CN115259993B - Preparation method of hexafluorobutadiene - Google Patents
Preparation method of hexafluorobutadiene Download PDFInfo
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- CN115259993B CN115259993B CN202210845020.3A CN202210845020A CN115259993B CN 115259993 B CN115259993 B CN 115259993B CN 202210845020 A CN202210845020 A CN 202210845020A CN 115259993 B CN115259993 B CN 115259993B
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- 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 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 102
- 239000007789 gas Substances 0.000 claims abstract description 58
- 239000007788 liquid Substances 0.000 claims abstract description 42
- 239000011949 solid catalyst Substances 0.000 claims abstract description 40
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000002243 precursor Substances 0.000 claims abstract description 38
- 239000002994 raw material Substances 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 36
- 238000012719 thermal polymerization Methods 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000002156 mixing Methods 0.000 claims abstract description 32
- 238000010992 reflux Methods 0.000 claims abstract description 29
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000011701 zinc Substances 0.000 claims abstract description 22
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000012535 impurity Substances 0.000 claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 17
- 238000009835 boiling Methods 0.000 claims abstract description 14
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910000043 hydrogen iodide Inorganic materials 0.000 claims abstract description 13
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000460 chlorine Substances 0.000 claims abstract description 11
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 11
- 238000007142 ring opening reaction Methods 0.000 claims abstract description 11
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000004064 recycling Methods 0.000 claims abstract description 10
- 238000007146 photocatalysis Methods 0.000 claims abstract description 4
- 230000001699 photocatalysis Effects 0.000 claims abstract description 4
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 40
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 32
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 20
- 229910001634 calcium fluoride Inorganic materials 0.000 claims description 20
- 235000003270 potassium fluoride Nutrition 0.000 claims description 20
- 239000011698 potassium fluoride Substances 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 19
- 239000003054 catalyst Substances 0.000 claims description 18
- 238000006555 catalytic reaction Methods 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 238000005286 illumination Methods 0.000 claims description 8
- KWXXMLHQBFNLOR-UHFFFAOYSA-N 3,4-dichloro-1,1,2,3,4,4-hexafluorobut-1-ene Chemical group FC(F)=C(F)C(F)(Cl)C(F)(F)Cl KWXXMLHQBFNLOR-UHFFFAOYSA-N 0.000 claims description 6
- LMHAGAHDHRQIMB-UHFFFAOYSA-N 1,2-dichloro-1,2,3,3,4,4-hexafluorocyclobutane Chemical group FC1(F)C(F)(F)C(F)(Cl)C1(F)Cl LMHAGAHDHRQIMB-UHFFFAOYSA-N 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000011049 filling Methods 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims 4
- 239000011541 reaction mixture Substances 0.000 claims 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 112
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 21
- 238000001816 cooling Methods 0.000 description 21
- 229910052802 copper Inorganic materials 0.000 description 21
- 239000010949 copper Substances 0.000 description 21
- 238000004519 manufacturing process Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 9
- 238000007259 addition reaction Methods 0.000 description 8
- 238000005660 chlorination reaction Methods 0.000 description 7
- 150000001804 chlorine Chemical class 0.000 description 7
- 239000005457 ice water Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000005194 fractionation Methods 0.000 description 5
- 238000004817 gas chromatography Methods 0.000 description 4
- BSRRYOGYBQJAFP-UHFFFAOYSA-N 1,1,1,2,2,3-hexafluorobutane Chemical compound CC(F)C(F)(F)C(F)(F)F BSRRYOGYBQJAFP-UHFFFAOYSA-N 0.000 description 3
- QVHWOZCZUNPZPW-UHFFFAOYSA-N 1,2,3,3,4,4-hexafluorocyclobutene Chemical compound FC1=C(F)C(F)(F)C1(F)F QVHWOZCZUNPZPW-UHFFFAOYSA-N 0.000 description 3
- IRHYACQPDDXBCB-UHFFFAOYSA-N 1,2,3,4-tetrachloro-1,1,2,3,4,4-hexafluorobutane Chemical compound FC(F)(Cl)C(F)(Cl)C(F)(Cl)C(F)(F)Cl IRHYACQPDDXBCB-UHFFFAOYSA-N 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000006298 dechlorination reaction Methods 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/23—Preparation of halogenated hydrocarbons by dehalogenation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/08—Halides
- B01J27/12—Fluorides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/013—Preparation of halogenated hydrocarbons by addition of halogens
- C07C17/04—Preparation of halogenated hydrocarbons by addition of halogens to unsaturated halogenated hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- 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
- C07C17/278—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions of only halogenated hydrocarbons
- C07C17/281—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions of only halogenated hydrocarbons of only one compound
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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
- C07C17/354—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction by hydrogenation
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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
- C07C17/357—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction by dehydrogenation
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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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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/04—Systems containing only non-condensed rings with a four-membered ring
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the field of new energy, and particularly relates to a preparation method of hexafluorobutadiene. The method comprises the following steps: 1) Placing a liquid chlorotrifluoroethylene raw material at the bottom of a reaction kettle, heating and boosting the temperature, and then carrying out thermal polymerization reaction to obtain a precursor; 2) Fractionating in a high-pressure water bath to obtain an intermediate with a low boiling point, and recovering a residual liquid for later use; 3) Adding the intermediate into ethanol, performing zinc catalytic reflux reaction, collecting a gas product, mixing the gas product with hydrogen iodide gas, performing high-temperature ring-opening reaction, and condensing and recycling to obtain a condensate; 4) Mixing the condensate with the residual liquid obtained in the step 2), reacting with chlorine water under photocatalysis, adding into butyl carbitol, carrying out zinc catalytic heating reaction, condensing, refluxing and removing impurities, and allowing the gas product to pass through a high-temperature porous solid catalyst to obtain the hexafluorobutadiene. The preparation process can produce and prepare the hexafluorobutadiene from the low-cost raw material of the chlorotrifluoroethylene, and improve the yield to at least 85 percent, thereby greatly improving the preparation effect of the hexafluorobutadiene.
