chlorine into the reaction kettle at the speed of hydrogen fluoride being less than 250L/h, tetrachloroethylene being less than 180L/h and chlorine being 12Kg/h when the temperature of the reaction kettle is heated to 100 ℃ by steam, controlling the pressure of the reaction kettle to be 0.4-0.45 Mpa and the reaction temperature to be 100-105 ℃, opening a valve of a gas buffer tank, and controlling the temperature of a reaction bubbler to be 65-70 ℃; opening a water inlet valve of a condenser, and controlling the top temperature of the condenser to be 40-45 ℃; starting a cryogenic system, cooling the vented tail gas, collecting the vented tail gas, rectifying the collected crude HCFC-123 by a rectifying tower to remove alkali, washing by water, and then sending to a chlorotrifluoroethylene working section;
2) adding a potassium hydroxide solution into a chlorotrifluoroethylene reaction kettle, wherein the concentration of the potassium hydroxide solution is 20 percent, and the addition amount of the potassium hydroxide solution is 1000 kg; opening a hot water valve on the reaction kettle and heating to 60 ℃; starting the reaction kettle for stirring, continuously pumping the intermediate HCFC-123 into the reaction kettle through an HCFC-123 metering tank and a metering pump, and simultaneously starting a cooling water inlet and outlet valve of a fractionating tower;
3) when the pressure of the kettle rises to 0.5MPa, slowly opening a gas phase valve and a reflux valve, when the pressure of the fractionating tower rises to 0.8MPa, slowly opening a discharge valve, and normally opening a feed valve of the lightness removing kettle;
controlling the temperature of the reaction kettle to be 60 ℃ by adjusting a water inlet valve of the reaction kettle; by adjusting a discharge valve, the kettle pressure is kept at 0.5-0.55MPa, when the HCFC-123 metering tank shows that 1500kg is finished, an HCFC-123 metering pump is closed, an HCFC-123 feeding valve on the reaction kettle is closed, HCFC-123 feeding is stopped, stirring is continued, the kettle temperature is kept at 58-60 ℃ until the pressure of the reaction kettle is reduced to 0.1MPa, the discharge valve is closed, and materials in the reaction kettle are pressed into a distillation kettle for distillation;
4) opening a light component removal kettle feed valve and a west rectifying kettle feed valve, simultaneously opening a light component removal tower condenser frozen brine inlet and outlet valve, collecting the discharged material of the reaction kettle, starting to slowly heat up after the reaction material collection is finished, maintaining the pressure of the light component removal kettle at 0.75-0.80 Mpa, slightly opening a light component removal tower top discharge valve, taking a light component removal tower middle sample at regular time, and sending the kettle material into an east rectifying tower to rectify qualified chlorotrifluoroethylene products after the kettle sample is qualified;
5) after materials in the reaction kettle are pressed into the distillation kettle, slowly opening a steam valve and a drain valve, stopping heating when the temperature of the distillation kettle is raised to 95 ℃, starting cooling water to cool to 40 ℃ at the heating rate of 20 ℃ per hour, and sending to a post-treatment working section; the distilled materials are layered, the lower layer materials are rectified in a light component removal tower, and the upper layer water is sent to prepare a potassium hydroxide solution.
The product content in the embodiment reaches more than 99.8 percent, the moisture is less than 10ppm, the conversion rate of the chlorotrifluoroethylene reaches 65 percent, and the selectivity of the chlorotrifluoroethylene reaches 99 percent.
