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WO2013161692A1 - Procédé de production en parallèle de trans-1,3,3,3-tétrafluoropropène et de 1,1,1,3,3-pentafluoropropane - Google Patents

Procédé de production en parallèle de trans-1,3,3,3-tétrafluoropropène et de 1,1,1,3,3-pentafluoropropane Download PDF

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WO2013161692A1
WO2013161692A1 PCT/JP2013/061591 JP2013061591W WO2013161692A1 WO 2013161692 A1 WO2013161692 A1 WO 2013161692A1 JP 2013061591 W JP2013061591 W JP 2013061591W WO 2013161692 A1 WO2013161692 A1 WO 2013161692A1
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hydrogen fluoride
tetrafluoropropene
reaction
trans
chloro
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冬彦 佐久
吉川　悟
覚 岡本
祥雄 西口
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Central Glass Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/07—Preparation of halogenated hydrocarbons by addition of hydrogen halides
    • C07C17/087—Preparation of halogenated hydrocarbons by addition of hydrogen halides to unsaturated halogenated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B7/00—Halogens; Halogen acids
    • C01B7/01—Chlorine; Hydrogen chloride
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B7/00—Halogens; Halogen acids
    • C01B7/19—Fluorine; Hydrogen fluoride
    • C01B7/191—Hydrogen fluoride
    • C01B7/195—Separation; Purification
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B7/00—Halogens; Halogen acids
    • C01B7/19—Fluorine; Hydrogen fluoride
    • C01B7/191—Hydrogen fluoride
    • C01B7/195—Separation; Purification
    • C01B7/196—Separation; Purification by distillation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
    • C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
    • C07C17/202—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction
    • C07C17/206—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction the other compound being HX
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
    • C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
    • C07C17/21—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms with simultaneous increase of the number of halogen atoms
    • 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/30—Materials not provided for elsewhere for aerosols
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/02—Materials undergoing a change of physical state when used
    • C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
    • C09K5/041—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems
    • C09K5/044—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds
    • C09K5/045—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds containing only fluorine as halogen

Definitions

  • Trans-1,3,3,3-tetrafluoropropene and 1,1,1,3,3-pentafluoropropane are propellants that are propellants for aerosols in intermediate raw materials such as medical pesticides or functional materials, sprays, etc. It is useful as a protective gas used in manufacturing a magnesium alloy, an etching gas used in manufacturing a semiconductor, a foaming agent, a fire extinguishing agent, a heat medium or a refrigerant.
  • Fluorohydrocarbons have shifted to alternative chlorofluorocarbons with a low ozone depletion coefficient rather than specific chlorofluorocarbons that are regulated to protect the ozone layer by international treaties.
  • Trans-1,3,3,3-tetrafluoropropene and 1,1,1,3,3-pentafluoropropane which are alternative fluorocarbons with a low global warming potential, in addition to the ozone depletion potential, convert raw material compounds It has been studied to obtain a reaction efficiently and efficiently.
  • Patent Documents 1 to 3 disclose methods for obtaining 1,1,1,3,3-pentafluoropropane using 1-chloro-3,3,3-trifluoropropene as a raw material compound.
  • Patent Document 1 discloses a method for liquid-phase fluorination of 1-chloro-3,3,3-trifluoropropene with hydrogen fluoride in the presence of an antimony catalyst.
  • Patent Document 2 discloses that 1,1,1,3-tetrafluoro-3-chloropropane is added to 1-chloro-3,3,3-trifluoropropene by adding hydrogen fluoride in the presence of an addition catalyst. And then disproportionating the 1,1,1,3-tetrafluoro-3-chloropropane in the presence of a disproportionation catalyst.
  • Patent Document 3 discloses a method for producing 1,1,1,3,3-pentafluoropropane from 1-chloro-3,3,3-trifluoropropene and hydrogen fluoride in the presence of chlorine.
  • a fluorination reactor comprising a reactor (A) and a reactor (B) each filled with antimony pentachloride-supported activated carbon, and a first reactor set at 150 ° C.
  • the second reactors set at ° C are arranged in series, and in the first time section, the reactor (A) is the first reactor, the reactor (B) is the second reactor, and the second time section
  • the reaction is carried out using the reactor (B) as the first reactor and the reactor (A) as the second reactor, and then repeating the exchange of the reactor (A) and the reactor (B) in the same manner as described above.
  • a method comprising performing
  • Patent Document 4 1-chloro-3,3,3-trifluoropropene is fluorinated in the gas phase in the presence of a fluorination catalyst to obtain 1,3,3,3-tetrafluoropropene.
  • An oxide, fluoride, chloride, fluorinated chloride, oxyfluoride, oxychloride or at least one metal selected from chromium, titanium, aluminum, manganese, nickel or cobalt as the fluorination catalyst The use of activated carbon carrying oxyfluoride chloride has been reported.
  • Patent Document 5 discloses 1, 3, 3, 3 in the presence of a hydrogen halide addition catalyst, which is a halide of at least one metal selected from the group consisting of aluminum, tin, bismuth, antimony and iron.
  • a hydrogen halide addition catalyst which is a halide of at least one metal selected from the group consisting of aluminum, tin, bismuth, antimony and iron.
  • 1,3,3,3-tetrafluoropropene using 1-chloro-3,3,3-trifluoropropene as a starting compound, 1-chloro-3,3,3-trifluoropropene are known, and 1,1,1,3,3-pentafluoropropane is obtained in a known manner.
  • the target compound, trans-1,3,3,3-tetrafluoropropene and 1,1,1,3,3-pentafluoropropane are known. 1,3,3-pentafluoropropane can be obtained in good yield.
  • the present invention provides a method for efficiently producing trans-1,3,3,3-tetrafluoropropene and 1,1,3,3-pentafluoropropane in parallel with a raw material compound.
  • the present invention includes the following inventions 1 to 7.
  • a purification step to obtain residue F The residue E after dehydration in the dehydration step is rectified and contains trans-1,3,3,3-tetrafluoropropene and cis-1,3,3,3-tetrafluoropropene as fractions.
  • Fluorination catalyst is chromium, titanium, aluminum, manganese, nickel, cobalt, iron, copper, zinc, silver, molybdenum, zirconium, niobium, tantalum, iridium, tin, hafnium, vanadium, magnesium, lithium, sodium, potassium, calcium And at least one metal selected from the group consisting of antimony and nitrate, chloride, oxide, sulfate, fluoride, fluoride, oxyfluoride, oxychloride, or oxyfluoride The average production method.
  • invention 5 The parallel production method of inventions 1 to 4, wherein in the hydrogen fluoride separation step, hydrogen fluoride is absorbed and recovered by sulfuric acid.
  • the present invention uses readily available 1-chloro-3,3,3-trifluoropropene as a starting material compound, trans-1,3,3,3-tetrafluoropropene and 1,1,1,3,3 -Pentafluoropropane can be produced efficiently and in parallel.
  • the present invention uses 1-chloro-3,3,3-trifluoropropene and hydrogen fluoride in a gas phase in a gas phase, using a fluorination catalyst, at a temperature of 200 ° C. or higher and 450 ° C. or lower, a pressure of 0.05 MPa or higher, and 0.3 MPa.
