Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C17/00—Preparation of halogenated hydrocarbons
  • C07C17/25—Preparation of halogenated hydrocarbons by splitting-off hydrogen halides from halogenated hydrocarbons
• • 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
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
  • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J23/85—Chromium, molybdenum or tungsten
  • B01J23/86—Chromium
  • B01J23/868—Chromium copper and chromium
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
  • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
  • C07B2200/09—Geometrical isomers

Definitions

• This disclosure relates to a method for producing fluoroethylene.
• Patent Document 1 describes 1,2-difluoroethylene (HFO) in which 1-chloro-1,2-difluoroethylene (HCFO-1122a) and hydrogen are reacted in a gas phase in the presence of a hydrogenation catalyst. The manufacturing method of -1132) is disclosed.
• the challenge is to provide a method for efficiently obtaining fluoroethylene.
• Item 1 (Z) and / or (E) -1,2-difluoroethylene (HFO-1132 (Z / E)), 1,1-difluoroethylene (HFO-1132a), and 1,1,2-trifluoroethylene (A method for producing at least one fluoroethylene compound selected from the group consisting of HFO-1123).
• 1,1,2,2-Tetrafluoroethan (HFC-134) With at least one fluoroethane compound selected from the group consisting of 1,1,1,2-tetrafluoroethane (HFC-134a) and 1,1,1,2,2-pentafluoroethane (HFC-125).
• H 2 1,1,1,2,2-pentafluoroethane
• Item 2 A method for producing (Z) and / or (E) -1,2-difluoroethylene (HFO-1132 (Z / E)) with 1,1,2,2-tetrafluoroethane (HFC-134).
• Item 2 The production method according to Item 1, which comprises a step of reacting with hydrogen (H 2).
• Item 3 After the reaction, HFO-1132 (Z / E) is recovered from the reaction product, and the stream containing HFC-134 as the main component and the stream containing hydrogen fluoride (HF) generated after the reaction as the main component are separated. Including the process Item 2.
• the production method according to Item 2 which comprises a step of recycling at least a part of a stream containing HFC-134 as a main component into the reaction and reacting with hydrogen (H 2) again.
• Item 4 A method for producing 1,1-difluoroethylene (HFO-1132a).
• Item 2. The production method according to Item 1, which comprises a step of reacting 1,1,1,2-tetrafluoroethane (HFC-134a) with hydrogen (H 2).
• Item 5 After the reaction, it comprises a step of recovering HFO-1132a from the reaction product and separating a stream containing HFC-134a as a main component and a stream containing hydrogen fluoride (HF) as a main component generated after the reaction.
• Item 4. The production method according to Item 4, which comprises a step of recycling at least a part of a stream containing HFC-134a as a main component into the reaction and reacting with hydrogen (H 2) again.
• Item 6 A method for producing 1,1,2-trifluoroethylene (HFO-1123). Including the step of reacting 1,1,1,2,2-pentafluoroethane (HFC-125) with hydrogen (H 2), Item 1. The manufacturing method according to Item 1.
• HFO-1123 is recovered from the reaction product and includes a step of separating the stream containing HFC-125 as a main component and the stream containing hydrogen fluoride (HF) as a main component generated after the reaction, which comprises a step of separating HFC.
• Item 6 The production method according to Item 6, wherein at least a part of the stream containing -125 as a main component is recycled into the reaction and reacted with hydrogen (H 2) again.
• Item 8 The production method according to any one of Items 1 to 7, wherein the reaction is carried out by a gas phase flow system.
• Item 9 The production method according to any one of Items 1 to 8, wherein the reaction is carried out at a temperature of 400 ° C. or higher.
• Item 10 Item 2. The above item 1 to 9, wherein the reaction is carried out with the amount of hydrogen (H 2 ) used being 0.1 to 10 mol (H 2 / molar ratio of the raw material compound) with respect to 1 mol of the raw material compound. Production method.
• Item 11 The production method according to any one of Items 1 to 10, wherein the reaction is carried out using a metal catalyst.
• the metal catalyst includes chromium oxide, chromium fluoride oxide, chromium fluoride, copper chromium oxide, copper fluoride chromium oxide, aluminum oxide, aluminum fluoride oxide, aluminum fluoride, iron oxide, iron fluoride oxide, and foot. At least one metal catalyst selected from the group consisting of iron oxide, nickel oxide, nickel fluoride oxide, nickel fluoride, copper oxide, copper fluoride oxide, magnesium oxide, magnesium fluoride oxide, and magnesium fluoride.
• Item 11 The manufacturing method according to Item 11.
