CN107445794B - Method for preparing halogenated five-membered cyclic olefin by gas phase isomerization reaction - Google Patents

Method for preparing halogenated five-membered cyclic olefin by gas phase isomerization reaction Download PDF

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CN107445794B
CN107445794B CN201710672426.5A CN201710672426A CN107445794B CN 107445794 B CN107445794 B CN 107445794B CN 201710672426 A CN201710672426 A CN 201710672426A CN 107445794 B CN107445794 B CN 107445794B
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hexafluorocyclopentene
fluoride
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trichloropentafluorocyclopentene
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CN107445794A (en
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张呈平
贾晓卿
权恒道
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Beijing Yuji Science and Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/35—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction
    • C07C17/358—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction by isomerisation
    • 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
    • B01J27/125—Halogens; Compounds thereof with scandium, yttrium, aluminium, gallium, indium or thallium
    • 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
    • B01J27/128—Halogens; Compounds thereof with iron group metals or platinum group metals
    • 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
    • B01J27/132—Halogens; Compounds thereof with chromium, molybdenum, tungsten or polonium
    • 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
    • B01J27/138—Halogens; Compounds thereof with alkaline earth metals, magnesium, beryllium, zinc, cadmium or mercury

Abstract

The invention relates to a method for preparing halogenated five-membered cyclic olefin by gas phase isomerization reaction, which uses halogenated five-membered cyclic olefin C5HxFyClzThe method comprises the following steps of taking the raw material as a raw material, carrying out gas phase isomerization reaction in the presence of an isomerization catalyst to obtain an isomer of halogenated five-membered cyclic olefin, wherein X is an integer of 0-2, Y is an integer of 4-7, Z is an integer of 0-4, and X + Y + Z is 8, and the isomerization catalyst takes at least one of lithium fluoride, potassium fluoride, sodium fluoride, rubidium fluoride or cesium fluoride as an active component and is loaded on at least one carrier of aluminum fluoride, magnesium fluoride, iron fluoride, chromium fluoride and zinc fluoride. The method has the advantages of easily obtained raw materials, cheap isomerization catalyst and higher yield of isomers, and is suitable for preparing the isomers of the halogenated five-membered cyclic olefin by large-scale gas phase reaction.

Description

Method for preparing halogenated five-membered cyclic olefin by gas phase isomerization reaction
Technical Field
The invention relates to a method for preparing halogenated five-membered cyclic olefin through gas phase isomerization reaction, in particular to a method for preparing an isomer of halogenated five-membered cyclic olefin through isomerization reaction of halogenated five-membered cyclic olefin under the catalysis of an isomerization catalyst.
Background
Halogenated five-membered cycloolefins are a very important class of chemical raw materials or intermediates. For example, 1, 2-dichlorohexafluorocyclopentene, hexachlorocyclopentadiene and the like are important fluorine-containing blocks. Therefore, the synthesis of halogenated five-membered cycloolefins has been one of the research focuses in the field of fluorine chemistry.
Literature [ chemische borichte; vol.117; nb.3; (1984) (ii) a p.1153-1160] reports that 1,2,3,4, 5-pentachloropentafluoropentane is used as a raw material and reacts with Na-Ag-Hg alloy to obtain three isomers of trichloropentafluorocyclopentene, namely (3S,4S,5R) -3,4, 5-trichloropentafluorocyclopentene, (3S,4R,5R) -3,4, 5-trichloropentafluorocyclopentene, (3R,5R) -3,4, 5-trichloropentafluorocyclopentene, and the total yield of the three isomers is 8%.
Literature [ j.gen.chem.ussr (engl.transl.); vol.59; nb.3.2; (1989) (ii) a p.622-630,551-558 reports that 1, 4-dichloro-2, 5-difluorocyclohexane is used as a raw material, the reaction temperature is 600 ℃, the contact time is 3.8 seconds, and three isomers of trichloropentafluorocyclopentene, namely (3S,4S,5R) -3,4, 5-trichloropentafluorocyclopentene, (3S,4R,5R) -3,4, 5-trichloropentafluorocyclopentene, (3R,5R) -3,4, 5-trichloropentafluorocyclopentene, are obtained by pyrolysis, and the total yield of the three isomers is 8.7%.
Literature [ chemische borichte; vol.117; nb.3; (1984) (ii) a p.1153-1160] reports that hexachlorocyclopentadiene as a raw material, chloroform as a solvent, xenon difluoride and fluorine gas react to obtain four isomers of (3R, 4R/S) -1,2,3,4,5, 5-hexachloro-3, 4-difluorocyclopentene and (4S,5R/S) -1,2,3,3,4, 5-hexachloro-4, 5-difluorocyclopentene.
Japanese patent JP2001247493A reports that a mixture of 1, 2-dichlorohexafluorocyclopentene, trichloropentafluorocyclopentene and tetrachlorotetrafluorocyclopentene is subjected to a liquid-phase fluorine-chlorine exchange reaction with potassium fluoride in a mixed solvent of dimethyldimethylamide and toluene to obtain 1-chloroheptafluorocyclopentene as a main product and a mixture of two isomers of 1, 3-dichlorohexafluorocyclopentene and 1, 4-dichlorohexafluorocyclopentene as by-products at a yield of up to 17.2%.
Patent ZL201510694890.5 reports the isomerization of chlorofluoro cyclopentene in the solvent dimethylformamide, dimethylsulfoxide or sulfolane in the presence of catalysts ammonium fluoride, ammonium bifluoride, potassium fluoride, lithium fluoride, sodium fluoride, rubidium fluoride or cesium fluoride to give isomers of chlorofluoro cyclopentene.
The above method has the following disadvantages: (1) the technology for preparing trichloro-pentafluorocyclopentene isomer is too harsh, Na-Ag-Hg alloy which is difficult to control and has high toxicity is adopted, or high-temperature (600 ℃) pyrolysis is adopted, or a fluoridation reagent xenon difluoride is too expensive; (2) the yield of the chloro-fluoro cyclopentene isomer is low, and is mostly about 10%; (3) most reaction routes adopt liquid phase reaction, use a large amount of organic solvents and metal fluorides, are difficult to recover and are easy to cause serious environmental pollution; in addition, no literature reports on the preparation of halogenated five-membered cycloolefins by gas phase isomerization.
Disclosure of Invention
The technical problem to be solved by the invention is to solve the defects in the background technology and provide a method which not only has easily obtained raw materials, cheap and easily recycled catalyst, but also has higher yield of isomers and is suitable for preparing halogenated five-membered ring olefin isomers by large-scale gas phase reaction.