  • the following reaction is conducted to produce trans-1,3,3,3-tetrafluoropropene and cis-1,3,3,3-tetrafluoropropene, 1,1,1,3,3-pentafluoropropane and chloride.
  • the residue E after dehydration in the dehydration step is rectified and contains trans-1,3,3,3-tetrafluoropropene and
  • the method of the present invention reacts a raw material compound, that is, 1-chloro-3,3,3-trifluoropropene as a reactant with hydrogen fluoride, Operation to produce the desired product, trans-1,3,3,3-tetrafluoropropene,
  • the target compound trans-1,3,3,3-tetrafluoropropene after the “reaction step” and the by-product cis-1,3,3,3-tetrafluoropropene, Distilling reaction product A containing 1,1,1,3,3-pentafluoropropane and hydrogen chloride and unreacted 1-chloro-3,3,3-trifluoropropene and hydrogen fluoride, An operation of recovering unreacted 1-chloro-3,3,3-trifluoropropene and hydrogen fluoride as bottoms and supplying them to the “reaction step”;
  • the “hydrogen fluoride separation step” an operation of separating and recovering hydrogen fluor
  • unreacted 1-chloro-3,3,3-trifluoropropene and hydrogen fluoride in the “reaction step” are recovered in the “distillation step”, and the “reaction step”
  • the product is returned to the reaction system and reused as a raw material compound.
  • the provision of the “distillation step” for generally recovering hydrogen fluoride reduces the burden of the subsequent steps “hydrogen fluoride separation step” and “hydrogen chloride separation step”.
  • the subsequent provision of the “dehydration drying step” reduces the load of the “purification step” for purifying trans-1,3,3,3-tetrafluoropropene by rectification.
  • hydrogen fluoride separated and recovered from the reaction product in the “hydrogen fluoride separation step” can be returned to the “reaction step”, and cis-1,3,3,3 in the residue F of the “purification step” can be returned.
  • 3-tetrafluoropropene is converted to 1,1,1,3,3-pentafluoropropane.
  • 1-chloro-3,3,3-trifluoropropene which is a starting material, is reacted with hydrogen fluoride to efficiently produce trans-1,3,3,3- Tetrafluoropropene and 1,1,1,3,3-pentafluoropropane can be produced in parallel, which is useful for mass production of these alternative chlorofluorocarbons in industrial plants.
  • the efficiency is further improved by selecting a fluorination catalyst to be used.
  • reaction product A means trans-1,3,3,3-tetrafluoropropene as the target compound, 1-chloro-3,3,3-trifluoropropene as an unreacted product, and fluorine.
  • This refers to the mixture after the “reaction step” including hydrogen chloride and by-products such as hydrogen chloride and organic substances (including cis-1,3,3,3-tetrafluoropropene).
  • the bottom liquid means a liquid rich in low volatility components obtained from the bottom of the distillation column after distillation.
  • 1-chloro-3,3,3-trifluoropropene refers to a cis isomer or a trans isomer or a mixture thereof, and 1,3,3,3-tetrafluoropropene and Refers to cis or trans isomers or mixtures thereof.
  • Rectification refers to an operation of purifying a target compound by distillation. Specifically, the residue E, which is a mixture of trans-1,3,3,3-tetrafluoropropene and cis-1,3,3,3-tetrafluoropropene in the “purification step”, is purified by distillation. This refers to an operation for obtaining pure trans-1,3,3,3-tetrafluoropropene.
  • reaction step is a process in which 1-chloro-3,3,3-trifluoropropene as a raw material compound and hydrogen fluoride are used in a gas phase in a reactor, using a fluorination catalyst, at a temperature of 200 ° C. or higher and 450 ° C. or lower.
  • the reaction is performed at a pressure of 0.05 MPa or more and 0.3 MPa or less, and the target product, trans-1,3,3,3-tetrafluoropropene, and the by-product, cis-1,3,3,3- Reaction product A containing tetrafluoropropene, 1,1,1,3,3-pentafluoropropane and hydrogen chloride and unreacted 1-chloro-3,3,3-trifluoropropene and hydrogen fluoride It is the process of obtaining.
  • 1-chloro-3,3,3-trifluoropropene which is the starting material, is fluorinated with hydrogen fluoride using a fluorination catalyst, and trans-1,3,3,3-tetrafluoropropene is converted to obtain.
  • the raw material 1-chloro-3,3,3-trifluoro It is preferable to supply an excess amount of hydrogen fluoride relative to propene into the reaction system, specifically into the reactor. Further, excessive supply of hydrogen fluoride leads to protection of the fluorination catalyst, and has an effect of prolonging the lifetime having catalytic activity.
  • the starting compound in this step, 1-chloro-3,3,3-trifluoropropene exists in cis form or trans form, but only in cis form or trans form, or a mixture of cis form and trans form. Even if it exists, the reaction in this step proceeds.
  • the fluorination catalyst used in this step is chromium, titanium, aluminum, manganese, nickel, cobalt, iron, copper, zinc, silver, molybdenum, zirconium, niobium, tantalum, iridium, tin, hafnium, vanadium, magnesium, lithium Nitrate, chloride, oxide, sulfate, fluoride, fluorinated chloride, oxyfluoride, oxychloride or oxyfluorinated chloride of at least one metal selected from the group consisting of sodium, potassium, calcium and antimony Things can be exemplified.
  • the metal oxide is preferably one in which part or all of the oxygen atoms are replaced with fluorine atoms using hydrogen fluoride or a fluorine-containing organic compound.
  • alumina, chromia, zirconia, titania or magnesia is fluorinated. It can be selected from fluorinated oxides in which some or all of the oxygen atoms are substituted with fluorine atoms.
  • fluorinated oxide of alumina and specific examples include fluorinated alumina prepared by fluorinating activated alumina with hydrogen fluoride or the like.
  • the metal fluorinated oxide may be simply referred to as “metal oxide”.
  • the metal oxide can be a commercially available product, and can be prepared by a known method.
  • a metal oxide can be prepared by adjusting the pH of an aqueous solution of a metal salt using ammonia or the like to precipitate a hydroxide, and drying or baking the precipitate.
  • the obtained metal oxide may be used after being pulverized or molded.
  • alumina is usually obtained by shaping or dewatering a precipitate produced by adding ammonia or the like to an aqueous solution of an aluminum salt.
  • ⁇ -alumina commercially available for catalyst support or for drying can be preferably used.
  • titania, zirconia, etc. can be prepared by the same method, and a commercial item can be used.
  • These metal oxides may be a composite oxide prepared by a coprecipitation method or the like, and can be suitably used as a fluorination catalyst in this step.
  • a metal-supported catalyst can be used as the fluorination catalyst.
  • the type, amount, and method of the supported metal can be selected based on ordinary knowledge of those skilled in the art of catalyst.
  • Metal-supported catalyst As the metal-supported catalyst, nitrate, chloride, oxide of at least one metal selected from the group consisting of chromium, titanium, aluminum, manganese, nickel, cobalt, zirconium, iron, copper, silver, molybdenum, and antimony,
  • a metal-supported catalyst in which sulfate, fluoride, fluorinated chloride, oxyfluoride, oxychloride or oxyfluorinated chloride is supported on a support such as fluorinated alumina or activated carbon can be employed.