Description
Technical Field
The invention belongs to the field of new energy, and particularly relates to a preparation method of hexafluorobutadiene.
Background
The hexafluorobutadiene is an effective gas for the new generation dry etching, can be effectively used for etching dielectric materials such as silicon dioxide and silicon nitride, and belongs to an electronic industry system as a special electronic gas. Currently, the electronic industry has become a core industrial system supporting the sustainable development of national economy and guaranteeing the safety of national strategy. The special electronic gas is one of the key raw materials of the whole electronic industrial system, and has extremely wide application in the aspects of national defense and military, aerospace, novel solar cells, electronic products and the like.
However, most of the existing methods for preparing hexafluorobutadiene have the problems of low productivity, low yield, low conversion rate from raw materials to products in the actual production process and the like. The new schemes disclosed in Miller and Haszeldine have product yields of only less than 30% and about 14%, respectively, which limits the productive production of hexafluorobutadiene.
Therefore, the development of a high-yield and high-yield preparation process of the hexafluorobutadiene is the key for the development of the technical field of the hexafluorobutadiene and new energy.
Disclosure of Invention
The invention provides a preparation method of hexafluorobutadiene, which aims to solve the problems of low product yield, low purity of obtained products, high purification difficulty and the like of the existing preparation process of hexafluorobutadiene.
The invention aims to: the product yield of the hexafluorobutadiene is obviously improved to more than 85%, and the purity of the hexafluorobutadiene product can be effectively ensured to reach more than 99.99%.
In order to achieve the purpose, the invention adopts the following technical scheme.
A method of making hexafluorobutadiene, said method comprising:
1) Placing a liquid chlorotrifluoroethylene raw material at the bottom of a reaction kettle, heating and boosting the temperature, guiding the liquid chlorotrifluoroethylene raw material into a reaction vessel for thermal polymerization, condensing and recovering a thermal polymerization product, mixing the thermal polymerization product into the raw material until the raw material and/or the thermal polymerization product are not boiled again, and stopping recovering to obtain a precursor;
2) Fractionating the precursor in a high-pressure water bath to obtain an intermediate with a low boiling point, and recovering a residual liquid for later use after the volume of the precursor is not reduced;
3) Adding the intermediate into ethanol, adding simple substance zinc as a catalyst, collecting a gas product after reflux reaction, mixing the gas product with hydrogen iodide gas, performing high-temperature ring-opening reaction, condensing and recycling to obtain a condensate;
4) Mixing the condensate with the residual liquid obtained in the step 2), reacting with chlorine water under photocatalysis, adding into butyl carbitol, adding simple substance zinc as a catalyst, heating for reaction, condensing, refluxing and removing impurities, and allowing the gas product to pass through a high-temperature porous solid catalyst to obtain the hexafluorobutadiene.
Preferably, in step 1), the temperature and pressure raising control conditions are: firstly, controlling the pressure in the reaction kettle to be 0.6-0.8 MPa, and then heating to 42-45 ℃.
Preferably, the reaction temperature of the thermal polymerization reaction in the step 1) is 575 to 580 ℃, and the reaction time is 10 to 12 s.
Preferably, the high-pressure water bath fractionation in the step 2) is specifically as follows: placing the precursor in a boiling water bath in a waterproof way, and controlling the pressure in a container in which the precursor is positioned to be 0.5-0.7 MPa.
Preferably, the gaseous product in the step 3) is mixed with hydrogen iodide gas and then subjected to high-temperature catalytic reaction at 285-295 ℃ for 22-26 h.
Preferably, the light reaction in the step 4) is carried out for more than or equal to 24 h; the light reaction is carried out under the irradiation of UV light.
Preferably, the heating reaction in the step 4) is controlled at 145-150 ℃ and the reaction time is 6-8 h.
Preferably, the porous solid catalyst is composed of activated carbon, potassium fluoride and calcium fluoride; the molar ratio of the potassium fluoride to the calcium fluoride is 1: (0.95-1.05), and the activated carbon accounts for 50-65 wt% of the total mass of the porous solid catalyst.
Preferably, the porous solid catalyst is prepared by uniformly mixing activated carbon, potassium fluoride and calcium fluoride and then filling the mixture into a tubular container, and controlling the flow rate of a gas product to enable the gas product to pass through the tubular container in 12-14 s.