Example 3
A method for preparing 1,1, 2-trifluoro-2-chloroethylene, comprising the following steps:
1) adding a catalyst into a reaction kettle, wherein the catalyst is antimony pentachloride, continuously adding hydrogen fluoride, tetrachloroethylene and chlorine into the reaction kettle at the speed of hydrogen fluoride being less than 250L/h, tetrachloroethylene being less than 180L/h and chlorine being 14Kg/h when the temperature of the reaction kettle is heated to 100 ℃ by steam, controlling the pressure of the reaction kettle to be 0.4-0.45 Mpa and the reaction temperature to be 105-110 ℃, opening a valve of a gas buffer tank, and controlling the temperature of a reaction bubbler to be 70-75 ℃; opening a water inlet valve of a condenser, and controlling the top temperature of the condenser to be 40-45 ℃; starting a cryogenic system, cooling the vented tail gas, collecting the vented tail gas, rectifying the collected crude HCFC-123 by a rectifying tower to remove alkali, washing by water, and then sending to a chlorotrifluoroethylene working section;
2) adding a potassium hydroxide solution into a chlorotrifluoroethylene reaction kettle, wherein the concentration of the potassium hydroxide solution is 20 percent, and the addition amount of the potassium hydroxide solution is 1000 kg; opening a hot water valve on the reaction kettle and heating to 60 ℃; starting the reaction kettle for stirring, continuously pumping the intermediate HCFC-123 into the reaction kettle through an HCFC-123 metering tank and a metering pump, and simultaneously starting a cooling water inlet and outlet valve of a fractionating tower;
3) when the pressure of the kettle rises to 0.5MPa, slowly opening a gas phase valve and a reflux valve, when the pressure of the fractionating tower rises to 0.8MPa, slowly opening a discharge valve, and normally opening a feed valve of the lightness removing kettle;
controlling the temperature of the reaction kettle to be 60 ℃ by adjusting a water inlet valve of the reaction kettle; by adjusting a discharge valve, the kettle pressure is kept at 0.5-0.55MPa, when the HCFC-123 metering tank shows that 1500kg is finished, an HCFC-123 metering pump is closed, an HCFC-123 feeding valve on the reaction kettle is closed, HCFC-123 feeding is stopped, stirring is continued, the kettle temperature is kept at 58-60 ℃ until the pressure of the reaction kettle is reduced to 0.1MPa, the discharge valve is closed, and materials in the reaction kettle are pressed into a distillation kettle for distillation;
4) opening a light component removal kettle feed valve and a west rectifying kettle feed valve, simultaneously opening a light component removal tower condenser frozen brine inlet and outlet valve, collecting the discharged material of the reaction kettle, starting to slowly heat up after the reaction material collection is finished, maintaining the pressure of the light component removal kettle at 0.75-0.80 Mpa, slightly opening a light component removal tower top discharge valve, taking a light component removal tower middle sample at regular time, and sending the kettle material into an east rectifying tower to rectify qualified chlorotrifluoroethylene products after the kettle sample is qualified;
5) after materials in the reaction kettle are pressed into the distillation kettle, slowly opening a steam valve and a drain valve, stopping heating when the temperature of the distillation kettle is raised to 95 ℃, starting cooling water to cool to 40 ℃ at the heating rate of 20 ℃ per hour, and sending to a post-treatment working section; the distilled materials are layered, the lower layer materials are rectified in a light component removal tower, and the upper layer water is sent to prepare a potassium hydroxide solution.
The product content in the embodiment reaches more than 99.8 percent, the moisture is less than 10ppm, the conversion rate of the chlorotrifluoroethylene reaches 65 percent, and the selectivity of the chlorotrifluoroethylene reaches 99 percent.
Example 4
A method for preparing 1,1, 2-trifluoro-2-chloroethylene, comprising the following steps:
1) adding a catalyst into a reaction kettle, wherein the catalyst is titanium tetrachloride, continuously adding hydrogen fluoride, tetrachloroethylene and chlorine into the reaction kettle at the speed of less than 250L/h of hydrogen fluoride, less than 180L/h of tetrachloroethylene and 15Kg/h of chlorine when the temperature of the reaction kettle is heated to 100 ℃ by steam, controlling the pressure of the reaction kettle to be 0.4-0.45 Mpa and the reaction temperature to be 110-115 ℃, opening a valve of a gas buffer tank, and controlling the temperature of a reaction bubbler to be 75-80 ℃; opening a water inlet valve of a condenser, and controlling the top temperature of the condenser to be 40-45 ℃; starting a cryogenic system, cooling the vented tail gas, collecting the vented tail gas, rectifying the collected crude HCFC-123 by a rectifying tower to remove alkali, washing by water, and then sending to a chlorotrifluoroethylene working section;
2) adding a potassium hydroxide solution into a chlorotrifluoroethylene reaction kettle, wherein the concentration of the potassium hydroxide solution is 20 percent, and the addition amount of the potassium hydroxide solution is 1000 kg; opening a hot water valve on the reaction kettle and heating to 60 ℃; starting the reaction kettle for stirring, continuously pumping the intermediate HCFC-123 into the reaction kettle through an HCFC-123 metering tank and a metering pump, and simultaneously starting a cooling water inlet and outlet valve of a fractionating tower;