  • a method for preparing the metal-supported catalyst a method in which a carrier is impregnated with a solution in which one or more kinds of metal compounds are dissolved in a solvent, or is sprayed and adhered can be used.
  • Examples of the metal compound soluble in the solvent include nitrates, chlorides, oxides and sulfates of the above metals. Specifically, chromium nitrate, chromium trichloride, chromium trioxide, potassium dichromate, iron chloride, iron sulfate, iron nitrate, titanium trichloride, titanium tetrachloride, manganese nitrate, manganese chloride, manganese dioxide, nickel nitrate, Examples thereof include nickel chloride, cobalt nitrate, cobalt chloride, copper nitrate, copper sulfate, copper chloride, silver nitrate, copper chromite, copper dichromate, silver dichromate, and sodium dichromate.
  • the solvent is not particularly limited as long as it dissolves the metal compound and does not alter the metal compound.
  • water alcohols such as methanol, ethanol or isopropanol, ketones such as methyl ethyl ketone or acetone, ethyl acetate or Examples thereof include carboxylic acid esters such as butyl acetate, halogen compounds such as methylene chloride, chloroform and trichloroethylene, and aromatics such as benzene and toluene.
  • the dissolution may be accelerated by adding an acid such as hydrochloric acid, sulfuric acid nitrate or aqua regia, or an alkali such as sodium hydroxide, potassium hydroxide or ammonia water. it can.
  • an acid such as hydrochloric acid, sulfuric acid nitrate or aqua regia
  • an alkali such as sodium hydroxide, potassium hydroxide or ammonia water. it can.
  • a catalyst in order to increase the reaction rate, selectivity of trans-1,3,3,3-tetrafluoropropene and yield in this step, as a catalyst, chromium, iron or copper nitrate, chloride, oxide as fluorinated alumina Alternatively, a metal-supported catalyst supporting sulfate or the like can be used.
  • the selectivity and yield of trans-1,3,3,3-tetrafluoropropene, nitrate, chloride, oxide or sulfuric acid selected from chromium, iron or copper A metal-supported catalyst in which a salt is supported on activated carbon can be used, and a metal compound selected from chromium oxide, fluoride, chloride, fluorinated chloride, oxyfluoride, oxychloride or oxyfluorinated chloride is activated carbon.
  • a metal-supported catalyst supported on the catalyst can be used.
  • the activated carbon supporting the fluorination catalyst which is a catalyst, includes vegetation based on wood, sawdust, charcoal, coconut shell charcoal, palm kernel charcoal, or raw ash, peat, lignite, lignite, bituminous coal, anthracite, etc.
  • a raw material coal-based, petroleum residue, sulfuric acid sludge or oil carbon as a raw material, or synthetic resin as a raw material.
  • Such activated carbon is commercially available and can be selected from commercially available products and used in this reaction step.
  • activated carbon (trade name, Calgon granular activated carbon CAL, manufactured by Calgon Carbon Japan Co., Ltd., etc.), coconut shell charcoal (manufactured by Nippon Enviro Chemicals Co., Ltd.) and the like manufactured from bituminous coal can be exemplified.
  • the activated carbon used in the parallel production method of the present invention is not limited to these types and manufacturers.
  • activated carbon is normally used in a granular form, the shape, particle size, and the like are not particularly limited.
  • the activated carbon may be used as it is, or activated carbon previously modified with a halogen such as hydrogen fluoride, hydrogen chloride, chlorinated fluorinated hydrocarbon, or the like.
  • the amount of metal supported on the carrier is 0.1% by mass or more and 80% by mass or less, preferably 1% by mass or more and 50% by mass or less based on the carrier.
  • the amount is less than 0.1% by mass, the catalytic effect is thin, and it is difficult to support more than 80% by mass and there is no necessity.
  • fluorine such as hydrogen fluoride, fluorinated hydrocarbon or fluorinated chlorinated hydrocarbon is previously used at a temperature equal to or higher than a predetermined reaction temperature before use in the reaction. It is effective to heat together with the agent to prevent changes in the composition of the catalyst during the reaction.
  • the amount of the fluorination catalyst added is preferably equal to or less than the amount of the raw material compound supplied to the reactor. It is not necessary to use more than 1x.
  • a gas such as oxygen, air or chlorine may be added as a companion gas in the reaction vessel as long as the reaction is not hindered.
  • An inert gas having poor reactivity such as nitrogen, argon, or helium, is preferable.
  • the supply amount of the gas is less than 1 times the total volume of organic substances and hydrogen chloride as reactants. If the amount of inert gas supplied to the reactor is 1 or more times, it is difficult to recover trans-1,3,3,3-tetrafluoropropene in the subsequent “purification step” (sixth step). .
  • activation of fluorination catalyst For the activation (activation or regeneration) of the fluorination catalyst used, a usual method used for regeneration of the fluorination catalyst can be employed.
  • the catalyst having reduced activity at a temperature equal to or higher than the reaction temperature employed in this step can be activated by appropriately contacting it with dry air, chlorine, hydrogen fluoride or the like while controlling heat generation.
  • reaction temperature The reaction temperature in this step is 200 ° C. or higher and 450 ° C. or lower, preferably 350 ° C. or higher and 400 ° C. or lower.
  • reaction temperature is lower than 200 ° C.
  • the reaction rate is slow and the reaction is difficult to proceed, which is not practical.
  • reaction temperature exceeds 450 ° C., the reaction proceeds rapidly, but decomposition products, high molecular weight organic substances, etc. are generated, and the selectivity for trans-1,3,3,3-tetrafluoropropene is lowered, which is not preferable. .
  • the higher the reaction temperature the faster the reaction proceeds because the equilibrium state in the reactor is closer to the target product.
  • reaction pressure is preferably reduced or equal to normal pressure (atmospheric pressure, about 0.1 MPa, the same shall apply hereinafter), but is not limited as long as it does not inhibit the reaction even if the pressure is higher than atmospheric pressure.
  • normal pressure atmospheric pressure, about 0.1 MPa, the same shall apply hereinafter
  • the existing hydrogen fluoride and organic matter do not have to be liquefied in the reaction system of this step, and the pressure is 0.05 MPa or more and 0.3 MPa or less.
  • reaction time The contact time (reaction time) in the gas phase reaction is usually from 0.1 seconds to 300 seconds, preferably from 3 seconds to 60 seconds. If the contact time is shorter than 0.1 seconds, the reaction may not proceed, and preferably 3 seconds or more. If it is longer than 300 seconds, it takes too much process work time (tact time) in the actual production in the plant, which is not efficient. Preferably, it is 60 seconds or less.
  • the molar ratio of hydrogen fluoride to 1-chloro-3,3,3-trifluoropropene should basically be such that hydrogen fluoride is greater than the theoretical value, but trans-1,3,3,
  • hydrogen fluoride: 1-chloro-3,3,3-trifluoropropene range 8: 1 to 25: 1 It is preferable that If hydrogen fluoride is excessively supplied so that this ratio exceeds 25: 1, unreacted hydrogen fluoride contained in the reaction product A of this step and the target product 1,3,3,3- This hinders separation of organic substances such as tetrafluoropropene by distillation.