Preferably, the porous solid catalyst in the step 4) is preheated to 665-670 ℃.
According to the technical scheme, chlorotrifluoroethylene is used as a raw material, boiling and/or volatilization of chlorotrifluoroethylene is inhibited under high pressure, the chlorotrifluoroethylene can reach a higher temperature and then slowly boil or slowly volatilize, and then is guided to a reaction vessel for high-temperature thermal polymerization, if the chlorotrifluoroethylene is directly heated under no high pressure to be thermally boiled or quickly volatilized and guided to the reaction vessel for thermal polymerization, only 3,4-dichloro-hexafluoro-1-butene of about 22-24% can be obtained, 1,2-dichlorohexafluoro cyclobutane of about 38-41% is generated as an impurity product, the total yield of the two is not higher than 65%, the two can not be directly and effectively utilized, and 3,4-dichloro-hexafluoro-1-butene also needs to be subjected to high-temperature reaction treatment to obtain the hexafluorobutadiene. In the technical scheme of the invention, selective conversion and more effective utilization of raw materials are realized by slow reaction and control of the reaction process.
In the technical scheme of the invention, the 3,4-dichloro-hexafluoro-1-butene product yield can be improved to more than 47% by controlling the reaction process and continuously carrying out repeated treatment and reaction at the same time, and the 1,2-dichlorohexafluorocyclobutane yield can be improved to more than 49%, so that the reaction sufficiency is greatly improved, the total product yield is remarkably improved, and the utilization rate of raw materials is also remarkably improved.
In addition, the invention realizes the effective separation of two intermediate products by a high-pressure water bath fractionation mode, the intermediate 1,2-dichlorohexafluorocyclobutane is obtained by separate separation, then zinc catalytic dechlorination and hydrogen iodide catalytic hydrogenation ring opening are carried out to obtain hexafluorobutane, the hexafluorobutane is condensed and recycled and is mixed with the collected raffinate 3,4-dichloro-hexafluoro-1-butene, and the hexafluorobutane and chlorine water are subjected to addition reaction under photocatalysis to obtain the important prepositive product 1,2,3,4-tetrachlorohexafluorobutane (CF) 2 Cl-CFCl-CFCl-CF 2 C) And refluxing the obtained 1,2,3,4-tetrachlorohexafluorobutane under the catalysis of zinc to obtain the target product hexafluorobutadiene.
In the process of the scheme, the most important is the temperature rise and pressure rise reaction in the step 1), which is the key for realizing high product yield, the product yield is obviously reduced to be lower than 60% by participating in the thermal polymerization reaction after the gasification at the normal temperature, and the high-pressure water bath fractionation in the step 2) is the key for improving the product purity and guaranteeing the product yield, and two kinds of boiling point substances, namely 1,2-dichlorohexafluorocyclobutane and 3,4-dichloro-hexafluoro-1-butene, can be effectively separated so as to avoid the generation of impurities in side reactions or reduce target products. The step 3) is a conventional conversion reaction process, but in the step 4), the two components are jointly processed by a one-step method, so that the construction period can be greatly shortened, the production cost can be reduced, the production efficiency and the production cost performance of actual enterprises can be improved, and the industrial value and the practical value of the technical scheme are improved. In addition, the hexafluoro-cyclobutene generated and participated in the preparation process is a main impurity component generated in the production process of the invention and the production process of the prior art, and usually needs to be removed by a complicated separation process, but the hexafluoro-cyclobutene is converted into the target product of the hexafluoro-butadiene after the isomerization conversion of the hexafluoro-cyclobutene is realized by the porous solid catalyst, so that the yield and the purity of the product of the invention are greatly improved while the filtration and impurity removal steps are reduced, and the porous solid catalyst can remove impurities such as water, gas and the like.
The invention has the beneficial effects that: 1) By the preparation process, the yield of the hexafluorobutadiene in the existing industrialized production and preparation process of the low-cost raw material chlorotrifluoroethylene can be increased from about 40% to at least 85%, and the preparation effect of the hexafluorobutadiene is greatly improved; 2) The obtained product has high purity which can basically reach more than 99.99 percent and meet the use requirements of the existing industry; 3) The scheme is suitable for industrial large-scale production and preparation.
Detailed Description
The present invention will be described in further detail with reference to specific examples. Those skilled in the art will be able to implement the invention based on these teachings. Moreover, the embodiments of the present invention described in the following description are generally only some embodiments of the present invention, and not all embodiments. Therefore, all other embodiments obtained by a person of ordinary skill in the art based on the embodiments of the present invention without any creative effort shall fall within the protection scope of the present invention.
Unless otherwise specified, all the raw materials used in the examples of the present invention are commercially available or available to those skilled in the art; unless otherwise specified, the methods used in the examples of the present invention are all those known to those skilled in the art.
Unless otherwise specified, the reactor used in the examples of the present invention was a high-pressure polymerization reactor which was purchased from the Wailan autonomous system and equipped with a condensing reflux unit.