3) when the pressure of the kettle rises to 0.5MPa, slowly opening a gas phase valve and a reflux valve, when the pressure of the fractionating tower rises to 0.8MPa, slowly opening a discharge valve, and normally opening a feed valve of the lightness removing kettle;
controlling the temperature of the reaction kettle to be 60 ℃ by adjusting a water inlet valve of the reaction kettle; by adjusting a discharge valve, the kettle pressure is kept at 0.5-0.55MPa, when the HCFC-123 metering tank shows that 1500kg is finished, an HCFC-123 metering pump is closed, an HCFC-123 feeding valve on the reaction kettle is closed, HCFC-123 feeding is stopped, stirring is continued, the kettle temperature is kept at 58-60 ℃ until the pressure of the reaction kettle is reduced to 0.1MPa, the discharge valve is closed, and materials in the reaction kettle are pressed into a distillation kettle for distillation;
4) opening a light component removal kettle feed valve and a west rectifying kettle feed valve, simultaneously opening a light component removal tower condenser frozen brine inlet and outlet valve, collecting the discharged material of the reaction kettle, starting to slowly heat up after the reaction material collection is finished, maintaining the pressure of the light component removal kettle at 0.75-0.80 Mpa, slightly opening a light component removal tower top discharge valve, taking a light component removal tower middle sample at regular time, and sending the kettle material into an east rectifying tower to rectify qualified chlorotrifluoroethylene products after the kettle sample is qualified;
5) after materials in the reaction kettle are pressed into the distillation kettle, slowly opening a steam valve and a drain valve, stopping heating when the temperature of the distillation kettle is raised to 95 ℃, starting cooling water to cool to 40 ℃ at the heating rate of 20 ℃ per hour, and sending to a post-treatment working section; the distilled materials are layered, the lower layer materials are rectified in a light component removal tower, and the upper layer water is sent to prepare a potassium hydroxide solution.
The product content in the example reaches more than 99.8%, the moisture is less than 10ppm, the conversion rate of the chlorotrifluoroethylene reaches 64.8%, and the selectivity of the chlorotrifluoroethylene reaches 98.5%.
In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.
Claims (8)
- A process for the preparation of 1,1, 2-trifluoro-2-chloroethylene, characterized in that: the preparation method comprises the following steps:1) adding a catalyst into a reaction kettle, heating the reaction kettle to 100 ℃ by using steam, continuously adding hydrogen fluoride, tetrachloroethylene and chlorine into the reaction kettle at a certain speed, controlling the pressure of the reaction kettle to be 0.4-0.45 Mpa and the reaction temperature to be 100-115 ℃, opening a valve to a gas buffer tank, and controlling the temperature of a reaction bubbler to be 65-85 ℃; starting a water inlet valve of a condenser, starting a cryogenic system, cooling the vented tail gas, collecting the collected crude HCFC-123, rectifying the crude HCFC-123 by a rectifying tower to remove alkali, washing the crude HCFC-123 by water, and sending the crude HCFC-123 to a chlorotrifluoroethylene working section;2) adding a potassium hydroxide solution into a chlorotrifluoroethylene reaction kettle, opening a hot water valve on the reaction kettle for heating, starting the reaction kettle for stirring, continuously pumping an intermediate HCFC-123 into the reaction kettle through an HCFC-123 metering tank and a metering pump, and simultaneously starting a cooling water inlet and outlet valve of a fractionating tower;3) when the pressure of the kettle rises to 0.5MPa, slowly opening a gas phase valve and a reflux valve, when the pressure of the fractionating tower rises to 0.8MPa, slowly opening a discharge valve, and normally opening a feed valve of the lightness removing kettle;controlling the temperature of the reaction kettle to be 60 ℃ by adjusting a water inlet valve of the reaction kettle; by adjusting a discharge valve, the kettle pressure is kept at 0.5-0.55MPa, when the HCFC-123 metering tank shows that 1500kg is finished, an HCFC-123 metering pump is closed, an HCFC-123 feeding valve on the reaction kettle is closed, HCFC-123 feeding is stopped, stirring is continued, the kettle temperature is kept at 58-62 ℃ until the pressure of the reaction kettle is reduced to 0.1MPa, the discharge valve is closed, and materials in the reaction kettle are pressed into a distillation kettle for distillation;4) opening a light component removal kettle feed valve and a west rectifying kettle feed valve, simultaneously opening a light component removal tower condenser frozen brine inlet and outlet valve, collecting the reaction kettle discharge, starting to slowly heat up after reaction material collection is finished, maintaining the light component removal kettle pressure, slightly opening a light component removal tower top discharge valve, taking a light component removal tower middle sample at fixed time, and sending the kettle material to an east rectifying tower to rectify qualified chlorotrifluoroethylene products after the kettle sample is qualified;5) after materials in the reaction kettle are pressed into the distillation kettle, slowly opening a steam valve and a drain valve, stopping heating when the temperature of the distillation kettle is raised to 95 ℃, opening cooling water to reduce the temperature to 40 ℃, and sending the materials to a post-treatment working section; the distilled materials are layered, the lower layer materials are rectified in a light component removal tower, and the upper layer water is sent to prepare a potassium hydroxide solution.