  • hydrogen fluoride is supplied too little so that this ratio is smaller than 8: 1, the reaction rate is lowered and the selectivity for trans-1,3,3,3-tetra
  • the material of the reactor should be heat resistant and have corrosion resistance against hydrogen fluoride and hydrogen chloride, and it is preferable to use stainless steel, nickel alloy, platinum or the like.
  • Hastelloy (trade name) with nickel as the main component and molybdenum, nickel or chromium added
  • Monel product name with nickel as the main component and copper
  • the fraction B in this step is hydrogen fluoride that could not be recovered from the reaction product A in this step, the target product, trans-1,3,3,3-tetrafluoropropene, and the by-product chloride. And other organics.
  • the fraction B is sent to the “hydrogen fluoride separation step” (third step) of the next step.
  • the fraction B has a different composition depending on the reaction conditions of the preceding step “reaction step” (first step), but is generally 1-chloro-based on 1 mol of 1,3,3,3-tetrafluoropropene.
  • 3,3,3-trifluoropropene is 0.5 mol or more and 1 mol or less
  • 1,1,1,3,3-pentafluoropropane is 0.1 mol or more and 0.2 mol or less
  • hydrogen chloride is 1
  • the moles are 1.5 moles or more and 1.5 moles or less
  • hydrogen fluoride is 0.5 moles or more and 10 moles or less.
  • distillation conditions in this step are preferably 0.1 MPa or more and 1.0 MPa or less as the operating pressure.
  • the temperature conditions are the tower bottom temperature of 5 ° C. or more and 25 ° C. or less, the tower top temperature ⁇ 20 degreeC or more and 5 degrees C or less are preferable.
  • the cooling heat transfer area of the separation tower can be reduced. In that case, it is preferable to provide a compressor at the inlet of the separation tower and a pressure regulating valve at the outlet.
  • the packing material for the separation tower includes hydrogen fluoride, stainless steel that is corrosion resistant to hydrogen chloride, nickel, the nickel alloy such as the trade name Hastelloy or the trade name Monel, tetrafluoroethylene resin, chlorotrifluoroethylene resin, and vinylidene fluoride.
  • Regular packing made of fluororesin such as resin or tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer resin (hereinafter sometimes abbreviated as PFA), or irregular packing such as lessing ring, pole ring or sulzer packing Can be used.
  • Number of separation towers The number of stages of the separation column varies depending on the operating pressure, but it may be 15 or more at normal pressure.
  • Hydrogen fluoride separation process (third process) In the “hydrogen fluoride separation step”, hydrogen fluoride is recovered from the fraction B after the bottoms are recovered in the “distillation step” (second step) and supplied to the gas phase reactor in the reaction step. It is a process.
  • the fraction B contains hydrogen fluoride, hydrogen chloride, trans-1,3,3,3-tetrafluoropropene and other organic substances distilled from the separation column in the “distillation step” (second step).
  • hydrogen fluoride is absorbed into sulfuric acid by a contact operation between fraction B and sulfuric acid. That is, a liquid phase part mainly composed of hydrogen fluoride and sulfuric acid, 1,3,3,3-tetrafluoropropene, 1-chloro-3,3,3-trifluoropropene and 1,1,1,3, Hydrogen fluoride can be separated and recovered by dividing it into an organic substance such as 3-pentafluoropropane and a gas phase portion mainly composed of hydrogen chloride, and mainly separating hydrogen fluoride from the liquid phase portion.
  • the gas phase portion is supplied as the residue C to the subsequent “hydrogen chloride separation step” (fourth step).
  • the liquid phase part mainly composed of hydrogen fluoride and sulfuric acid obtained in this step evaporates hydrogen fluoride by heating, and then condenses it to separate and recover hydrogen fluoride.
  • the recovered hydrogen fluoride can be supplied again to the “reaction step” (first step).
  • any apparatus configuration and operation method may be adopted as long as hydrogen fluoride can be absorbed into sulfuric acid, but it is preferable that fraction B is brought into contact with sulfuric acid in a gaseous state. Therefore, the liquid temperature of sulfuric acid is preferably 10 ° C. or higher and 50 ° C. or lower, more preferably 10 ° C. or higher and 30 ° C. or lower at normal pressure. Sulfuric acid and hydrogen fluoride form fluorosulfuric acid (fluorosulfonic acid) by reaction, but it is difficult to operate when the temperature of sulfuric acid is 10 ° C. or lower, and 1,3,3,3 in the reaction product at 50 ° C. or higher.
  • -Tetrafluoropropene and the like are not preferable because they are polymerized.
  • a method in which sulfuric acid is put into a tank and a fraction B is blown in a gas state, a method in which a fraction B is blown into a sulfuric acid washing tower filled with a packing, and a gas in the fraction B and sulfuric acid are brought into countercurrent contact is adopted.
  • absorption of hydrogen fluoride into sulfuric acid is possible, not only these methods but also other methods may be used.
  • Hydrogen chloride separation process (4th process) In this step, hydrogen chloride is brought into contact with the residue C after recovering hydrogen fluoride from the fraction B in the “hydrogen fluoride separation step” (third step) in the previous step, and then contacted with water or an aqueous sodium hydroxide solution. This is a step of separating and removing.
  • the residue C is washed with water by a method in which the residual C is blown into the water tank so as to be in a fine bubble state, a method in which the residue C is blown into the water washing tower filled with the packing and brought into countercurrent contact, and the hydrogen chloride is absorbed in water.
  • Liquid phase ie hydrochloric acid, 1,3,3,3-tetrafluoropropene, 1-chloro-3,3,3-trifluoropropene and 1,1,1,3,3-pentafluoropropane Hydrogen chloride is separated and removed from organic substances such as
  • any apparatus configuration and operation method may be adopted as long as hydrogen chloride can be separated and removed from the residue C.
  • the organic substance separated from hydrogen chloride can be recovered in a gas or liquid state.
  • a mixture having a high composition of low-boiling trans-1,3,3,3-tetrafluoropropene (boiling point ⁇ 19 ° C.)
  • it is absorbed in contact with water in a gaseous state, and hydrogen chloride is removed from the mixture of organic matter and hydrogen chloride. It is preferable to separate and recover.
  • the hydrochloric acid recovered by absorbing hydrogen chloride in water in this step can be purified using known means such as adsorbing impurities such as hydrogen fluoride and organic substances on an adsorbent such as zeolite.
  • hydrogen chloride may be separated and recovered by contacting the residue C after the “hydrogen fluoride separation step” (third step) in the previous step with an aqueous sodium hydroxide solution.
  • the solubility of hydrogen chloride in water is preferably 25% by mass in normal conditions and 37% by mass in saturated conditions at normal temperature and normal pressure. If the water is less than 3, excess hydrogen chloride is liable to vaporize and easily volatilize. Absent.
  • the “dehydration step” is a step of dehydrating the residue D after separating and removing hydrogen chloride in the “hydrogen chloride separation step” (fourth step) of the previous step.
  • Residue D is accompanied by entrained water such as water, gaseous mist, etc. by water washing in the preceding step “hydrogen chloride separation step” (fourth step) or contact with an aqueous sodium hydroxide solution.
  • entrained water such as water, gaseous mist, etc.