Example 1
A method of preparing hexafluorobutadiene, the method comprising: 1) Placing a liquid chlorotrifluoroethylene raw material at the bottom of a reaction kettle, boosting the pressure to 0.75 MPa, then raising the temperature to 45 ℃, slowly gasifying chlorotrifluoroethylene, guiding the gasified chlorotrifluoroethylene into a copper pipe preheated to 575 ℃ for thermal polymerization reaction, controlling the flow rate during the flow guiding so that the gasified chlorotrifluoroethylene passes through a heat pipe in 12 s, cooling to less than or equal to 40 ℃ after the reaction, condensing and recovering a thermal polymerization product, mixing the thermal polymerization product into the raw material, placing the raw material at the bottom of the reaction kettle in the bottom of the reaction kettle until the material at the bottom of the reaction kettle is not boiled any more, stopping the reaction, releasing the pressure, maintaining the constant temperature for 10 min, cooling to room temperature, and recovering to obtain a precursor; 2) Putting the precursor into a container, boosting the pressure to 0.6 MPa, putting the container into a boiling water bath to obtain a low-boiling-point intermediate generated by gasifying the precursor, and recovering residual liquid in the container for later use after the volume of the precursor is not reduced; 3) Cooling the intermediate to room temperature, adding the cooled intermediate into ethanol with 1.2 times of volume, adding 0.05 times of mass of elemental zinc as a catalyst, carrying out reflux reaction at 75 ℃, collecting a gas product, and mixing the gas product with hydrogen iodide gas in a volume ratio of 1:1, placing the mixture at 290 ℃ for ring opening reaction, performing ice-water bath condensation and recycling to obtain condensate after 24 h; 4) Mixing the condensate with the residual liquid obtained in the step 2) to obtain a mixed liquid, adding excessive saturated chlorine water, carrying out UV illumination on 24 h under the catalysis of the chlorine water to carry out chlorination addition reaction to obtain a pre-product solution, adding the pre-product solution into 1.2 times of butyl carbitol, adding 0.05 times of simple substance zinc as a catalyst, heating to 145 ℃ for reflux reaction to obtain 8 h, condensing and refluxing in the process to remove impurities, collecting a gas product at a constant temperature of 65 ℃, enabling the gas product to pass through a copper pipe filled with a porous solid catalyst in 12 s, wherein the porous solid catalyst in the copper pipe is composed of activated carbon, potassium fluoride and calcium fluoride, and the molar ratio of the potassium fluoride to the calcium fluoride is 1:1, the active carbon accounts for 65 wt% of the total mass of the porous solid catalyst, the porous solid catalyst is preheated to 670 ℃, and then the target product of the hexafluorobutadiene is obtained.
Example 2
A method of preparing hexafluorobutadiene, the method comprising: 1) Placing a liquid chlorotrifluoroethylene raw material at the bottom of a reaction kettle, boosting the pressure to 0.6 MPa, heating to 42 ℃, slowly gasifying the chlorotrifluoroethylene, guiding the gasified chlorotrifluoroethylene into a copper pipe preheated to 580 ℃ for thermal polymerization reaction, controlling the flow rate during the flow guiding so that the gasified chlorotrifluoroethylene passes through a heat pipe in 12 s, cooling to be less than or equal to 40 ℃ after the reaction, condensing and recovering a thermal polymerization product, mixing the thermal polymerization product into the raw material, placing the raw material at the bottom of the reaction kettle, stopping the reaction until the material at the bottom of the reaction kettle does not boil any more, releasing the pressure, maintaining the constant temperature for 10 min, cooling to room temperature, and recovering to obtain a precursor; 2) Putting the precursor into a container, boosting the pressure to 0.7 MPa, putting the container into a boiling water bath to obtain a low-boiling-point intermediate generated by gasifying the precursor, and recovering residual liquid in the container for later use after the volume of the precursor is not reduced; 3) Cooling the intermediate to room temperature, adding the cooled intermediate into ethanol with 1.2 times of volume, adding 0.05 times of mass of elemental zinc as a catalyst, carrying out reflux reaction at 75 ℃, collecting a gas product, and mixing the gas product with hydrogen iodide gas in a volume ratio of 1:1, placing the mixture in a condition of 295 ℃ for ring opening reaction, 23 h, and then condensing and recycling the mixture in an ice water bath to obtain condensate; 4) Mixing the condensate with the residual liquid obtained in the step 2) to obtain a mixed liquid, adding excessive saturated chlorine water, carrying out UV illumination on 24 h under the catalysis of the chlorine water to carry out chlorination addition reaction to obtain a pre-product solution, adding the pre-product solution into 1.2 times of butyl carbitol, adding 0.05 times of simple substance zinc as a catalyst, heating to 150 ℃, carrying out reflux reaction to obtain 6 h, condensing and refluxing in the process to remove impurities, collecting a gas product at a constant temperature of 65 ℃, enabling the gas product to pass through a copper pipe filled with a porous solid catalyst in 14 s, wherein the porous solid catalyst in the copper pipe is composed of activated carbon, potassium fluoride and calcium fluoride, and the molar ratio of the potassium fluoride to the calcium fluoride is 1:1, the active carbon accounts for 65 wt% of the total mass of the porous solid catalyst, and the porous solid catalyst is preheated to 670 ℃, and then the target product of hexafluorobutadiene is obtained.