A process for preparing halogenated penta-cyclic olefins by gas phase isomerization, which comprises the steps of:
with halogenated five-membered cyclic olefins C5HxFyClzThe method comprises the following steps of taking the raw material as a raw material, carrying out gas phase isomerization reaction in the presence of an isomerization catalyst to obtain an isomer of halogenated five-membered cyclic olefin, wherein X is an integer of 0-2, Y is an integer of 4-7, Z is an integer of 0-4, and X + Y + Z is 8, and the isomerization catalyst takes at least one of lithium fluoride, potassium fluoride, sodium fluoride, rubidium fluoride or cesium fluoride as an active component and is loaded on at least one carrier of aluminum fluoride, magnesium fluoride, iron fluoride, chromium fluoride and zinc fluoride.
The mass percentage of the active component to the carrier is 0-10%: 90 to 100 percent.
The preparation method of the isomerization catalyst comprises the following steps: (1) dissolving carrier metal soluble salt in water, dropwise adding concentrated ammonia water for precipitation, adjusting the pH value to 7.0-7.5, then aging for 10-15 hours, washing with water, filtering, drying in an oven at 70-100 ℃ for 12-48 hours, and then roasting at 300-500 ℃ for 5-20 hours under the protection of nitrogen to obtain carrier metal oxide which is a precursor of a metal fluoride carrier; (2) according to the percentage composition of active component alkali metal fluoride and carrier metal fluoride, at 40-50 deg.C, adopting impregnation method to impregnate and load active component alkali metal fluoride on carrier metal oxide, filtering, drying at 70-100 deg.C for 5-48 hr, pulverizing obtained solid, tabletting and forming to obtain catalyst precursor; (3) loading the catalyst precursor into a tubular reactor, introducing nitrogen, roasting at 500 ℃ for 5-20 hours at the nitrogen airspeed of 200h-1And then, at the temperature of 200-400 ℃, introducing a material with the mass ratio of 1: 2, the total space velocity of the gas is 220h-1And activating for 5-20 hours, and stopping the mixed gas to prepare the isomerization catalyst.
The preparation method of the isomerization catalyst comprises the following steps: (1) dissolving the carrier metal in a saltDissolving in water, dropwise adding concentrated ammonia water for precipitation, adjusting the pH value to 7.5, then aging for 12 hours, washing with water, filtering, drying in an oven at 80 ℃ for 36 hours, and then roasting at 450 ℃ for 8 hours under the protection of nitrogen to obtain a carrier metal oxide which is a precursor of a metal fluoride carrier; (2) according to the percentage composition of active component alkali metal fluoride and carrier metal fluoride, at 50 deg.C, adopting impregnation method to impregnate and load active component alkali metal fluoride on carrier metal oxide, filtering, drying at 80 deg.C for 12 hr, pulverizing obtained solid, tabletting and forming to obtain catalyst precursor; (3) loading the catalyst precursor into a tubular reactor, introducing nitrogen, roasting at 450 ℃ for 8 hours, wherein the space velocity of the nitrogen is 200h-1Then, the temperature is reduced to 300 ℃, and simultaneously the mass ratio of the introduced substances is 1: 2, the total space velocity of the gas is 220h-1And activating for 12 hours, and stopping the mixed gas to prepare the isomerization catalyst.
The carrier metal soluble salt is a chloride or nitrate of a metal.
The halogenated five-membered cyclic olefin is 1, 4-dichlorohexafluorocyclopentene (F6-14), 1, 3-dichlorohexafluorocyclopentene (F6-13), 1,4, 4-trichloropentafluorocyclopentene (F5-144), 1,3, 3-trichloropentafluorocyclopentene (F5-133), 1,2, 4-trichloropentafluorocyclopentene (F5-124), 1,2, 3-trichloropentafluorocyclopentene (F5-123), 1,2,3, 3-tetrachlorotetrafluorocyclopentene (F4-1233), 1,2,4, 4-tetrachlorotetrafluorocyclopentene (F4-1244), 1H-3-chlorohexafluorocyclopentene (F6E-3Cl), 1H-4-chlorohexafluorocyclopentene (F6E-3Cl), 4H-heptafluorocyclopentene (F7E-4H), 3H-heptafluorocyclopentene (F7E-3H), 4H-hexafluorocyclopentene (F6E-44H), 3H-hexafluorocyclopentene (F6E-33H), 1H, 5H-hexafluorocyclopentene (F6E-15H), 1H, 4H-hexafluorocyclopentene (F6E-14H), 1H, 3H-hexafluorocyclopentene (F6E-13H).
The reaction conditions are as follows: the reaction pressure is 0.1MPa-0.5MPa, the reaction temperature is 50-400 ℃, and the contact time is 0.5-50 s;
the reaction conditions are as follows: the reaction pressure is 0.1MPa-0.5MPa, the reaction temperature is 150-300 ℃, and the contact time is 5-25 s;
preparing 1, 3-dichlorohexafluorocyclopentene and 1, 2-dichlorohexafluorocyclopentene (F6-12) by using the raw material 1, 4-dichlorohexafluorocyclopentene;
or 1, 3-dichlorohexafluorocyclopentene as a raw material to prepare 1, 4-dichlorohexafluorocyclopentene and 1, 2-dichlorohexafluorocyclopentene;
or 1,4, 4-trichloropentafluorocyclopentene as a raw material to prepare 1,3, 3-trichloropentafluorocyclopentene, 1,2, 3-trichloropentafluorocyclopentene and 1,2, 4-trichloropentafluorocyclopentene;
or 1,3, 3-trichloropentafluorocyclopentene as a raw material to prepare 1,4, 4-trichloropentafluorocyclopentene, 1,2, 3-trichloropentafluorocyclopentene and 1,2, 4-trichloropentafluorocyclopentene;
or preparing 1,2, 3-trichloropentafluorocyclopentene from the raw material 1,2, 4-trichloropentafluorocyclopentene;
or preparing 1,2, 4-trichloropentafluorocyclopentene from the raw material 1,2, 3-trichloropentafluorocyclopentene;
or 1,2,3, 3-tetrachloro-tetrafluorocyclopentene is used as a raw material to prepare 1,2,4, 4-tetrachloro-tetrafluorocyclopentene;
or 1,2,4, 4-tetrachloro-tetrafluorocyclopentene is used as a raw material to prepare 1,2,3, 3-tetrachloro-tetrafluorocyclopentene;
or 1H-3-chlorohexafluorocyclopentene as a raw material to prepare 1H-4-chlorohexafluorocyclopentene and 1H-2-chlorohexafluorocyclopentene (F6E-2 Cl);
or 1H-4-chloro-hexafluorocyclopentene as a raw material to prepare 1H-3-chloro-hexafluorocyclopentene and 1H-2-chloro-hexafluorocyclopentene;
or 4H-heptafluorocyclopentene as a raw material to prepare 3H-heptafluorocyclopentene and 1H-heptafluorocyclopentene (F7E-1H);
or 3H-heptafluorocyclopentene as a raw material to prepare 4H-heptafluorocyclopentene and 1H-heptafluorocyclopentene;
or 4H, 4H-hexafluorocyclopentene as a raw material to prepare 3H, 3H-hexafluorocyclopentene, 1H, 5H-hexafluorocyclopentene, 1H, 4H-hexafluorocyclopentene, 1H, 3H-hexafluorocyclopentene and 1H, 2H-hexafluorocyclopentene (F6E-12H);
or 3H, 3H-hexafluorocyclopentene as a raw material to prepare 4H, 4H-hexafluorocyclopentene, 1H, 5H-hexafluorocyclopentene, 1H, 4H-hexafluorocyclopentene, 1H, 3H-hexafluorocyclopentene and 1H, 2H-hexafluorocyclopentene;
or 1H, 4H-hexafluorocyclopentene is used as a raw material to prepare 1H, 3H-hexafluorocyclopentene and 1H, 2H-hexafluorocyclopentene; or 1H, 3H-hexafluorocyclopentene is used as a raw material to prepare 1H, 4H-hexafluorocyclopentene and 1H, 2H-hexafluorocyclopentene;
or 1H, 5H-hexafluorocyclopentene as a raw material to prepare 1H, 2H-hexafluorocyclopentene.