  • hydroxide separation step fourth step
  • aqueous sodium hydroxide solution aqueous sodium hydroxide solution.
  • a residue D containing a large amount of water exceeding the saturated water amount after the “hydrogen chloride separation step” (fourth step) in the previous step a mixed gas in which organic substances such as 1,3,3,3-tetrafluoropropene, 1-chloro-3,3,3-trifluoropropene, 1,1,1,3,3-pentafluoropropane are mixed Is introduced into a heat exchanger set to a temperature equal to or lower than the condensation temperature of these organic substances, and condensed on a cooling surface, which is a cooled heat transfer surface, to substantially remove entrained water.
  • the melted frozen water is discharged from the lower part of the heat exchanger as a dehydrator in the state of water or steam.
  • the molten water containing this organic substance can be used in the “hydrogen chloride separation step” (fourth step) in the previous step.
  • the heat exchanger used for freezing the entrained water in the residue D is preferably a partition-type heat exchanger, and is cooled through the partition walls of the partition-type heat exchanger. Heat exchange is performed between the medium and the residue D.
  • the partition wall is provided with a heat transfer surface in contact with the cooling medium and a cooling surface for freezing and solidifying the mixed water of the mixed gas. Examples of such a partition wall type heat exchanger include a double tube type, a cylindrical multiple tube type, a cylindrical coil type, or a cylindrical heat exchanger with a jacket.
  • a heat exchanger in which the heat transfer area is expanded by attaching an external jacket to a cylindrical multi-tube type or a cylindrical coil type can also be used.
  • the material of the heat exchanger is preferably a metal having high thermal conductivity, such as iron, steel, copper, lead, zinc, brass, stainless steel, titanium, aluminum, magnesium, or nickel such as trade name Monel, trade name Inconel or Hastelloy.
  • a heat exchanger in which a resin lining, ceramics, glass lining, or the like is applied to the heat transfer surface on the side where the mixed gas is cooled and condensed can be used.
  • the heat transfer area of the heat exchanger depends on the temperature of the cooling medium used, but at a minimum, the area sufficient to condense the gaseous residue D and exchange the amount of heat necessary to freeze the accompanying water. It is preferable that there is. In addition, since the heat transfer coefficient decreases when entrained water freezes and solidifies on the cooling surface of the heat exchanger, it is preferable to take at least 1.5 times the heat transfer area necessary for calculation.
  • a heat exchanger with fins attached to the heat transfer surface can be used.
  • it is also effective from the viewpoint of heat transfer efficiency to attach fins to the cooling surface side with which the residue D is in contact to expand the heat transfer area.
  • Examples of the method for introducing the residue D into the heat exchanger include a flow-through method in which the residue D is passed through a heat exchanger having a sufficient heat transfer area.
  • the direction of introduction of the residue D which is a mixed gas, is preferably such that the gas is introduced from the top when the heat exchanger is a vertical type, in which case freezing and solidification of the entrained water starts from the top of the cooling surface of the heat exchanger. Since it occurs and closes, it is desirable to provide a plurality of inlets at the bottom and move the introduction of the residue D to the bottom.
  • the heat exchanger can be used as a horizontal type, and in this case as well, it is desirable to introduce the residue D from the top, and a plurality of inlets can be provided in parallel.
  • the cooling medium used for heat exchange is not particularly limited, but an aqueous medium, inorganic brine, or organic brine can be selected and used depending on the cooling temperature.
  • the liquefied gas is evaporated again and supplied to the distillation tower.
  • the latent heat of vaporization of liquefied trans-1,3,3,3-tetrafluoropropene can be used. If evaporation of the liquefied gas is performed on the cooling medium flow side of the heat exchange dehydrator, the heating and heat removal load by the external heat source can be reduced, which is also effective from the viewpoint of energy saving.
  • the heat exchange dehydrator Preferably employed.
  • the set temperature of the cooling surface in the heat exchanger is not particularly limited, but gaseous trans-1,3,3,3-tetrafluoropropene (boiling point ⁇ 19 ° C.) is condensed under the operating pressure. Lower the temperature below the The cooling temperature is ⁇ 50 ° C. or higher and ⁇ 20 ° C. or lower, and preferably ⁇ 40 ° C. or higher and ⁇ 25 ° C. or lower at normal pressure.
  • the entrained water is removed by freezing and solidification, and the condensed and liquefied mixed gas is collected in a receiving tank provided at the lower part of the heat exchanger.
  • the temperature of the receiving tank is preferably not higher than the temperature at which trans-1,3,3,3-tetrafluoropropene is condensed.
  • a U-shaped or coil-type cooling pipe is installed inside the receiving tank, and liquefied 1,3,3,3-tetrafluoropropene, 1-chloro-3,3,3-trifluoropropene and 1,1,3 It is also possible to remove the entrained water in the residue D containing 1,3,3-pentafluoropropane by freezing and solidifying.
  • the dehydration using the heat exchanger in this step may be performed under pressurized conditions, and the pressure of the mixed gas in the heat exchanger is usually preferably 0.1 MPa or more and 1 MPa or less.
  • the cooling temperature under the pressurizing condition can be appropriately selected according to the processing pressure.
  • the linear velocity of the residue D to be dehydrated in the heat exchanger is about 30 m / hr or more and 1200 m / hr or less, and preferably 60 m / hr or more and 600 m / hr or less. If the linear velocity is less than 30 m / hr, the dehydration time becomes longer, which is not preferable. When it is higher than 1200 m / hr, the freezing and coagulation of the entrained water in the residue D and the condensation of the organic matter become insufficient, which is not preferable.
  • the amount of frozen water adhering to the cooling surface of the heat exchanger which is a dehydrator, increases as the flow time of the mixed gas containing water increases. For this reason, it is necessary to melt and remove frozen water after a certain period of time.
  • a method for melting and removing frozen water a method can be used in which a dried inert gas having a temperature of 5 ° C. or higher and 200 ° C. or lower is circulated from the top of the heat exchanger as a dehydrator.
  • the temperature of the inert gas may be high, but is preferably 20 ° C. or higher and 100 ° C.
  • the cooling medium and the heating medium are not limited to be the same substance or different substances.
  • the type of inert gas is not particularly limited, but it is desirable to use dry air or dry nitrogen from the viewpoint of economy.
  • a method of dehydrating using an adsorbent for example, a method of dehydrating by contacting with a specific zeolite is carried out regardless of whether 1,3,3,3-tetrafluoropropene in the residue D is in a gaseous state or a liquid state. It is possible and excellent.
  • this dehydration method is carried out using a dehydration tower packed with zeolite, the residue D after the “hydrogen chloride separation step” (fourth step) in the previous step contains water vapor and has a water content of 1000 ppm or more.
  • the residue D when further moisture reduction is desired, the residue D is dehydrated such as calcium chloride, calcium oxide, magnesium sulfate, or diphosphorus pentoxide at a later stage of this step. It can be dried by contacting with an adsorbent or an adsorbent such as silica gel or zeolite.
  • the “purification step” is a step of rectifying the residue E after dehydration in the previous step “dehydration step” (fifth step) to obtain a fraction containing trans-1,3,3,3-tetrafluoropropene. It is. In this case, a residue F containing cis-1,3,3,3-tetrafluoropropene is obtained.