Example 3
A method of preparing hexafluorobutadiene, the method comprising: 1) Placing a liquid chlorotrifluoroethylene raw material at the bottom of a reaction kettle, boosting the pressure to 0.75 MPa, then raising the temperature to 42 ℃, slowly gasifying chlorotrifluoroethylene, guiding the gasified chlorotrifluoroethylene into a copper pipe preheated to 580 ℃ for thermal polymerization reaction, controlling the flow rate during the flow guiding so that the gasified chlorotrifluoroethylene passes through a heat pipe in 10 s, cooling to the temperature of less than or equal to 40 ℃ after the reaction, condensing and recovering a thermal polymerization product, mixing the thermal polymerization product into the raw material, placing the raw material at the bottom of the reaction kettle in the bottom of the reaction kettle until the material at the bottom of the reaction kettle is not boiled any more, stopping the reaction, releasing the pressure, maintaining the constant temperature for 10 min, and then cooling to room temperature for recovery to obtain a precursor; 2) Putting the precursor into a container, boosting the pressure to 0.6 MPa, putting the container into a boiling water bath to obtain a low-boiling-point intermediate generated by gasifying the precursor, and recovering residual liquid in the container for later use after the volume of the precursor is not reduced; 3) Cooling the intermediate to room temperature, adding the cooled intermediate into ethanol with 1.2 times of volume, adding 0.05 times of mass of elemental zinc as a catalyst, carrying out reflux reaction at 75 ℃, collecting a gas product, and mixing the gas product with hydrogen iodide gas in a volume ratio of 1:1, placing the mixture at 290 ℃ for ring opening reaction, performing ice-water bath condensation and recycling to obtain condensate after 24 h; 4) Mixing the condensate liquid and the residual liquid obtained in the step 2) to obtain a mixed liquid, adding excess saturated chlorine water, performing UV illumination 24 h under the catalysis of the chlorine water to perform chlorination addition reaction to obtain a pre-product solution, adding the pre-product solution into butyl carbitol with the volume being 1.2 times of that of the pre-product solution, adding 0.05 time of elemental zinc as a catalyst, heating to 145 ℃ for reflux reaction to 8 h, condensing and refluxing in the process to remove impurities, collecting a gas product at a constant temperature of 65 ℃, enabling the gas product to pass through a copper pipe filled with a porous solid catalyst in 12 s, wherein the porous solid catalyst in the copper pipe is composed of activated carbon, potassium fluoride and calcium fluoride, and the molar ratio of the potassium fluoride to the calcium fluoride is 1:1, the active carbon accounts for 65 wt% of the total mass of the porous solid catalyst, the porous solid catalyst is preheated to 670 ℃, and then the target product of the hexafluorobutadiene is obtained.
Example 4
A method of preparing hexafluorobutadiene, the method comprising: 1) Placing a liquid chlorotrifluoroethylene raw material at the bottom of a reaction kettle, boosting the pressure to 0.6 MPa, then raising the temperature to 42 ℃, slowly gasifying chlorotrifluoroethylene, guiding the gasified chlorotrifluoroethylene into a copper pipe preheated to 580 ℃ for thermal polymerization reaction, controlling the flow rate during the flow guiding so that the gasified chlorotrifluoroethylene passes through a heat pipe in 12 s, cooling to the temperature of less than or equal to 40 ℃ after the reaction, condensing and recovering a thermal polymerization product, mixing the thermal polymerization product into the raw material, placing the raw material at the bottom of the reaction kettle in the bottom of the reaction kettle until the material at the bottom of the reaction kettle is not boiled any more, stopping the reaction, releasing the pressure, maintaining the constant temperature for 10 min, cooling to room temperature, and recovering to obtain a precursor; 2) Putting the precursor into a container, boosting the pressure to 0.7 MPa, putting the container into a boiling water bath to obtain a low-boiling-point intermediate generated by gasifying the precursor, and recovering residual liquid in the container for later use after the volume of the precursor is not reduced; 3) Cooling the intermediate to room temperature, adding the cooled intermediate into ethanol with 1.2 times of volume, adding 0.05 times of mass of elemental zinc as a catalyst, carrying out reflux reaction at 75 ℃, collecting a gas product, and mixing the gas product with hydrogen iodide gas in a volume ratio of 1:1, placing the mixture at 285 ℃ for ring opening reaction of 25 h, and then condensing and recycling the mixture in an ice water bath to obtain condensate; 4) Mixing the condensate with the residual liquid obtained in the step 2) to obtain a mixed liquid, adding excessive saturated chlorine water, carrying out UV illumination on 24 h under the catalysis of the chlorine water to carry out chlorination addition reaction to obtain a pre-product solution, adding the pre-product solution into 1.2 times of butyl carbitol, adding 0.05 times of simple substance zinc as a catalyst, heating to 145 ℃ for reflux reaction to 8 h, condensing and refluxing in the process to remove impurities, collecting a gas product at a constant temperature of 65 ℃, enabling the gas product to pass through a copper pipe filled with a porous solid catalyst in 14 s, wherein the porous solid catalyst in the copper pipe is composed of activated carbon, potassium fluoride and calcium fluoride, and the molar ratio of the potassium fluoride to the calcium fluoride is 1:1, the active carbon accounts for 65 wt% of the total mass of the porous solid catalyst, and the porous solid catalyst is preheated to 665 ℃, and then the target product of hexafluorobutadiene is obtained.