• fluoroethylene can be efficiently obtained.
• HFO fluoroethane compound of HFC-134, HFC-134a, or HFC-125 with hydrogen (H 2), respectively. It has been found that a fluoroethylene compound of -1132 (Z / E), HFO-1132a, or HFO-1123 can be produced and the above problems can be solved.
• the production method of the present disclosure is a production method of at least one fluoroethylene compound selected from the group consisting of HFO-1132 (Z / E), HFO-1132a, and HFO-1123, and is a production method of HFC-134, HFC-. It comprises the step of reacting hydrogen (H 2 ) with at least one fluoroethane compound selected from the group consisting of 134a and HFC-125.
• the production method of the present disclosure is preferably a production method of HFO-1132 (Z / E)), which comprises a step of reacting HFC-134 with hydrogen (H 2).
• the production method of the present disclosure is preferably a production method of HFO-1132a, which comprises a step of reacting HFC-134a with hydrogen (H 2).
• the production method of the present disclosure is preferably a production method of HFO-1123, which comprises a step of reacting HFC-125 with hydrogen (H 2).
• a fluoroethane compound (raw material compound) of HFC-134, HFC-134a, or HFC-125 is reacted with hydrogen (H 2 ) to generate carben species by thermal decomposition.
• HFC-134 HFC-134a
• HFC-125 the carbene species generated by thermal decomposition are different.
• CFH carbene is generated in the thermal decomposition of HFC-134.
• Pyrolysis of HFC-134a produces CH 2 carbene and CF 2 carbene.
• Pyrolysis of HFC-125 produces CF 2 carbene and CFH carbene.
• the reaction is preferably carried out by a vapor phase flow method.
• the reaction is preferably carried out at a temperature of 400 ° C. or higher.
• the reaction uses 0.1 to 10 mol of hydrogen (H 2 ) chlorine with respect to 1 mol of the starting compound (HFC-134, HFC-134a or HFC-125). (H 2 / molar ratio of raw material compound).
• the reaction is preferably carried out using a metal catalyst.
• the production method of the present disclosure is HFO-1132 (Z / E), HFO-, respectively, from a fluoroethane compound (raw material compound) of HFC-134, HFC-134a, or HFC-125 by one step (one-pot synthesis).
• a fluoroethylene compound (target compound) of 1132a or HFO-1123 can be produced.
• the manufacturing method of the present disclosure is, in particular, from the inexpensive HFC-134, HFC-134a, or HFC-125 (raw material compound), efficiently and efficiently, respectively, to the above-mentioned HFO-1132 (Z / E) and HFO-1132a.
• HFO-1123 target compound
• the production methods of the present disclosure are HFO-1132 (Z), respectively, by thermal decomposition of a fluoroethane compound (raw material compound) of HFC-134, HFC-134a, or HFC-125 in the presence of hydrogen (H 2). / E), a process for producing a fluoroethylene compound (target compound) of HFO-1132a, or HFO-1123.
• the thermal decomposition produces a carbene species as a precursor of HFO-1132 (Z / E), HFO-1132a, or HFO-1123.
• the raw material compound of the production method of the present disclosure is HFC-134, HFC-134a, or HFC-125.
• These halogenated ethanes are widely used as refrigerants, solvents, foaming agents, propellants and the like, and are generally available.
• the production method of the present disclosure is a fluoroethane compound (raw material compound) of HFC-134, HFC-134a, or HFC-125 in the presence of hydrogen (H 2). It is a method for producing a fluoroethylene compound (target compound) of HFO-1132 (Z / E), HFO-1132a, or HFO-1123, respectively, by thermal decomposition.
• a carbene species is produced as a precursor of the target compound by the thermal decomposition.
• HFO-1132 (Z / E), which is the target compound
• HFO-1132a which is a target compound
• HFO-1123 which is a target compound
• HFC-125 is used as a raw material compound.
• the method for producing HFO-1132 (Z / E) includes a step of reacting HFC-134 with hydrogen (H 2).
• the method for producing HFO-1132a includes a step of reacting HFC-134a with hydrogen (H 2).
• the method for producing HFO-1123 includes a step of reacting HFC-125 with hydrogen (H 2).
• the step of reacting the raw material compound with hydrogen (H 2 ) is preferably carried out in the gas phase, and more preferably in the gas phase flow system.
• the production method of the present disclosure is particularly preferably carried out by a gas phase continuous flow system using a fixed bed reactor. When the gas phase continuous flow method is used, the equipment, operation, etc. can be simplified and it is economically advantageous.
• the step of reacting the raw material compound with hydrogen (H 2 ) is preferably carried out in the presence of a catalyst and in the gas phase.