The isomerization reaction of the invention takes the halogenated five-membered cyclic olefin as the raw material, and the isomer of the halogenated five-membered cyclic olefin is obtained through gas phase isomerization reaction. The main reaction is as follows:
Figure BDA0001373459290000041
Figure BDA0001373459290000051
Figure BDA0001373459290000061
the invention can be carried out at normal pressure or under elevated pressure. Since the reaction is a gas phase reaction involving a gas phase raw material or product, pressurization greatly affects the reaction involved in the present invention. Therefore, the preferred pressure for the present invention is from 0.1MPa to 0.5 MPa.
The invention can be carried out in a reactor made of stainless steel 316 or Incan alloy.
The invention provides a preparation method of isomers capable of co-producing halogenated five-membered cycloolefins, wherein dichlorohexafluorocyclopentene isomers comprise 1, 2-dichlorohexafluorocyclopentene, 1, 3-dichlorohexafluorocyclopentene and 1, 4-dichlorohexafluorocyclopentene. The trichloropentafluorocyclopentene isomers include 1,2, 4-trichloropentafluorocyclopentene, 1,2, 3-trichloropentafluorocyclopentene, 1,3, 3-trichloropentafluorocyclopentene and 1,4, 4-trichloropentafluorocyclopentene. Isomers of tetrachlorotetrafluorocyclopentene include 1,2,4, 4-tetrachlorotetrafluorocyclopentene, 1,2,3, 3-tetrachlorotetrafluorocyclopentene. The isomers of chlorohexafluorocyclopentene include 1H-3-chlorohexafluorocyclopentene, 1H-4-chlorohexafluorocyclopentene and 1H-2-chlorohexafluorocyclopentene. The heptafluorocyclopentene includes 4H-heptafluorocyclopentene, 3H-heptafluorocyclopentene and 1H-heptafluorocyclopentene. The hexafluorocyclopentene includes 4H, 4H-hexafluorocyclopentene, 3H-hexafluorocyclopentene, 1H, 5H-hexafluorocyclopentene, 1H, 4H-hexafluorocyclopentene, 1H, 3H-hexafluorocyclopentene and 1H, 2H-hexafluorocyclopentene. Only the isomerization product of the halogenated five-membered cyclic olefin needs to be refined, and the corresponding product can be obtained: the boiling point of the 1, 4-dichlorohexachlorocyclopentene is 80-84 ℃ (760mmHg), the boiling point of the 1, 3-dichlorohexachlorocyclopentene is 86-88 ℃ (760mmHg), the boiling point of the 1, 2-dichlorohexafluorocyclopentene is 90-91 ℃ (760mmHg), the boiling point of the 1,4, 4-trichloropentachlorocyclopentene is 109-113 ℃ (760mmHg), the boiling point of the 1,3, 3-trichloropentachlorocyclopentene is 115-117 ℃ (760mmHg), the boiling point of the 1,2, 4-trichloropentachlorocyclopentene is 123-124 ℃ (760mmHg), the boiling point of the 1,2, 3-trichloropentachlorocyclopentene is 129-130 ℃ (760mmHg), the boiling point of the 1,2,4, 4-tetrachlorocyclopentene is 154-156 ℃ (760mmHg), the boiling point of the 1,2,3, 3-tetrachlorocyclopentene is 148-152 ℃ (760), the boiling point of the 1H-3-chlorohexafluorocyclopentene is 77-84 ℃ (760mmHg), the boiling point of the 1H-4-chlorohexafluorocyclopentene is 68-70 ℃ (760mmHg), the boiling point of the 1H-2-chlorohexafluorocyclopentene is 73-74 ℃ (760mmHg), the boiling point of the 4H-heptafluorocyclopente is 42-44 ℃ (760mmHg), the boiling point of the 3H-heptafluorocyclopente is 51 ℃ (760mmHg), the boiling point of the 1H-heptafluorocyclopente is 46 ℃ (760mmHg), the boiling point of the 4H, 4H-hexafluorocyclopentene is 48-55 ℃ (760mmHg), the boiling point of the 3H, 3H-hexafluorocyclopentene is 58-63 ℃ (760mmHg), the boiling point of the 1H, 5H-hexafluorocyclopentene is 74 ℃ (760mmHg), the boiling point of the 1H, 4H-hexafluorocyclopentene is 66 ℃ (760mmHg), the boiling point of the 1, the boiling point of 1H, 2H-hexafluorocyclopentene was 70 deg.C (760 mmHg).
The invention has the advantages that: the technical method provided by the invention can be used for co-producing the isomers of the halogenated five-membered cyclic olefin, and the raw materials are easy to obtain, the isomerization catalyst is cheap, and the method is suitable for preparing the isomers of the halogenated five-membered cyclic olefin through large-scale liquid phase isomerization.
Detailed Description
An analytical instrument: shimadzu GC-2010, column DB-VRX caliper column (i.d.0.32mm; length 30 m; J & W Scientific Inc.).
GC analysis method: and washing, alkali washing and drying the reaction product, and then taking a gas sample for GC analysis. The temperature of the detector is 250 ℃, the temperature of the vaporization chamber is 250 ℃, the initial temperature of the column is 40 ℃, the temperature is kept for 10 minutes, the temperature is increased to 230 ℃ at the speed of 15 ℃/min, and the temperature is kept for 8 minutes.