Comparative example 1
A method of preparing hexafluorobutadiene, the method comprising: 1) Placing a liquid chlorotrifluoroethylene raw material at the bottom of a reaction kettle, boosting the pressure to 0.75 MPa, then raising the temperature to 45 ℃, slowly gasifying chlorotrifluoroethylene, guiding the gasified chlorotrifluoroethylene into a copper pipe preheated to 575 ℃ for thermal polymerization reaction, controlling the flow rate during the flow guiding so that the gasified chlorotrifluoroethylene passes through a heat pipe in 12 s, cooling to be less than or equal to 40 ℃ after the reaction, condensing and recovering a thermal polymerization product, mixing the thermal polymerization product into the raw material, placing the raw material at the bottom of the reaction kettle, stopping the reaction until the material at the bottom of the reaction kettle is not boiled any more, releasing the pressure, cooling to room temperature, and recovering to obtain a precursor; 2) Putting the precursor into a container, boosting the pressure to 0.6 MPa, putting the container into a boiling water bath to obtain a low-boiling-point intermediate generated by gasifying the precursor, and recovering residual liquid in the container for later use after the volume of the precursor is not reduced; 3) Cooling the intermediate to room temperature, adding the cooled intermediate into ethanol with 1.2 times of volume, adding 0.05 times of mass of elemental zinc as a catalyst, carrying out reflux reaction at 75 ℃, collecting a gas product, and mixing the gas product with hydrogen iodide gas in a volume ratio of 1:1, placing the mixture at 290 ℃ for ring opening reaction, performing ice-water bath condensation and recycling to obtain condensate after 24 h; 4) Mixing the condensate liquid and the residual liquid obtained in the step 2) to obtain a mixed liquid, adding excess saturated chlorine water, performing UV illumination 24 h under the catalysis of the chlorine water to perform chlorination addition reaction to obtain a pre-product solution, adding the pre-product solution into butyl carbitol with the volume being 1.2 times of that of the pre-product solution, adding 0.05 time of elemental zinc as a catalyst, heating to 145 ℃ for reflux reaction to 8 h, condensing and refluxing in the process to remove impurities, collecting a gas product at a constant temperature of 65 ℃, enabling the gas product to pass through a copper pipe filled with a porous solid catalyst in 12 s, wherein the porous solid catalyst in the copper pipe is composed of activated carbon, potassium fluoride and calcium fluoride, and the molar ratio of the potassium fluoride to the calcium fluoride is 1:1, the active carbon accounts for 65 wt% of the total mass of the porous solid catalyst, the porous solid catalyst is preheated to 670 ℃, and then the target product of the hexafluorobutadiene is obtained.
Comparative example 2
A method of making hexafluorobutadiene, said method comprising: 1) Placing a liquid chlorotrifluoroethylene raw material at the bottom of a reaction kettle, heating to 45 ℃, slowly gasifying chlorotrifluoroethylene, guiding the gasified chlorotrifluoroethylene into a copper pipe preheated to 575 ℃ for thermal polymerization reaction, controlling the flow rate during the guiding so that the gasified chlorotrifluoroethylene passes through a heat pipe in 12 s, cooling to less than or equal to 40 ℃ after the reaction, condensing and recovering a thermal polymerization product, mixing the thermal polymerization product into the raw material, placing the raw material at the bottom of the reaction kettle until the material at the bottom of the reaction kettle is not boiled any more, stopping the reaction, releasing pressure, maintaining the constant temperature for 10 min, and cooling to room temperature for recovery to obtain a precursor; 2) Putting the precursor into a container, boosting the pressure to 0.6 MPa, putting the container into a boiling water bath to obtain a low-boiling-point intermediate generated by gasifying the precursor, and recovering residual liquid in the container for later use after the volume of the precursor is not reduced; 3) Cooling the intermediate to room temperature, adding the intermediate into ethanol with 1.2 times of volume of the intermediate, adding 0.05 times of mass of elemental zinc as a catalyst, performing reflux reaction at 75 ℃, collecting a gas product, and mixing the gas product with hydrogen iodide gas in a volume ratio of 1:1, placing the mixture at 290 ℃ for ring opening reaction of 24 h, and then condensing and recycling the mixture in an ice water bath to obtain condensate; 4) Mixing the condensate with the residual liquid obtained in the step 2) to obtain a mixed liquid, adding excessive saturated chlorine water, carrying out UV illumination on 24 h under the catalysis of the chlorine water to carry out chlorination addition reaction to obtain a pre-product solution, adding the pre-product solution into 1.2 times of butyl carbitol, adding 0.05 times of simple substance zinc as a catalyst, heating to 145 ℃ for reflux reaction to obtain 8 h, condensing and refluxing in the process to remove impurities, collecting a gas product at a constant temperature of 65 ℃, enabling the gas product to pass through a copper pipe filled with a porous solid catalyst in 12 s, wherein the porous solid catalyst in the copper pipe is composed of activated carbon, potassium fluoride and calcium fluoride, and the molar ratio of the potassium fluoride to the calcium fluoride is 1:1, the active carbon accounts for 65 wt% of the total mass of the porous solid catalyst, and the porous solid catalyst is preheated to 670 ℃, and then the target product of hexafluorobutadiene is obtained.