• the catalyst used in this step is preferably activated carbon and / or a metal catalyst.
• the metal catalyst is more preferably chromium oxide, chromium fluoride oxide, chromium fluoride, copper chromium oxide, copper fluoride chromium oxide, aluminum oxide, aluminum fluoride oxide, aluminum fluoride, iron oxide, fluoride. At least one metal selected from the group consisting of iron oxide, iron fluoride, nickel oxide, nickel fluoride oxide, nickel fluoride, copper oxide, copper oxide, magnesium oxide, magnesium fluoride and magnesium fluoride. It is a catalyst.
• chromium oxide, chromium fluoride oxide, chromium fluoride, copper chromium oxide, copper fluoride chromium oxide, aluminum oxide, and foot are more preferable because the conversion rate of the reaction can be increased.
• Aluminum oxide, aluminum fluoride, etc. are used.
• the catalyst may be in the form of powder, but the form of pellets is preferable for the gas phase continuous flow type reaction.
• the specific surface area (hereinafter, also referred to as BET specific surface area) measured by the BET method of the catalyst is usually 10 m 2 / g to 3,000 m 2 / g, preferably 10 m 2 / g to 400 m 2 / g. It is more preferably 20 m 2 / g to 375 m 2 / g, and even more preferably 30 m 2 / g to 350 m 2 / g.
• the BET specific surface area of the catalyst is in the above range, the density of the particles of the catalyst is not too small, so that the target compound can be obtained with a high selectivity. It is also possible to improve the conversion rate of the raw material compound.
• activated carbon When activated carbon is used as a catalyst, it is preferable to use powdered activated carbon such as crushed charcoal, briquette, granulated charcoal, and spherical charcoal. As the powdered activated carbon, it is preferable to use powdered activated carbon having a particle size of 4 mesh (4.76 mm) to 100 mesh (0.149 mm) in the JIS test.
• a metal catalyst When a metal catalyst is used as the catalyst, it is preferably supported on a carrier.
• the carrier include carbon, alumina (Al 2 O 3 ), zirconia (ZrO 2 ), silica (SiO 2 ), titania (TiO 2 ) and the like.
• carbon activated carbon, amorphous carbon, graphite, diamond and the like can be used.
• the lower limit of the reaction temperature is a viewpoint that the reaction can proceed more efficiently and the target compound can be obtained with a higher selectivity. From the viewpoint of suppressing a decrease in the conversion rate, the temperature is usually about 400 ° C, preferably about 500 ° C, and more preferably about 600 ° C.
• the upper limit of the reaction temperature is selected from the viewpoint that the raw material compound and hydrogen (H 2 ) can be reacted more efficiently to obtain the target compound with a higher selectivity, and the reaction product is decomposed or polymerized. From the viewpoint of suppressing the decrease in the rate, the temperature is usually about 1,200 ° C, preferably about 1,000 ° C.
• the step of reacting the raw material compound with hydrogen (H 2 ) in the present disclosure it is preferable to carry out the reaction in the range of about 400 ° C to 1,200 ° C.
• the contact time is preferably 5 sec to 300 sec, more preferably 10 sec to 200 sec, from the viewpoint of improving the conversion rate of the raw material compound and suppressing the equipment cost. , More preferably, it is 15 gsec to 150 sec.
• the contact time of the raw material compound means the residence time of the raw material compound in the pipe when the reaction temperature is reached.
• the reaction time is the contact time of the raw material compound with the catalyst (W / F 0 ) [W: weight of the catalyst (g). ), F 0 : Flow rate of raw material compound (cc / sec)].
• the contact time (W / F 0 ) of the raw material compound with the catalyst is preferably 5 g ⁇ sec / from the viewpoint of improving the conversion rate of the raw material compound and suppressing the equipment cost. It is cc to 300 g / sec / cc, more preferably 10 g / sec / cc to 200 g / sec / cc, and further preferably 15 g / sec / cc to 150 g / sec / cc.
• the contact time of the raw material compound with the catalyst means the time of contact between the raw material compound and the catalyst.
• the step of reacting the raw material compound with hydrogen (H 2 ) is carried out in the gas phase in the presence of a catalyst, and the reaction temperature and the reaction time (contact time) are appropriately adjusted according to the catalyst in particular. Therefore, the target compound can be obtained with a higher selectivity.