The present invention will be described in further detail with reference to the following examples, which are not intended to limit the scope of the present invention.
Preparation of isomerization catalyst: dissolving metal soluble salt in water, dropwise adding concentrated ammonia water for precipitation, adjusting the pH value to 7.5, then aging for 12 hours, washing with water, filtering, drying in an oven at 80 ℃ for 36 hours, and then roasting at 450 ℃ for 8 hours under the protection of nitrogen to obtain metal oxide which is a precursor of a metal fluoride carrier. According to the percentage composition of 0-10% and 10% -90% of alkali metal fluoride and metal fluoride carrier, at 50 deg.C, adopting impregnation method to impregnate alkali metal fluoride on metal oxide, filtering, drying at 80 deg.C for 12 hr, pulverizing obtained solid, tabletting and forming to obtain catalyst precursor, placing 10mL of catalyst precursor into tubular reactor made of Monel material whose internal diameter is 1/2 inch and length is 30cm, introducing nitrogen gas and roasting at 450 deg.C for 8 hr, and its nitrogen gas space velocity is 200 hr-1Then, the temperature is reduced to 300 ℃, and simultaneously the mass ratio of the introduced substances is 1: 2, the total space velocity of the gas is 220h-1And activating for 12 hours, and stopping the mixed gas to prepare the isomerization catalyst. In the above method, the metal-soluble salt may be a chloride or nitrate of the metal. An isomerization catalyst in which an alkali metal fluoride is supported on a catalyst carrier such as aluminum fluoride, magnesium fluoride, iron fluoride, chromium fluoride, zinc fluoride, etc., can be prepared according to the above method, wherein the composition of the isomerization catalyst used in examples 1 to 18 is shown in table 1:
examples Isomerization catalyst Isomerization catalyst composition
1 100％CrF3 100％CrF3
2 5％CsF/CrF3 5％CsF、95％CrF3
3 10％CsF/CrF3 10％CsF、90％CrF3
4 5％LiF/CrF3 5％LiF、95％CrF3
5 5％NaF/CrF3 5％NaF、95％CrF3
6 5％KF/CrF3 5％KF、95％CrF3
7 5％RbF/CrF3 5％RbF、95％CrF3
8 100％FeF3 100％FeF3
9 100％AlF3 100％AlF3
10 100％MgF2 100％MgF2
11 100％ZnF2 100％ZnF2
12 5％RbF/AlF3 5％RbF、95％AlF3
13 5％CsF/AlF3 5％CsF、95％AlF3
14 5％CsF/FeF3 5％CsF、95％FeF3
15 5％CsF/MgF2 5％CsF、95％MgF2
16 5％CsF/ZnF2 5％CsF、95％ZnF2
17 5％LiF/AlF3 5％LiF、95％AlF3
18 5％NaF/AlF3 5％NaF、95％AlF3
Example 1
A tubular reactor of Incan alloy having an inner diameter of 1/2 inches and a length of 30cm was charged with 10ml of the 100% CrF isomerization catalyst prepared by the above method3. The reaction conditions are as follows: the temperature of the reaction is increased to 120 ℃, the contact time of the 1, 4-dichlorohexachlorocyclopentene is 5s, and the reaction pressure is 0.1 MPa. After the reaction is carried out for 100 hours, washing and separating the reaction product to obtain organic matters, drying and dewatering, and analyzing the composition of the organic matters by using gas chromatography, wherein the reaction result is as follows: the conversion of 1, 4-dichlorohexafluorocyclopentene was 75.0%, the selectivity for 1, 3-dichlorohexafluorocyclopentene was 63.4%, and the selectivity for 1, 2-dichlorohexafluorocyclopentene was 36.6%.
And (3) rectifying the organic phase to obtain isomers of the dichlorohexafluorocyclopentene, namely the 1, 4-dichlorohexachlorocyclopentene with the boiling point of 80-84 ℃ (760mmHg), the 1, 3-dichlorohexachlorocyclopentene with the boiling point of 86-88 ℃ (760mmHg), and the 1, 2-dichlorohexafluorocyclopentene with the boiling point of 90-91 ℃ (760 mmHg).
Example 2
10ml of the isomerization catalyst 5% CsF/CrF prepared by the above method was charged in a tubular reactor made of Incar having an inner diameter of 1/2 inches and a length of 30cm3. The reaction conditions are as follows: the temperature of the reaction is raised to 400 ℃, the contact time of the 1, 4-dichlorohexachlorocyclopentene is 5s, and the reaction pressure is 0.1 MPa. After the reaction is carried out for 100 hours, washing and separating the reaction product to obtain organic matters, drying and dewatering, and analyzing the composition of the organic matters by using gas chromatography, wherein the reaction result is as follows: the conversion of 1, 4-dichlorohexafluorocyclopentene was 100%, the selectivity for 1, 3-dichlorohexafluorocyclopentene was 0.7%, and the selectivity for 1, 2-dichlorohexafluorocyclopentene was 99.3%.
And (3) rectifying the organic phase to obtain an isomer of the dichlorohexafluorocyclopentene, namely the 1, 2-dichlorohexafluorocyclopentene, with a boiling point of 90-91 ℃ (760 mmHg).
Example 3
10ml of the isomerization catalyst 10% CsF/CrF prepared by the above method was charged in a tubular reactor made of Incar having an inner diameter of 1/2 inches and a length of 30cm3. The reaction conditions are as follows: the temperature of the reaction is increased to 300 ℃, the contact time of the 1, 3-dichlorohexachlorocyclopentene is 5s, and the reaction pressure is 0.1 MPa. After the reaction is carried out for 100 hours, washing and separating the reaction product to obtain organic matters, drying and dewatering, and analyzing the composition of the organic matters by using gas chromatography, wherein the reaction result is as follows: the conversion of 1, 3-dichlorohexafluorocyclopentene was 89.2%, the selectivity for 1, 4-dichlorohexafluorocyclopentene was 25.4%, and the selectivity for 1, 2-dichlorohexafluorocyclopentene was 74.6%.
And (3) rectifying the organic phase to obtain isomers of the dichlorohexafluorocyclopentene, namely the 1, 4-dichlorohexachlorocyclopentene with the boiling point of 80-84 ℃ (760mmHg), the 1, 3-dichlorohexachlorocyclopentene with the boiling point of 86-88 ℃ (760mmHg), and the 1, 2-dichlorohexafluorocyclopentene with the boiling point of 90-91 ℃ (760 mmHg).