Comparative example 3
A method of preparing hexafluorobutadiene, the method comprising: 1) Placing a liquid chlorotrifluoroethylene raw material at the bottom of a reaction kettle, boosting the pressure to 0.75 MPa, then raising the temperature to 45 ℃, slowly gasifying chlorotrifluoroethylene, guiding the gasified chlorotrifluoroethylene into a copper pipe preheated to 575 ℃ for thermal polymerization reaction, controlling the flow rate during the flow guiding so that the gasified chlorotrifluoroethylene passes through a heat pipe in 12 s, cooling to less than or equal to 40 ℃ after the reaction, condensing and recovering a thermal polymerization product, mixing the thermal polymerization product into the raw material, placing the raw material at the bottom of the reaction kettle in the bottom of the reaction kettle until the material at the bottom of the reaction kettle is not boiled any more, stopping the reaction, releasing the pressure, maintaining the constant temperature for 10 min, cooling to room temperature, and recovering to obtain a precursor; 2) Shunting at constant temperature of 60 ℃ under normal pressure to obtain a low-boiling-point intermediate generated by gasifying the precursor, and recovering residual liquid in a container for later use after the volume of the precursor is not reduced; 3) Cooling the intermediate to room temperature, adding the cooled intermediate into ethanol with 1.2 times of volume, adding 0.05 times of mass of elemental zinc as a catalyst, carrying out reflux reaction at 75 ℃, collecting a gas product, and mixing the gas product with hydrogen iodide gas in a volume ratio of 1:1, placing the mixture at 290 ℃ for ring opening reaction of 24 h, and then condensing and recycling the mixture in an ice water bath to obtain condensate; 4) Mixing the condensate with the residual liquid obtained in the step 2) to obtain a mixed liquid, adding excessive saturated chlorine water, carrying out UV illumination on 24 h under the catalysis of the chlorine water to carry out chlorination addition reaction to obtain a pre-product solution, adding the pre-product solution into 1.2 times of butyl carbitol, adding 0.05 times of simple substance zinc as a catalyst, heating to 145 ℃ for reflux reaction to obtain 8 h, condensing and refluxing in the process to remove impurities, collecting a gas product at a constant temperature of 65 ℃, enabling the gas product to pass through a copper pipe filled with a porous solid catalyst in 12 s, wherein the porous solid catalyst in the copper pipe is composed of activated carbon, potassium fluoride and calcium fluoride, and the molar ratio of the potassium fluoride to the calcium fluoride is 1:1, the active carbon accounts for 65 wt% of the total mass of the porous solid catalyst, the porous solid catalyst is preheated to 670 ℃, and then the target product of the hexafluorobutadiene is obtained.
The purity and yield of the hexafluorobutadiene products prepared in examples 1 to 4 and comparative examples 1 to 3 were measured and characterized. Wherein the calculated yield of the product in the example 1 is 91.2%, the product purity is more than 99.99% VOL by the gas chromatography, the calculated yield of the product in the example 2 is 88.7%, the product purity is more than 99.99% VOL by the gas chromatography, the calculated yield of the product in the example 3 is 90.2%, the product purity is more than 99.99% VOL by the gas chromatography, the calculated yield of the product in the example 4 is 89.6%, and the product purity is more than 99.99% VOL by the gas chromatography. It can be seen that the yield of the product obtained in the embodiment of the invention can reach more than 88%, and the industrial production yield is slightly reduced but can still be maintained at more than 85% after the trial production (2022/5/1-2022/5/15) for half a month in a factory, and the purity of the product can be maintained to be more than 99.99% VOL. In comparative example 1, the product yield can still be kept high, reaching about 88.9% VOL, but the purity is reduced to about 98.91% VOL, mainly because in the constant temperature process after the reaction in step 1), part of impurities which are difficult to remove in the subsequent process can be volatilized and removed, while in comparative example 1, after the constant temperature step is omitted, the solution is rapidly cooled, and part of impurities can be retained. And in the industrial trial production (2022/4/28-2022/4/30), the product purity is reduced to about 96.13 percent VOL, which produces very obvious reduction and is not beneficial to industrial mass production. In the comparative example 2, the rapid thermal polymerization reaction is directly carried out under the non-high pressure condition, a large amount of impurities are generated, the reaction sufficiency and selectivity are obviously reduced, the calculated yield of the final product is only about 69.4%, the product purity is relatively kept high, and the purity can reach more than 99% of VOL. But the product yield is obviously reduced, and the cost and the benefit of factory batch and large-scale production are obviously reduced. In comparative example 3, atmospheric fractionation was employed wherein the atmospheric boiling points of the two components were about 59 deg.C and 63.5 deg.C, respectively, and the atmospheric control of 60 deg.C resulted in poor fractionation, thereby reducing the actual product yield to about 81.4% VOL and the purity to about 98.69%. In addition, in the pilot production process (2022/4/25-2022/4/26), the product yield is only about 72.9% VOL, and the reduction range is huge.