- 2. The process for the preparation of 1,1, 2-trifluoro-2-chloroethylene according to claim 1, characterized in that: the adding speeds of the hydrogen fluoride, the tetrachloroethylene and the chlorine in the step 1) are respectively as follows: the hydrogen fluoride is less than 250L/h, the tetrachloroethylene is less than 180L/h, and the chlorine is 12-15 Kg/h.
- 3. The process for the preparation of 1,1, 2-trifluoro-2-chloroethylene according to claim 1, characterized in that: the catalyst in the step 1) is antimony pentachloride or titanium tetrachloride.
- 4. The process for the preparation of 1,1, 2-trifluoro-2-chloroethylene according to claim 1, characterized in that: the top temperature of the condenser in the step 1) is controlled to be 40-45 ℃.
- 5. The process for the preparation of 1,1, 2-trifluoro-2-chloroethylene according to claim 1, characterized in that: the concentration of the potassium hydroxide solution in the step 2) is 20%, and the addition amount of the potassium hydroxide aqueous solution is 1000 kg.
- 6. The process for the preparation of 1,1, 2-trifluoro-2-chloroethylene according to claim 1, characterized in that: the temperature of the reaction kettle in the step 2) is heated to 60 ℃.
- 7. The process for the preparation of 1,1, 2-trifluoro-2-chloroethylene according to claim 1, characterized in that: and 4) keeping the kettle pressure of the lightness removing kettle in the step 4) at 0.75-0.80 Mpa.
- 8. The process for the preparation of 1,1, 2-trifluoro-2-chloroethylene according to claim 1, characterized in that: the temperature rise rate of the distillation kettle in the step 5) is 20 ℃ per hour.
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Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1042344A (en) * | 1988-10-25 | 1990-05-23 | 纳幕尔杜邦公司 | Preparation 1,1,1, the 2-tetrafluoro is improved one's methods for ethane |
| CN1057643A (en) * | 1990-06-28 | 1992-01-08 | 纳幕尔杜邦公司 | Fluoridizing of haloolefin |
| CN1099375A (en) * | 1993-08-24 | 1995-03-01 | 中国科学院上海有机化学研究所 | Method of producing fluoro halohydrocarbon and fluorohydrocarbon by gas-phase catalysis |
| CN1312241A (en) * | 2000-02-29 | 2001-09-12 | 阿托菲纳公司 | preparation for 1,1,1,-trifluoro-2,2-dichloroethane |
| CN101151233A (en) * | 2005-02-09 | 2008-03-26 | 霍尼韦尔国际公司 | Method of making 1,1,1-trifluoroethane |
| CN101402546A (en) * | 2008-11-13 | 2009-04-08 | 山东华安新材料有限公司 | Method for preparing dichloro-trifluoro-ethane |
| CN101648846A (en) * | 2009-09-15 | 2010-02-17 | 浙江三美化工股份有限公司 | Producing process for synthesizing 1, 1, 1, 2-tetrafluoroethane by liquid phase-gas phase method |
| CN101696149A (en) * | 2009-10-29 | 2010-04-21 | 江苏康泰氟化工有限公司 | Method for preparing 1,1,1-trifluoro-2-chloroethane |
| US20100324345A1 (en) * | 2009-06-22 | 2010-12-23 | Honeywell International Inc. | SYSTEMS AND PROCESSES FOR CFO-1113 FORMATION FROM HCFC-123a |