Example 4
10ml of the isomerization catalyst prepared by the above method, 5% LiF/CrF, was charged in a tubular reactor made of Incan alloy having an inner diameter of 1/2 inches and a length of 30cm3. The reaction conditions are as follows: the temperature of the reaction is increased to 300 ℃, the contact time of the 1,4, 4-trichloro-pentafluorocyclopentene is 5s, and the reaction pressure is 0.1 MPa. After the reaction is carried out for 100 hours, washing and separating the reaction product to obtain organic matters, drying and dewatering, and analyzing the composition of the organic matters by using gas chromatography, wherein the reaction result is as follows: the conversion of 1,4, 4-trichloropentafluorocyclopentene was 91.0%, the selectivity for 1,3, 3-trichloropentafluorocyclopentene was 68.2%, the selectivity for 1,2, 4-trichloropentafluorocyclopentene was 25.6%, and the selectivity for 1,2, 3-trichloropentafluorocyclopentene was 6.2%.
The organic phase is rectified to obtain the isomers of the trichloropentafluorocyclopentene, namely, the boiling point of the 1,4, 4-trichloropentafluorocyclopentene is 109-113 ℃ (760mmHg), the boiling point of the 1,3, 3-trichloropentafluorocyclopentene is 115-117 ℃ (760mmHg), the boiling point of the 1,2, 4-trichloropentafluorocyclopentene is 123-124 ℃ (760mmHg), and the boiling point of the 1,2, 3-trichloropentafluorocyclopentene is 129-130 ℃ (760 mmHg).
Example 5
A tubular reactor of 30cm length having an inner diameter of 1/2 inches and made of Incar was charged with 10ml of the isomerization catalyst 5% NaF/CrF prepared by the above method3. The reaction conditions are as follows: the temperature of the reaction is increased to 300 ℃, the contact time of the 1,3, 3-trichloro-pentafluorocyclopentene is 5s, and the reaction pressure is 0.1 MPa. After the reaction is carried out for 100 hours, washing and separating the reaction product to obtain organic matters, drying and dewatering, and analyzing the composition of the organic matters by using gas chromatography, wherein the reaction result is as follows: the conversion of 1,3, 3-trichloropentafluorocyclopentene was 37.5%, the selectivity for 1,4, 4-trichloropentafluorocyclopentene was 26.2%, the selectivity for 1,2, 4-trichloropentafluorocyclopentene was 61.2%, and the selectivity for 1,2, 3-trichloropentafluorocyclopentene was 12.6%.
The organic phase is rectified to obtain the isomers of the trichloropentafluorocyclopentene, namely, the boiling point of the 1,4, 4-trichloropentafluorocyclopentene is 109-113 ℃ (760mmHg), the boiling point of the 1,3, 3-trichloropentafluorocyclopentene is 115-117 ℃ (760mmHg), the boiling point of the 1,2, 4-trichloropentafluorocyclopentene is 123-124 ℃ (760mmHg), and the boiling point of the 1,2, 3-trichloropentafluorocyclopentene is 129-130 ℃ (760 mmHg).
Example 6
A tubular reactor having an inner diameter of 1/2 inches and a length of 30cm and made of Incar was charged with 10ml of the isomerization catalyst 5% KF/CrF prepared by the above method3. The reaction conditions are as follows: the temperature of the reaction is raised to 370 ℃, the contact time of the 1,2, 3-trichloro-pentafluorocyclopentene is 5s, and the reaction pressure is 0.1 MPa. After the reaction is carried out for 100 hours, washing and separating the reaction product to obtain organic matters, drying and dewatering, and analyzing the composition of the organic matters by using gas chromatography, wherein the reaction result is as follows: the conversion rate of the 1,2, 3-trichloropentafluorocyclopentene was 98.5%, and the selectivity of the 1,2, 4-trichloropentafluorocyclopentene was 100%.
The organic phase is rectified to obtain the isomers of trichloropentafluorocyclopentene, namely, 1,2, 4-trichloropentafluorocyclopentene with a boiling point of 123-.
Example 7
A tubular reactor of 30cm length having an inner diameter of 1/2 inches was charged with 10ml of a solutionThe isomerization catalyst prepared by the method is 5 percent RbF/CrF3. The reaction conditions are as follows: the temperature of the reaction is raised to 150 ℃, the contact time of the 1,2, 4-trichloropentafluorocyclopentene is 5s, and the reaction pressure is 0.1 MPa. After the reaction is carried out for 100 hours, washing and separating the reaction product to obtain organic matters, drying and dewatering, and analyzing the composition of the organic matters by using gas chromatography, wherein the reaction result is as follows: the conversion rate of the 1,2, 4-trichloropentafluorocyclopentene was 91.8%, and the selectivity of the 1,2, 3-trichloropentafluorocyclopentene was 100%.
The organic phase is rectified to obtain the isomers of trichloropentafluorocyclopentene, namely, 1,2, 4-trichloropentafluorocyclopentene with a boiling point of 123-.
Example 8
A tubular reactor of Incan alloy having an inner diameter of 1/2 inches and a length of 30cm was charged with 10ml of 100% FeF, which was the isomerization catalyst prepared by the above-mentioned method3. The reaction conditions are as follows: the temperature of the reaction is raised to 200 ℃, the contact time of the 1,2,4, 4-tetrachloro-tetrafluorocyclopentene is 5s, and the reaction pressure is 0.1 MPa. After the reaction is carried out for 100 hours, washing and separating the reaction product to obtain organic matters, drying and dewatering, and analyzing the composition of the organic matters by using gas chromatography, wherein the reaction result is as follows: the conversion of 1,2,4, 4-tetrachlorotetrafluorocyclopentene was 85.2%, and the selectivity of 1,2,3, 3-tetrachlorotetrafluorocyclopentene was 100%.
And (3) rectifying the organic phase to obtain isomers of the tetrachloro-tetrafluorocyclopentene, namely 1,2,4, 4-tetrachloro-tetrafluorocyclopentene with a boiling point of 154-156 ℃ (760mmHg) and 1,2,3, 3-tetrachloro-tetrafluorocyclopentene with a boiling point of 148-152 ℃ (760 mmHg).
Example 9
A tubular reactor of Incan alloy having an inner diameter of 1/2 inches and a length of 30cm was charged with 10ml of 100% AlF, which was the isomerization catalyst prepared by the above-mentioned method3. The reaction conditions are as follows: the temperature of the reaction is raised to 380 ℃, the contact time of the 1,2,3, 3-tetrachloro-tetrafluorocyclopentene is 5s, and the reaction pressure is 0.1 MPa. After the reaction is carried out for 100 hours, washing and separating the reaction product to obtain organic matters, drying and dewatering, and analyzing the composition of the organic matters by using gas chromatography, wherein the reaction result is as follows: the conversion rate of 1,2,3, 3-tetrachlorotetrafluorocyclopentene was 92.4%, and the selectivity of 1,2,4, 4-tetrachlorotetrafluorocyclopentene was 100％。
And (3) rectifying the organic phase to obtain isomers of the tetrachloro-tetrafluorocyclopentene, namely 1,2,4, 4-tetrachloro-tetrafluorocyclopentene with a boiling point of 154-156 ℃ (760mmHg) and 1,2,3, 3-tetrachloro-tetrafluorocyclopentene with a boiling point of 148-152 ℃ (760 mmHg).