  • Rectification can be carried out either batchwise or continuously, and can be carried out at normal pressure or under pressure, but pressure conditions that can increase the condensation temperature in rectification should be selected. Is preferred.
  • Rectification can be carried out batchwise using a single multi-stage distillation column, but it is more efficient to carry out rectification continuously using a double distillation column comprising a first distillation column and a second distillation column. .
  • low-boiling point 3,3,3-trifluoropropyne, 2,3,3,3-tetrafluoropropene and the like, which are by-products contained in a trace amount in the residue E, are removed from the top of the distillation column. It is recovered as a distillate and returned again to the reaction system of the “reaction step” (first step), that is, supplied to the gas phase reactor for reuse and 1,1,1,3,3-penta Fluoropropane is obtained.
  • the bottoms of the first distillation column can be distilled, and the target trans-1,3,3,3-tetrafluoropropene can be recovered as a distillate from the top of the distillation column. .
  • cis-1,3,3,3-tetrafluoropropene and 1-chloro-3,3,3-trifluoropropene are recovered as a bottom boiling liquid, and the first “reaction step” (No. 1 step) and can be reused.
  • the recovered mixture of cis-1,3,3,3-tetrafluoropropene, 1-chloro-3,3,3-trifluoropropene and 1,1,1,3,3-pentafluoropropane If a distillation column is used, it can be separated and purified by operations such as extractive distillation.
  • the distillation column used in this step may be any wall as long as the wall surface is inert to the distillate, the wall surface may be made of glass or stainless steel, tetrafluoroethylene resin, chlorotrifluoroethylene resin on a substrate such as steel Also, a distillation column having a vinylidene fluoride resin, PFA resin or glass lined inside may be used.
  • the distillation column may be a plate type or a packed column packed with packing such as Raschig ring, Lessing ring, Dickson ring, pole ring, interlock saddle or sulzer packing.
  • the rectification can be performed at normal pressure, but it is preferable to perform the rectification under a pressurized condition because the pressure loss in the distillation column can be reduced and the load on the condenser can be reduced.
  • the number of distillation columns required for the rectification operation is not limited, but is preferably 5 to 100, more preferably 10 to 50. If the number of stages is less than 5, the purity of trans-1,3,3,3-tetrafluoropropene does not increase sufficiently, and if the number of stages is 100 or more, the economic burden of the distillation column itself increases. In addition, the time required for the rectification operation is increased, which is not preferable.
  • the boiling point of 1-chloro-3,3,3-trifluoropropene is 21 ° C. for the trans isomer and 39 ° C. for the cis isomer.
  • the boiling point of 1,3,3,3-tetrafluoropropene is ⁇ 19 ° C. for the trans isomer and 9 ° C. for the cis isomer.
  • the boiling point of 1,1,1,3,3-pentafluoropropane is 15 ° C. From these mixtures, trans-1,3,3,3-tetrafluoropropene is separated and purified by rectification due to the difference in boiling point. Is possible.
  • antimony pentachloride for example, to convert cis-1,3,3,3-tetrafluoropropene to 1,1,1,3,3-pentafluoropropane, antimony pentachloride, antimony trichloride, antimony pentabromide, triodor
  • At least one metal compound selected from antimony fluoride, tin tetrachloride, titanium tetrachloride, molybdenum pentachloride, tantalum pentachloride, niobium pentachloride, and the like can be used. It is preferable to use a metal-supported catalyst that is a solid catalyst supported on a support such as activated carbon, fluorinated alumina, or fluorinated zirconia.
  • Cis-1,3,3,3-tetrafluoropropene is preferably reacted with excess hydrogen fluoride in the gas phase or with hydrogen fluoride in the liquid phase, and in particular, antimony pentachloride is activated carbon. It is preferable to continuously react with hydrogen fluoride using a supported metal supported catalyst.
  • a distillation operation is performed in the “distillation step”, and the reaction product A after the “reaction step” is distilled to give unreacted 1-chloro-3,3,3-trifluoro. It is characterized in that most of propene and hydrogen fluoride are recovered by distillation as a bottoms which is a liquid rich in low volatility components obtained from the bottom of the distillation column.
  • reaction step if an excessive amount of hydrogen fluoride is supplied into the reaction system of the “reaction step”, a large amount of unreacted hydrogen fluoride remains in the reaction product A, and hydrogen fluoride remains. If the rectification to obtain trans-1,3,3,3-tetrafluoropropene by distilling the reaction product A in such a state, the rectification load increases. However, in the parallel production method of the present invention, most of the hydrogen fluoride was separated and recovered in the “distillation step” that follows the “reaction step”. In addition, the fraction B after the “distillation step” is sent to the “hydrogen fluoride separation step” in the next step, and the remaining hydrogen fluoride is separated and recovered to form a residue C.
  • the “hydrogen chloride separation step” in the next step The hydrogen chloride produced as a by-product is separated and removed to form a residue D, and the residue after dehydration in the next “dehydration step” is rectified in the “purification step”.
  • the reaction product (residue C) is washed with water or brought into contact with an aqueous sodium hydroxide solution to separate and remove hydrogen chloride, entrained water is mixed into the reaction product. Since the entrained water is dehydrated in the “dehydration step”, rectification of trans-1,3,3,3-tetrafluoropropene in the “purification step” is facilitated.
  • the common production method of the present invention is the above-mentioned “conversion step”, wherein cis-1,3,3,3-tetrafluoropropene in residue F after “purification step” is trans-1,3,3,3-tetrafluoro.
  • conversion step By converting to propene, 1,1,1,3,3-pentafluoropropane is obtained, and trans-1,3,3,3-tetrafluoropropene, 1,1,1,3,3-pentafluoropropane and Can be produced in parallel.
  • reaction product A From the reaction product A, most of unreacted 1-chloro-3,3,3-trifluoropropene and hydrogen fluoride were separated and recovered as bottoms, and the recovered 1-chloro-3,3,3- Returning trifluoropropene and hydrogen fluoride back to the initial “reaction step” is a recyclable and environmentally friendly process that is efficient in industrial production.
  • the parallel production method of the present invention comprises 1-chloro-3,3, after rectifying the residue E to obtain trans-1,3,3,3-tetrafluoropropene in the first “purification step”.
  • this step further re-feeding of unreacted substances and effective utilization of by-products can be achieved.
  • FIG. 1 is an example of the method of the present invention. The method of the present invention is not limited to the following method.
  • reaction step 1-chloro-3,3,3-trifluoropropene and hydrogen fluoride as raw materials a are reacted in the gas phase reactor 1 in the presence of a fluorination catalyst.
  • the reaction for obtaining trans-1,3,3,3-tetrafluoropropene is carried out.
  • the reaction product A after the reaction is supplied to the separation column 2 of the “distillation step” (second step) for distillation, and trans-1,3,3,3-tetrafluoropropene, hydrogen chloride and hydrogen fluoride. And the like and other fractions containing organic matter and unreacted 1-chloro-3,3,3-trifluoropropene and hydrogen fluoride in the bottom b of the separation column 2 are separated. Is supplied to the gas phase reactor 1 and reused as a raw material compound. Distillation B, which is a distillate rich in highly volatile components, is obtained from the top of the separation column 2 by distillation, and a bottom b, rich in low volatile components, is obtained from the bottom.