Thus, it can be seen from the above comparative experiments that, for the solution of the present invention, the fine adjustment of the parameters and processes has a great influence on the yield and purity of the product. Therefore, the strict control of the parameters of the preparation process is the key to realizing the technical effect of the invention.
Claims (6)
1. A method for preparing hexafluorobutadiene is characterized in that,
the method comprises the following steps:
1) Placing a liquid chlorotrifluoroethylene raw material at the bottom of a reaction kettle, sequentially controlling the pressure in the reaction kettle to be increased to 0.6-0.8 MPa and the temperature to be increased to 42-45 ℃, guiding the liquid chlorotrifluoroethylene raw material into the reaction kettle to perform thermal polymerization reaction, condensing and recovering a thermal polymerization product, mixing the thermal polymerization product into the raw material until the raw material and/or the thermal polymerization product are not boiled again, and stopping recovering to obtain a precursor;
2) Placing the precursor in a boiling water bath in a waterproof way, controlling the pressure in a container in which the precursor is positioned to be 0.5-0.7 MPa, fractionating the precursor in the water bath to obtain an intermediate with a low boiling point, and recovering a residual liquid for later use until the volume of the precursor is not reduced;
the intermediate component is 1,2-dichlorohexafluorocyclobutane, and the residual liquid component is 3,4-dichloro-hexafluoro-1-butene;
3) Adding the intermediate into ethanol, adding simple substance zinc as a catalyst, collecting a gas product after reflux reaction, mixing the gas product with hydrogen iodide gas, performing high-temperature ring opening reaction at 285-295 ℃, and condensing and recycling to obtain a condensate;
4) Mixing the condensate with the residual liquid obtained in the step 2), reacting with chlorine water under photocatalysis, adding the mixture into butyl carbitol, adding simple substance zinc serving as a catalyst, heating for reaction, condensing and refluxing to remove impurities, and preheating a gas product to 665-670 ℃ through a porous solid catalyst to obtain hexafluorobutadiene;
the porous solid catalyst is composed of activated carbon, potassium fluoride and calcium fluoride;
the molar ratio of the potassium fluoride to the calcium fluoride is 1: (0.95-1.05), and the activated carbon accounts for 50-65 wt% of the total mass of the porous solid catalyst.
2. The process according to claim 1, wherein the reaction mixture is a mixture of at least two of the above-mentioned monomers,
the reaction temperature of the thermal polymerization reaction in the step 1) is 575-580 ℃, and the reaction time is 10-12 s.
3. The process according to claim 1, wherein the reaction mixture is a mixture of at least two of the above-mentioned monomers,
mixing the gas product obtained in the step 3) with hydrogen iodide gas, and carrying out high-temperature catalytic reaction on the mixture to obtain 22-26 h.
4. The method of producing hexafluorobutadiene according to claim 1,
step 4) the illumination reaction is carried out to be more than or equal to 24 h;
the light reaction is carried out under the irradiation of UV light.
5. The process according to claim 1, wherein the reaction mixture is a mixture of at least two of the above-mentioned monomers,
and 4) controlling the heating reaction temperature to be 145-150 ℃, wherein the reaction time is 6-8 h.
6. The process according to claim 1, wherein the reaction mixture is a mixture of at least two of the above-mentioned monomers,
the porous solid catalyst is prepared by uniformly mixing active carbon, potassium fluoride and calcium fluoride, filling the mixture into a tubular container, and controlling the flow rate of a gas product to enable the gas product to pass through the tubular container in 12-14 s.
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| CN202210845020.3A CN115259993B (en) | 2022-07-19 | 2022-07-19 | Preparation method of hexafluorobutadiene |
| PCT/CN2022/116782 WO2024016438A1 (en) | 2022-07-19 | 2022-09-02 | Preparation method for hexafluorobutadiene |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2668182A (en) * | 1950-07-13 | 1954-02-02 | William T Miller | Polyunsaturated fluoroolefins |
| GB839756A (en) * | 1955-07-01 | 1960-06-29 | Robert Neville Haszeldine | Improvements in or relating to the preparation of 1,2,3,4-tetrahydroperfluorobutane and perfluorobutadiene |
| JP3840553B2 (en) * | 1993-08-27 | 2006-11-01 | ダイキン工業株式会社 | Process for producing (Z) -1,2,3,3,4,4-hexafluorocyclobutane |
| RU2264376C1 (en) * | 2004-06-15 | 2005-11-20 | Закрытое акционерное общество АСТОР ЭЛЕКТРОНИКС | Method for preparing hexafluorobutadiene and 1,2-dichlorohexafluorocyclobutane |
| CN104496748A (en) * | 2014-12-29 | 2015-04-08 | 上海三爱富新材料股份有限公司 | Method for preparing 3,4-dichlorohexafluoro-1-butene |
| CN113061074B (en) * | 2021-03-01 | 2022-11-25 | 上海化工研究院有限公司 | Preparation method of hexafluorobutadiene |
| CN114539021B (en) * | 2022-02-24 | 2024-02-02 | 福建省建阳金石氟业有限公司 | Production process of hexafluorobutadiene |
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