Example 10
A tubular reactor of Incan alloy having an inner diameter of 1/2 inches and a length of 30cm was charged with 10ml of 100% MgF, which was the isomerization catalyst prepared by the above method2. The reaction conditions are as follows: the temperature of the reaction is raised to 320 ℃, the contact time of the 4H-heptafluorocyclopentene is 5s, and the reaction pressure is 0.1 MPa. After the reaction is carried out for 100 hours, washing and separating the reaction product to obtain organic matters, drying and dewatering, and analyzing the composition of the organic matters by using gas chromatography, wherein the reaction result is as follows: the conversion of 4H-heptafluorocyclopentene was 100%, the selectivity for 3H-heptafluorocyclopentene was 23.8%, and the selectivity for 1H-heptafluorocyclopentene was 76.2%.
The organic phase was subjected to rectification to obtain the isomers of heptafluorocyclopentene, 4H-heptafluorocyclopentene having a boiling point of 42 to 44 ℃ (760mmHg), 3H-heptafluorocyclopentene having a boiling point of 51 ℃ (760mmHg), and 1H-heptafluorocyclopentene having a boiling point of 46 ℃ (760 mmHg).
Example 11
A tubular reactor of 30cm length having an inner diameter of 1/2 inches was charged with 10ml of 100% ZnF isomerization catalyst prepared by the above method2. The reaction conditions are as follows: the temperature of the reaction is raised to 320 ℃, the contact time of the 3H-heptafluorocyclopentene is 5s, and the reaction pressure is 0.1 MPa. After the reaction is carried out for 100 hours, washing and separating the reaction product to obtain organic matters, drying and dewatering, and analyzing the composition of the organic matters by using gas chromatography, wherein the reaction result is as follows: the conversion of 3H-heptafluorocyclopentene was 75.6%, the selectivity for 4H-heptafluorocyclopentene was 4.2%, and the selectivity for 1H-heptafluorocyclopentene was 95.8%.
The organic phase was subjected to rectification to obtain the isomers of heptafluorocyclopentene, 4H-heptafluorocyclopentene having a boiling point of 42 to 44 ℃ (760mmHg), 3H-heptafluorocyclopentene having a boiling point of 51 ℃ (760mmHg), and 1H-heptafluorocyclopentene having a boiling point of 46 ℃ (760 mmHg).
Example 12
Made of inconel having an inner diameter of 1/2 inches and a length of 30cmThe tubular reactor was charged with 10ml of the isomerization catalyst prepared above 5% RbF/AlF3. The reaction conditions are as follows: the temperature of the reaction is increased to 300 ℃, the contact time of the 4H, 4H-hexafluorocyclopentene is 5s, and the reaction pressure is 0.1 MPa. After the reaction is carried out for 100 hours, washing and separating the reaction product to obtain organic matters, drying and dewatering, and analyzing the composition of the organic matters by using gas chromatography, wherein the reaction result is as follows: the conversion of 4H, 4H-hexafluorocyclopentene was 100%, the selectivity for 3H, 3H-hexafluorocyclopentene was 5.2%, the selectivity for 1H, 4H-hexafluorocyclopentene was 15.5%, the selectivity for 1H, 3H-hexafluorocyclopentene was 18.2%, the selectivity for 1H, 5H-hexafluorocyclopentene was 3.2%, and the selectivity for 1H, 2H-hexafluorocyclopentene was 57.9%.
The organic phase is rectified to obtain isomers of the hexafluorocyclopentene, namely, the boiling point of 4H, 4H-hexafluorocyclopentene is 48-55 ℃ (760mmHg), the boiling point of 3H, 3H-hexafluorocyclopentene is 58-63 ℃ (760mmHg), the boiling point of 1H, 5H-hexafluorocyclopentene is 74 ℃ (760mmHg), the boiling point of 1H, 4H-hexafluorocyclopentene is 66 ℃ (760mmHg), the boiling point of 1H, 3H-hexafluorocyclopentene is 68-69 ℃ (760mmHg), and the boiling point of 1H, 2H-hexafluorocyclopentene is 70 ℃ (760 mmHg).
Example 13
A tubular reactor having an inner diameter of 1/2 inches and a length of 30cm and made of Incar was charged with 10ml of the isomerization catalyst 5% CsF/AlF prepared by the above method3. The reaction conditions are as follows: the temperature of the reaction is increased to 300 ℃, the contact time of the 3H, 3H-hexafluorocyclopentene is 5s, and the reaction pressure is 0.1 MPa. After the reaction is carried out for 100 hours, washing and separating the reaction product to obtain organic matters, drying and dewatering, and analyzing the composition of the organic matters by using gas chromatography, wherein the reaction result is as follows: the conversion of 3H, 3H-hexafluorocyclopentene was 85.4%, the selectivity for 4H, 4H-hexafluorocyclopentene was 2.8%, the selectivity for 1H, 4H-hexafluorocyclopentene was 18.2%, the selectivity for 1H, 3H-hexafluorocyclopentene was 17.3%, the selectivity for 1H, 5H-hexafluorocyclopentene was 5.7%, and the selectivity for 1H, 2H-hexafluorocyclopentene was 56.0%.
The organic phase is rectified to obtain isomers of the hexafluorocyclopentene, namely, the boiling point of 4H, 4H-hexafluorocyclopentene is 48-55 ℃ (760mmHg), the boiling point of 3H, 3H-hexafluorocyclopentene is 58-63 ℃ (760mmHg), the boiling point of 1H, 5H-hexafluorocyclopentene is 74 ℃ (760mmHg), the boiling point of 1H, 4H-hexafluorocyclopentene is 66 ℃ (760mmHg), the boiling point of 1H, 3H-hexafluorocyclopentene is 68-69 ℃ (760mmHg), and the boiling point of 1H, 2H-hexafluorocyclopentene is 70 ℃ (760 mmHg).