  • the bottoms b stored in the lower heating tank of the separation column 2 is an organic substance mainly composed of 1-chloro-3,3,3-trifluoropropene and 1,1,1,3,3-pentafluoropropane.
  • recovering the hydrogen fluoride and returning it to the gas phase reactor 1 in the reaction step reacts the raw material compound 1-chloro-3,3,3-trifluoropropene with hydrogen fluoride, trans-1, It is effective for obtaining 3,3,3-tetrafluoropropene and can improve the efficiency of the parallel production method of the present invention.
  • the fraction B is sent to the hydrogen fluoride absorption tower 3 and comes into contact with sulfuric acid, so that hydrogen fluoride is absorbed by sulfuric acid.
  • the mixture c containing sulfuric acid and hydrogen fluoride is sent to the stripping tower 4, hydrogen fluoride d is taken out, and the taken out hydrogen fluoride d is supplied to the gas phase reactor 1 and reused as a raw material compound. .
  • Residue C after the recovery of hydrogen fluoride d is introduced into hydrogen chloride absorption tower 5 in the “hydrogen chloride separation process” (fourth process), and in hydrogen chloride absorption tower 5, water or sodium hydroxide is introduced. It is washed with water by means such as contact mixing with an aqueous solution, for example, bubbling, and hydrogen chloride e is separated and removed.
  • the residue D from which the hydrogen chloride e has been separated and removed is introduced into the mist separator 6 and dehydrated to remove the moisture h1, if necessary, in the “dehydration step” (fifth step). Thereafter, the residue D is introduced into the heat exchanger 7, the entrained water in the residue D is cooled and frozen and solidified, and the organic matter in the residue D is cooled and condensed from the gas to become a liquefied product. Water h2 is removed.
  • the composition ratio of the reaction product in this example is such that a reaction product containing a distillate from a distillation column is directly injected into gas chromatography (hereinafter abbreviated as GC), and a hydrogen flame is applied to the detector. Measurement was performed using an ion detector (hereinafter abbreviated as FID). The composition ratio of each component is shown as a molar ratio determined from the area of the GC chart.
  • a fluorination catalyst used for the reaction for producing trans-1,3,3,3-tetrafluoropropene was prepared by the following procedure.
  • Activated alumina having a particle size of 2 mm to 4 mm (manufactured by Sumitomo Chemical Co., Ltd., trade name, NKHD-24, specific surface area, 340 m 2 / g) was weighed and washed at 1200 g. Next, 460 g of hydrogen fluoride was dissolved in 4140 g of water to prepare 10% by mass hydrofluoric acid. While stirring 10% by mass of hydrofluoric acid, the washed activated alumina was gradually added, and then allowed to stand for 3 hours. The activated alumina was again washed with water and filtered, and then heated to 200 ° C. in an electric furnace and dried for 2 hours.
  • SUS316L stainless steel
  • the flow rate of hydrogen fluoride and nitrogen and the ratio of hydrogen fluoride and nitrogen were adjusted so that the temperature of the activated alumina did not exceed 350 ° C.
  • the set temperature of the heat medium was changed to 450 ° C., and hydrogen fluoride and nitrogen were further introduced for 2 hours to prepare fluorinated alumina.
  • 2016 g of a commercially available special grade reagent, CrCl 3 .6H 2 O was dissolved in pure water to obtain a 1 L (1000 cm 3 ) aqueous solution.
  • 1500 ml (1500) of the prepared fluorinated alumina was immersed and allowed to stand overnight.
  • the fluorinated alumina was removed by filtration, and further dried in a hot air circulating dryer heated to 100 ° C. for a whole day and night to obtain a chromium-supported fluorinated alumina.
  • a hot air circulating dryer heated to 100 ° C. for a whole day and night to obtain a chromium-supported fluorinated alumina.
  • the temperature of the reaction tube was raised to 300 ° C. while flowing nitrogen gas, and water was retained from the reaction tube.
  • nitrogen fluoride was accompanied by hydrogen fluoride and introduced into the reaction tube to gradually increase the concentration of hydrogen fluoride.
  • the temperature of the reaction tube is increased to 450 ° C., then 1 hour at 450 ° C.
  • the fluorination catalyst was obtained by keeping the time.
  • CTFP 1-chloro-3,3,3-trifluoropropene
  • HF hydrogen fluoride
  • Fluorine prepared in Preparation Example 1 or Preparation Example 2 was added to a stainless steel (SUS316L) tubular gas phase reactor 1 made of a cylindrical reaction tube having a diameter of 1 inch (about 2.54 cm) and a length of 30 cm. 50 ml (50 cm 3 ) of the fluorination catalyst was charged.
  • SUS316L stainless steel
  • the reaction tube of the gas phase reactor 1 is heated to 200 ° C., then hydrogen fluoride is flowed at a flow rate of 0.10 g / min, In the reaction tube, the reaction tube was heated to 450 ° C. and kept for 1 hour while being accompanied by nitrogen.
  • the temperature of the reaction tube is lowered to 360 ° C. or 380 ° C., and hydrogen fluoride (HF) is supplied at a rate of 0.25 g / min or 0.49 g / min to pre-vaporize 1-chloro-3,3 , 3-trifluoropropene (CTFP) was fed to the gas phase reactor 1 at a rate of 0.16 g / min.
  • HF hydrogen fluoride
  • the reaction is stabilized after 1 hour from the start of the reaction, and then the product gas as the reaction product A distilled from the gas phase reactor 1 is blown into water for 2 hours, and then the acidic gas is separated and removed. 6.0 to 8.0 g of organic matter was collected with an acetone trap, and GC analysis of the collected organic matter was performed.
  • CTFP: HF 1: 8
  • CTFP 1-chloro-3,3,3-trifluoropropene
  • HF hydrogen fluoride
  • Table 1 shows the ratio (selectivity) of reaction product A to the reaction conditions measured by GC using an FID detector.
  • the unit is mol%, and is obtained from the area for each organic substance in the GC chart by the FID detector using an area percentage method in which the total area of the gas chromatography peak is 100%.
  • trans-1,3,3,3-tetrafluoropropene when the supply rate of hydrogen fluoride (HF) was 0.25 g / min.
  • HF feed rate 0.49 g / min
  • trans-1,3,3,3-tetrafluoropropene trans-TFP
  • the selectivity of trans-1,3,3,3-tetrafluoropropene is higher at 380 ° C. than at the reaction temperature of 360 ° C.
  • trans-1,3,3 under the conditions of HF supply rate of 0.25 g / min and reaction temperature of 360 ° C.
  • the selectivity of 1,3-tetrafluoropropene (trans-TFP) is 32.1 mol%, but 34.5% at a reaction temperature of 380 ° C.
  • the selectivity for trans-1,3,3,3-tetrafluoropropene (trans-TFP) at a feed rate of HF of 0.49 g / min and a reaction of 360 ° C. was 44.4 mol%, but the reaction temperature It is 46.6 mol% at 380 ° C.
  • trans-1,3,3,3-tetrafluoropropene (trans-TFP) under the conditions of HF supply rate of 0.25 g / min and reaction temperature of 360 ° C.