• the reaction pressure is preferably -0.05 MPa to 2 MPa, preferably -0.01 MPa, from the viewpoint of allowing the reaction to proceed more efficiently. It is more preferably ⁇ 1MPa, and even more preferably ⁇ 0.5MPa at normal pressure. In this disclosure, if there is no description about pressure, it shall be gauge pressure.
• the shape and structure of the reactor in which the raw material compound and the catalyst (metal catalyst, etc.) are brought into contact with each other to react are not particularly limited as long as they can withstand the above temperature and pressure.
• the reactor include a vertical reactor, a horizontal reactor, a multi-tube reactor and the like.
• the material of the reactor include glass, stainless steel, iron, nickel, iron-nickel alloy and the like.
• the step of reacting the raw material compound with hydrogen (H 2 ) is a distribution formula in which the raw material compound is continuously charged into the reactor and the target compound is continuously extracted from the reactor. It can be carried out by any of the batch methods. If the target compound stays in the reactor, the reaction can proceed further, so it is preferable to carry out the reaction by a distribution method.
• the step of reacting the raw material compound with hydrogen (H 2 ) is preferably carried out in the gas phase, and particularly preferably in the gas phase continuous flow system using a fixed bed reactor. When the gas phase continuous distribution method is used, the equipment, operation, etc. can be simplified and it is economically advantageous.
• the atmosphere during the reaction in addition to hydrogen (H 2 ) that reacts with the raw material compound, from the viewpoint of suppressing deterioration of the catalyst (metal catalyst, etc.), in the presence of an inert gas and / or in the presence of hydrogen fluoride.
• the inert gas is preferably at least one selected from the group consisting of nitrogen, helium, argon and carbon dioxide. Among these inert gases, nitrogen (N 2 ) is more preferable from the viewpoint of cost reduction.
• the concentration of the inert gas is preferably 0 mol% to 99 mol% of the gas component introduced into the reactor.
• purification treatment can be performed according to a conventional method as needed.
• the amount of hydrogen (H 2 ) used is not particularly limited.
• the amount of hydrogen (H 2 ) used is preferably 0.1 to 10 mol (H 2 / mol of the raw material compound) with respect to 1 mol of the raw material compound (HFC-134, HFC-134a or HFC-125). Ratio), more preferably 0.5 to 2 mol (H 2 / molar ratio of raw material compound).
• a carbene species is produced as a precursor by thermal decomposition of a raw material compound in the presence of hydrogen (H 2 ), and each has a high conversion rate (yield) and a high selectivity, HFO-1132 (Z). / E), HFO-1132a, or HFO-1123 (target compound) can be produced.
• the fluoroethylene compound of HFO-1132 (Z / E), HFO-1132a, or HFO-1123 is selected from the reaction product.
• (Target compound) is recovered, and the main component is a stream containing HFC-134, HFC-134a, or HFC-125 fluoroethane compound (raw material compound) as the main component, and hydrogen fluoride (HF) generated after the reaction as the main component.
• HF hydrogen fluoride
• the separated stream containing the fluoroethane compound of HFC-134, HFC-134a, or HFC-125 as a main component is recycled to the reaction and again.
• the content ratio of the target compound is further increased by repeatedly recovering the fluoroethylene compound (target compound) of HFO-1132 (Z / E), HFO-1132a, or HFO-1123.
• the composition can be obtained.
• a method including a step of recycling in the method of manufacturing HFO-1132 (Z / E) includes a step of reacting HFC-134 with hydrogen (H 2 ), and is preferable. After the reaction, HFO-1132 (Z / E) was recovered from the reaction product, and the stream containing HFC-134 as the main component and the stream containing hydrogen fluoride (HF) generated after the reaction as the main component were separated. Including the step of recycling at least a part of the stream containing HFC-134 as a main component into the reaction and reacting with hydrogen (H 2 ) again.
• a method including a step of recycling in the method for producing HFO-1132a includes a step of reacting HFC-134a with hydrogen (H 2 ), and preferably, after the reaction, HFO from the reaction product.
• a step of recovering -1132a and separating a stream containing HFC-134a as a main component and a stream containing hydrogen fluoride (HF) as a main component generated after the reaction is included, and the stream containing HFC-134a as a main component is included. It comprises a step of recycling at least a part of the reaction into the reaction and reacting with hydrogen (H2) again.