Example 14
A tubular reactor having an inner diameter of 1/2 inches and a length of 30cm and made of Incar was charged with 10ml of the isomerization catalyst 5% CsF/FeF prepared by the above method3. The reaction conditions are as follows: the temperature of the reaction is increased to 300 ℃, the contact time of the 1H, 4H-hexafluorocyclopentene is 5s, and the reaction pressure is 0.1 MPa. After the reaction is carried out for 100 hours, washing and separating the reaction product to obtain organic matters, drying and dewatering, and analyzing the composition of the organic matters by using gas chromatography, wherein the reaction result is as follows: the conversion of 1H, 4H-hexafluorocyclopentene was 83.8%, the selectivity for 1H, 3H-hexafluorocyclopentene was 19.2%, the selectivity for 1H, 5H-hexafluorocyclopentene was 7.3%, and the selectivity for 1H, 2H-hexafluorocyclopentene was 73.5%.
The organic phase is rectified to obtain the isomers of the hexafluorocyclopentene, namely, the boiling point of 1H, 5H-hexafluorocyclopentene is 74 ℃ (760mmHg), the boiling point of 1H, 4H-hexafluorocyclopentene is 66 ℃ (760mmHg), the boiling point of 1H, 3H-hexafluorocyclopentene is 68-69 ℃ (760mmHg), and the boiling point of 1H, 2H-hexafluorocyclopentene is 70 ℃ (760 mmHg).
Example 15
10ml of the isomerization catalyst 5% CsF/MgF prepared by the above method was charged in a tubular reactor made of Incar having an inner diameter of 1/2 inches and a length of 30cm2. The reaction conditions are as follows: the temperature of the reaction is increased to 300 ℃, the contact time of the 1H, 3H-hexafluorocyclopentene is 5s, and the reaction pressure is 0.1 MPa. After the reaction is carried out for 100 hours, washing and separating the reaction product to obtain organic matters, drying and dewatering, and analyzing the composition of the organic matters by using gas chromatography, wherein the reaction result is as follows: the conversion of 1H, 3H-hexafluorocyclopentene was 86.7%, the selectivity for 1H, 4H-hexafluorocyclopentene was 20.3%, the selectivity for 1H, 5H-hexafluorocyclopentene was 8.2%, and the selectivity for 1H, 2H-hexafluorocyclopentene was 71.5%.
The organic phase is rectified to obtain the isomers of the hexafluorocyclopentene, namely, the boiling point of 1H, 5H-hexafluorocyclopentene is 74 ℃ (760mmHg), the boiling point of 1H, 4H-hexafluorocyclopentene is 66 ℃ (760mmHg), the boiling point of 1H, 3H-hexafluorocyclopentene is 68-69 ℃ (760mmHg), and the boiling point of 1H, 2H-hexafluorocyclopentene is 70 ℃ (760 mmHg).
Example 16
A tubular reactor having an inner diameter of 1/2 inches and a length of 30cm and made of Incar was charged with 10ml of the above-prepared isomerization catalyst 5% CsF/ZnF3. The reaction conditions are as follows: the temperature of the reaction is increased to 300 ℃, the contact time of the 1H, 5H-hexafluorocyclopentene is 5s, and the reaction pressure is 0.1 MPa. After the reaction is carried out for 100 hours, washing and separating the reaction product to obtain organic matters, drying and dewatering, and analyzing the composition of the organic matters by using gas chromatography, wherein the reaction result is as follows: the conversion of 1H, 5H-hexafluorocyclopentene was 99.2%, and the selectivity of 1H, 2H-hexafluorocyclopentene was 100%.
The organic phase was subjected to rectification to obtain the isomeric hexafluorocyclopentenes, namely 1H, 5H-hexafluorocyclopentene having a boiling point of 74 ℃ (760mmHg) and 1H, 2H-hexafluorocyclopentene having a boiling point of 70 ℃ (760 mmHg).
Example 17
A tubular reactor of Incan alloy having an inner diameter of 1/2 inches and a length of 30cm was charged with 10ml of an isomerization catalyst prepared by the above method and containing 5% LiF/AlF3. The reaction conditions are as follows: the temperature of the reaction is increased to 300 ℃, the contact time of the 1H-3-chlorohexafluorocyclopentene is 5s, and the reaction pressure is 0.1 MPa. After the reaction is carried out for 100 hours, washing and separating the reaction product to obtain organic matters, drying and dewatering, and analyzing the composition of the organic matters by using gas chromatography, wherein the reaction result is as follows: the conversion of 1H-3-chlorohexafluorocyclopentene was 79.3%, the selectivity for 1H-4-chlorohexafluorocyclopentene was 11.4%, and the selectivity for 1-chlorohexafluorocyclopentene was 88.6%.
The organic phase is rectified to obtain the isomers of monochlorofluorocyclopentene, namely 1H-3-chlorohexafluorocyclopentene, which has a boiling point of 77-84 ℃ (760mmHg), 1H-4-chlorohexafluorocyclopentene, which has a boiling point of 68-70 ℃ (760mmHg), and 1H-2-chlorohexafluorocyclopentene, which has a boiling point of 73-74 ℃ (760 mmHg).
Example 18
A tubular reactor of 30cm length having an inner diameter of 1/2 inches and filled with 10ml of the isomerization catalyst 5% NaF/AlF prepared by the above method3. The reaction conditions are as follows: the temperature of the reaction is increased to 300 ℃, the contact time of the 1H-4-chlorohexafluorocyclopentene is 5s, and the reaction pressure is 0.1 MPa. After the reaction for 100h, washing the reaction product with water, separating to obtain organic matter, drying to remove water, and analyzing the composition of the organic matter by gas chromatographyThe reaction result is as follows: the conversion of 1H-4-chlorohexafluorocyclopentene was 92.7%, the selectivity for 1H-3-chlorohexafluorocyclopentene was 25.6%, and the selectivity for 1H-2-chlorohexafluorocyclopentene was 74.4%.
The organic phase is rectified to obtain the isomers of monochlorofluorocyclopentene, namely 1H-3-chlorohexafluorocyclopentene, which has a boiling point of 77-84 ℃ (760mmHg), 1H-4-chlorohexafluorocyclopentene, which has a boiling point of 68-70 ℃ (760mmHg), and 1H-2-chlorohexafluorocyclopentene, which has a boiling point of 73-74 ℃ (760 mmHg).