| CN102120715A (en) * | 2010-12-29 | 2011-07-13 | 江苏康泰氟化工有限公司 | Preparation method of 1,1,1-trifluoro-2-chloroethane |
| CN105237334A (en) * | 2015-09-30 | 2016-01-13 | 巨化集团技术中心 | Method for combined production of 1,1,2-trifluorotrichloroethane and 1,1,1-trifluorodichloroethane |
| CN106565413A (en) * | 2016-10-17 | 2017-04-19 | 邵武华航新材料有限公司 | A method of preparing trifluorochloroethene through gas-phase catalytic dehydrochlorination |
| CN106631679A (en) * | 2016-11-07 | 2017-05-10 | 浙江埃克盛化工有限公司 | Improved technology for producing 1,1,2-trichloro-1,2,2-trifluoroethane |
| CN108558650A (en) * | 2018-05-29 | 2018-09-21 | 江苏蓝色星球环保科技股份有限公司 | The method that tetrachloro-ethylene prepares trifluoro-acetyl chloride |
-
2020
- 2020-11-06 CN CN202011229710.3A patent/CN112341311A/en active Pending
Patent Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1042344A (en) * | 1988-10-25 | 1990-05-23 | 纳幕尔杜邦公司 | Preparation 1,1,1, the 2-tetrafluoro is improved one's methods for ethane |
| CN1057643A (en) * | 1990-06-28 | 1992-01-08 | 纳幕尔杜邦公司 | Fluoridizing of haloolefin |
| CN1099375A (en) * | 1993-08-24 | 1995-03-01 | 中国科学院上海有机化学研究所 | Method of producing fluoro halohydrocarbon and fluorohydrocarbon by gas-phase catalysis |
| CN1312241A (en) * | 2000-02-29 | 2001-09-12 | 阿托菲纳公司 | preparation for 1,1,1,-trifluoro-2,2-dichloroethane |
| CN101151233A (en) * | 2005-02-09 | 2008-03-26 | 霍尼韦尔国际公司 | Method of making 1,1,1-trifluoroethane |
| CN101402546A (en) * | 2008-11-13 | 2009-04-08 | 山东华安新材料有限公司 | Method for preparing dichloro-trifluoro-ethane |
| US20100324345A1 (en) * | 2009-06-22 | 2010-12-23 | Honeywell International Inc. | SYSTEMS AND PROCESSES FOR CFO-1113 FORMATION FROM HCFC-123a |
| CN101648846A (en) * | 2009-09-15 | 2010-02-17 | 浙江三美化工股份有限公司 | Producing process for synthesizing 1, 1, 1, 2-tetrafluoroethane by liquid phase-gas phase method |
| CN101696149A (en) * | 2009-10-29 | 2010-04-21 | 江苏康泰氟化工有限公司 | Method for preparing 1,1,1-trifluoro-2-chloroethane |
| CN102120715A (en) * | 2010-12-29 | 2011-07-13 | 江苏康泰氟化工有限公司 | Preparation method of 1,1,1-trifluoro-2-chloroethane |
| CN105237334A (en) * | 2015-09-30 | 2016-01-13 | 巨化集团技术中心 | Method for combined production of 1,1,2-trifluorotrichloroethane and 1,1,1-trifluorodichloroethane |
| CN106565413A (en) * | 2016-10-17 | 2017-04-19 | 邵武华航新材料有限公司 | A method of preparing trifluorochloroethene through gas-phase catalytic dehydrochlorination |
| CN106631679A (en) * | 2016-11-07 | 2017-05-10 | 浙江埃克盛化工有限公司 | Improved technology for producing 1,1,2-trichloro-1,2,2-trifluoroethane |
| CN108558650A (en) * | 2018-05-29 | 2018-09-21 | 江苏蓝色星球环保科技股份有限公司 | The method that tetrachloro-ethylene prepares trifluoro-acetyl chloride |
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