• a method including a step of recycling in the method for producing HFO-1123 includes a step of reacting HFC-125 with hydrogen (H 2 ), and preferably after the reaction, from the reaction product to HFO.
• a stream containing HFC-125 as a main component which comprises a step of recovering -1123 and separating a stream containing HFC-125 as a main component and a stream containing hydrogen fluoride (HF) as a main component generated after the reaction. It comprises a step of recycling at least a part of the reaction into the reaction and reacting with hydrogen (H2) again.
• the production methods of the present disclosure are HFO-1132 (Z), respectively, by thermal decomposition of a fluoroethane compound (raw material compound) of HFC-134, HFC-134a, or HFC-125 in the presence of hydrogen (H 2). / E), a process for producing a fluoroethylene compound (target compound) of HFO-1132a, or HFO-1123.
• the thermal decomposition produces a carbene species as a precursor of HFO-1132 (Z / E), HFO-1132a, or HFO-1123.
• the target compound of the production method of the present disclosure is a fluoroethylene compound of HFO-1132 (Z / E), HFO-1132a, or HFO-1123.
• the fluoroolefins of HFO-1132 (Z / E), HFO-1132a, or HFO-1123 are used in various applications such as refrigerants, solvents, foaming agents, propellants, resin product raw materials, organic synthetic intermediates, and heat media. , Can be used effectively.
• Example 1 Production of HFO-1132 (Z / E) under non-catalytic conditions HFO-1132 (Z / Z ) by thermal decomposition of HFC-134 (raw material compound) in the presence of hydrogen (H 2 ) in a reactor (material: SUS316). / E) (target compound) was produced.
• HFO-1114 Tetrafluoroethylene (HFO-1114)
• HFO-1141 Fluoroethylene c-318: Octafluorocyclobutane (perfluorocyclobutane)
• HFC-143 1,1,2-trifluoroethane
• CFH carbene can be generated by reacting HFC-134 with hydrogen (H 2 ) in a gas phase distribution system, and HFO-1132 (Z / E) can be synthesized by coupling. rice field.
• HFO-1132 (Z / E) can be efficiently produced by reacting HFC-134 (raw material compound) with hydrogen (H 2) by the production method of the present disclosure. ..
• Catalyst Copper Chromium Oxide (Calsicat: S-93-346A E-103TU) 5g Reaction temperature of Examples 2 to 6: 400 ° C Reaction temperature of Example 7: 500 ° C. Reaction pressure: normal pressure
• Example 2 The reaction was carried out in the presence of a copper chromium catalyst. Compared with the non-catalytic condition (500 ° C.) of Example 1, the reaction proceeded at a low temperature (400 ° C.), and the conversion rate of the raw material compound HFC-134 was improved to 3.9%. The selectivity of the target compound HFO-1132 (Z / E) was 47%, which was higher than that of the non-catalytic condition of Example 1.
• "Others" in Table 2 mainly contains hydrocarbon compounds such as ethane, ethylene, and propylene.
• Example 5 Compared with Example 2 (HFC-134: 50, H 2 : 50), the gas phase conditions were changed to HFC-134: 67, H 2 : 33.
• the conversion rate of the raw material compound HFC-134 and the selectivity of the target compound HFO-1132 (Z / E) were similar to those in Example 2.
• Example 6 Compared with Example 2 (HFC-134: 50, H 2 : 50), the gas phase conditions were changed to HFC-134: 40, H 2 : 60.
• the conversion rate of the raw material compound HFC-134 and the selectivity of the target compound HFO-1132 (Z / E) were similar to those in Example 2.
• Example 7 Compared with Example 4 (400 ° C), the reaction temperature was raised to 500 ° C. The conversion rate of the raw material compound HFC-134 was improved to 11% as compared with Example 4. Methane became the main product.
• HFO-1132 (Z / E) can be produced more efficiently by reacting HFC-134 (raw material compound) with hydrogen (H 2) in the presence of a metal catalyst. It was evaluated that it was possible.
• a metal catalyst preferably a copper-chromium catalyst
• chromium is used as Lewis acid. It can be understood that there is a de-HF effect.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Priority Applications (3)

Applications Claiming Priority (2)

Related Child Applications (1)

Publications (1)

Family

ID=78708610

Family Applications (1)

Country Status (5)

Cited By (1)

Families Citing this family (1)

Citations (4)

Family Cites Families (4)

• 2020
  • 2020-05-22 JP JP2020089833A patent/JP7395422B2/ja active Active
• 2021
  • 2021-05-21 EP EP21808582.7A patent/EP4155285A4/en active Pending
  • 2021-05-21 CN CN202180036947.6A patent/CN115667192A/zh active Pending
  • 2021-05-21 WO PCT/JP2021/019298 patent/WO2021235536A1/ja not_active Ceased
• 2022
  • 2022-04-15 JP JP2022067300A patent/JP2022087300A/ja not_active Withdrawn
  • 2022-11-21 US US17/990,961 patent/US20230101465A1/en active Pending

Patent Citations (4)

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events