Claims (6)

1. A process for preparing halogenated penta-cyclic olefins by gas phase isomerization, which comprises the steps of:
with halogenated five-membered cyclic olefins C5HxFyClzThe method comprises the following steps of taking the raw material as a raw material, carrying out gas phase isomerization reaction in the presence of an isomerization catalyst to obtain an isomer of halogenated five-membered cycloolefine, wherein X is an integer of 0-2, Y is an integer of 4-7, Z is an integer of 0-4, and X + Y + Z is 8, wherein the isomerization catalyst takes at least one of lithium fluoride, potassium fluoride, sodium fluoride, rubidium fluoride or cesium fluoride as an active component and is loaded on at least one carrier of aluminum fluoride, magnesium fluoride, iron fluoride, chromium fluoride and zinc fluoride; the preparation method of the isomerization catalyst comprises the following steps: (1) dissolving carrier metal soluble salt in water, dropwise adding concentrated ammonia water for precipitation, adjusting the pH value to 7.0-7.5, then aging for 10-15 hours, washing with water, filtering, drying in an oven at 70-100 ℃ for 12-48 hours, and then roasting at 300-500 ℃ for 5-20 hours under the protection of nitrogen to obtain carrier metal oxide which is a precursor of a metal fluoride carrier; (2) according to the percentage composition of active component alkali metal fluoride and carrier metal fluoride, at 40-50 deg.C, adopting impregnation method to impregnate and load active component alkali metal fluoride on carrier metal oxide, filtering, drying at 70-100 deg.C for 5-48 hr, pulverizing obtained solid, tabletting and forming to obtain catalyst precursor; (3) loading the catalyst precursor into a tubular reactor, introducing nitrogen, roasting at 500 ℃ for 5-20 hours at the nitrogen airspeed of 200h-1And then, at the temperature of 200-400 ℃, introducing a material with the mass ratio of 1: 2 hydrogen fluoride and nitrogen, gas mixtureSpace velocity of 220h-1Activating for 5-20 hours, stopping the mixed gas to prepare an isomerization catalyst;
preparing 1, 3-dichlorohexafluorocyclopentene and 1, 2-dichlorohexafluorocyclopentene from the raw material 1, 4-dichlorohexafluorocyclopentene;
or 1, 3-dichlorohexafluorocyclopentene as a raw material to prepare 1, 4-dichlorohexafluorocyclopentene and 1, 2-dichlorohexafluorocyclopentene;
or 1,4, 4-trichloropentafluorocyclopentene as a raw material to prepare 1,3, 3-trichloropentafluorocyclopentene, 1,2, 3-trichloropentafluorocyclopentene and 1,2, 4-trichloropentafluorocyclopentene;
or 1,3, 3-trichloropentafluorocyclopentene as a raw material to prepare 1,4, 4-trichloropentafluorocyclopentene, 1,2, 3-trichloropentafluorocyclopentene and 1,2, 4-trichloropentafluorocyclopentene;
or preparing 1,2, 3-trichloropentafluorocyclopentene from the raw material 1,2, 4-trichloropentafluorocyclopentene;
or preparing 1,2, 4-trichloropentafluorocyclopentene from the raw material 1,2, 3-trichloropentafluorocyclopentene;
or 1,2,3, 3-tetrachloro-tetrafluorocyclopentene is used as a raw material to prepare 1,2,4, 4-tetrachloro-tetrafluorocyclopentene;
or 1,2,4, 4-tetrachloro-tetrafluorocyclopentene is used as a raw material to prepare 1,2,3, 3-tetrachloro-tetrafluorocyclopentene;
or 1H-3-chloro-hexafluorocyclopentene as a raw material to prepare 1H-4-chloro-hexafluorocyclopentene and 1H-2-chloro-hexafluorocyclopentene;
or 1H-4-chloro-hexafluorocyclopentene as a raw material to prepare 1H-3-chloro-hexafluorocyclopentene and 1H-2-chloro-hexafluorocyclopentene;
or 4H-heptafluorocyclopentene as a raw material to prepare 3H-heptafluorocyclopentene and 1H-heptafluorocyclopentene;
or 3H-heptafluorocyclopentene as a raw material to prepare 4H-heptafluorocyclopentene and 1H-heptafluorocyclopentene;
or 4H, 4H-hexafluorocyclopentene as a raw material to prepare 3H, 3H-hexafluorocyclopentene, 1H, 5H-hexafluorocyclopentene, 1H, 4H-hexafluorocyclopentene, 1H, 3H-hexafluorocyclopentene and 1H, 2H-hexafluorocyclopentene;
or 3H, 3H-hexafluorocyclopentene as a raw material to prepare 4H, 4H-hexafluorocyclopentene, 1H, 5H-hexafluorocyclopentene, 1H, 4H-hexafluorocyclopentene, 1H, 3H-hexafluorocyclopentene and 1H, 2H-hexafluorocyclopentene;
or 1H, 4H-hexafluorocyclopentene is used as a raw material to prepare 1H, 3H-hexafluorocyclopentene and 1H, 2H-hexafluorocyclopentene;
or 1H, 3H-hexafluorocyclopentene is used as a raw material to prepare 1H, 4H-hexafluorocyclopentene and 1H, 2H-hexafluorocyclopentene;
or 1H, 5H-hexafluorocyclopentene as a raw material to prepare 1H, 2H-hexafluorocyclopentene.
2. The method according to claim 1, wherein the mass percentage of the active component to the carrier is 5-10%: 90 to 95 percent.
3. The process of claim 1, the isomerization catalyst is prepared by: (1) dissolving carrier metal soluble salt in water, dropwise adding concentrated ammonia water for precipitation, adjusting the pH value to 7.5, then aging for 12 hours, washing with water, filtering, drying in an oven at 80 ℃ for 36 hours, and then roasting at 450 ℃ for 8 hours under the protection of nitrogen to obtain carrier metal oxide which is a precursor of a metal fluoride carrier; (2) according to the percentage composition of active component alkali metal fluoride and carrier metal fluoride, at 50 deg.C, adopting impregnation method to impregnate and load active component alkali metal fluoride on carrier metal oxide, filtering, drying at 80 deg.C for 12 hr, pulverizing obtained solid, tabletting and forming to obtain catalyst precursor; (3) loading the catalyst precursor into a tubular reactor, introducing nitrogen, roasting at 450 ℃ for 8 hours, wherein the space velocity of the nitrogen is 200h-1Then, the temperature is reduced to 300 ℃, and simultaneously the mass ratio of the introduced substances is 1: 2, the total space velocity of the gas is 220h-1And activating for 12 hours, and stopping the mixed gas to prepare the isomerization catalyst.
4. The process of claim 1, the carrier metal soluble salt being a chloride or nitrate salt of a metal.
5. The method of claim 1, the reaction conditions being: the reaction pressure is 0.1MPa-0.5MPa, the reaction temperature is 50-400 ℃, and the contact time is 0.5-50 s.
6. The method of claim 5, the reaction conditions being: the reaction pressure is 0.1MPa-0.5MPa, the reaction temperature is 150-300 ℃, and the contact time is 5-25 s.
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Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011105625A (en) * 2009-11-16 2011-06-02 Nippon Zeon Co Ltd Method of isomerizing heptafluorocyclopentene, and use thereof
CN105294387A (en) * 2015-10-22 2016-02-03 北京宇极科技发展有限公司 Method for preparing chlorine fluorine cyclopentene isomeride

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