  • the selectivity of is 30.3 mol%, but it is 33.1 mol% at a reaction temperature of 380 ° C.
  • the catalyst of Catalyst Preparation Example 1 was used, the temperature of the reaction tube was set to 150 ° C., and hydrogen fluoride (HF) was supplied at a rate of 0.25 g / min or 0.49 g / min to vaporize in advance
  • HF hydrogen fluoride
  • CTFP Chloro-3,3,3-trifluoropropene
  • the reaction is stabilized after 1 hour from the start of the reaction, and then gas is distilled from the gas phase reactor 1 for 2 hours to blow water into the water to remove the acidic gas, and then 8.5 g of organic matter in a dry ice-acetone trap. Was collected, and gas chromatography analysis of the collected organic matter was performed.
  • Separation tower 2 is a distillation tower, having a heating tank for heating the bottoms at the bottom, a cooling condenser for liquefying the distillate at the top, and an inner diameter of separation tower 2 of 54.9 mm, The length was 40 cm and filled with 6 mm Raschig rings.
  • CTFP 1-chloro-3,3,3-trifluoropropene
  • HF hydrogen fluoride
  • reaction product A which is a gas
  • Table 2 shows the distillation conditions in the separation tower 2 and the composition measurement results of the distillate (fraction B).
  • distillation was performed under two types of distillation conditions in which the temperature setting of the heating tank and the temperature setting of the cooling condenser were changed. Specifically, as condition 1, the temperature of the heating tank is 24 ° C., the temperature of the cooling condenser is ⁇ 5 ° C., the pressure in the separation tower 2 is 0.2 MPa, and as the condition 2, the temperature of the heating tank is 25 ° C. Distillation was performed using the separation tower 2 at a condenser temperature of 1 ° C. and a pressure in the separation tower 2 of 0.2 MPa.
  • the distillation rate in Table 2 means the organic matter, HF or HCl in the fraction B, which is a distillate in distillation, when the amount of the organic matter, HF or HCl in the reaction product A is 100, respectively. Is expressed in mol%. That is, the calculation was performed by dividing the molar amount (in the fraction B) at the outlet by the molar amount (in the reaction product A) at the inlet of the separation tower 2 of each compound.
  • Distillation rate of organic substance in fraction B of condition 1 is 48.1 mol%, distillation rate of hydrogen fluoride (HF) is 6.9 mol%, distillation rate of hydrogen chloride is 91.8 mol%
  • concentration of trans-1,3,3,3-tetrafluoropropene (trans-TFP) in the organic substance is 26.0 mol% at the inlet of the separation tower 2 and 55.6 mol% at the outlet, and the concentration ratio Was 2.1.
  • the distillation rate of organic matter in fraction 2 of condition 2 is 63.8 mol%, the distillation rate of hydrogen fluoride (HF) is 10.2 mol%, and the distillation rate of hydrogen chloride is 91.5 mol%.
  • trans-1,3,3,3-tetrafluoropropene (trans-TFP) in the organic substance is 26.6 mol% at the inlet of the separation tower 2 and 42.5% at the distillate at the outlet of the separation tower 2.
  • concentration ratio was 2.1.
  • trans-1,3,3,3-tetrafluoropropene Is 26.0 mol%
  • cis-1,3,3,3-tetrafluoropropene cis-TFP1234zeZ
  • PFP 1,1,1,3,3-pentafluoropropane
  • CTFP 1-chloro-3,3,3-trifluoropropene
  • the composition of the organic substance in the outlet gas of the separation tower 2, that is, the fraction B of the separation tower 2 is 55.6 mol% of trans-1,3,3,3-tetrafluoropropene (trans-TFP).
  • Cis-1,3,3,3-tetrafluoropropene (cis-TFP) is 9.3 mol%
  • 1,1,1,3,3-pentafluoropropane (PFP) is 9.6 mol%
  • 1- Chloro-3,3,3-trifluoropropene (CTFP) was 25.3 mol%.
  • trans-1,3,3,3-tetrafluoropropene is the main component as the fraction B after the separation tower 2
  • trans-TFP trans-1,3,3,3-tetrafluoropropene
  • the above-mentioned condition 1 was adopted as the distillation condition using the separation tower 2 equipped with a cooling condenser at the top and a heating tank at the bottom, the inner diameter was 54.9 mm, the length was 40 cm, and 6 mm Raschig rings were packed.
  • a reaction for obtaining 3,3-tetrafluoropropene (trans-TFP) was carried out.
  • the reaction temperature is 360 ° C.
  • the supply of 1-chloro-3,3,3-trifluoropropene (CTFP) is 1.2 g / min
  • the supply of recovered organic matter is equal to 2.7 g / min.
  • the hydrogen fluoride (HF) was fed at 3.5 g / min or 7.1 g / min, and the reaction pressure was 0.1 MPa or 0.2 MPa.
  • 1,3,3,3-tetrafluoropropene (trans-TFP) was found to be 34.4 mol% and 29.2 mol when hydrogen fluoride (HF) was supplied at 3.5 g / min.
  • % Of hydrogen fluoride (HF) supplied at 7.1 g / min is 47.3 mol%
  • trans-1,3,3,3-tetrafluoropropene (trans-TFP) It was found that high selectivity can be obtained.
  • Residue C after separation of hydrogen fluoride was bubbled into water at a rate of 2.0 g / min in the hydrogen chloride absorption tower 5 in the hydrogen chloride separation step to remove hydrogen chloride e.
  • a SUS-316 mist separator 6 preliminarily filled with a SUS-316 filler and cooled with a refrigerant having a temperature of 5 ° C. was prepared. Residue D after separation of hydrogen chloride e was introduced into the prepared mist separator 6. The mist separator 6 removed mist-like entrained water h1 accompanying the residue D, which is a mixed gas. A gas in which a plurality of organic substances, which are the residue D at the outlet of the mist separator 6, was collected and the water content was measured by the Karl Fischer method. As a result, the water concentration was 1300 ppm.
  • the residue E which is an organic substance dehydrated by the above method, is rectified in the rectification column 8 in the purification step, and as a distillate, trans-1,3,3,3-tetrafluoropropene g (trans-TFP) is obtained. ) was isolated.
  • the water concentration measured by the Karl Fischer method was 78 ppm, and the purity measured by gas chromatography was 99.9%.
  • the generated hydrogen chloride is discharged from the pressure regulating valve provided at the rear of the reflux condenser, and after returning the pressure to normal pressure, the pressure regulating valve is closed, and the autoclave is cooled with dry ice-methanol to obtain cis-1,3,3, Add 114 g (1.0 mol) of 3-tetrafluoropropene and raise the reaction temperature to 50 ° C. while stirring. After 3.5 hours from the start of the reaction, cool the reactor to room temperature and lower the pressure to normal pressure. The gas distilled from the reactor through the aqueous layer and the concentrated sulfuric acid layer was collected in a trap cooled with dry ice-methanol.
  • the recovered organic substance weighed 123 g, and the product composition analyzed by gas chromatography was 98.5% 1,1,1,3,3-pentafluoropropane, 1,3,3,3-tetrafluoropropene. 0.4% and 1-chloro-3,3,3-trifluoropropene 0.1%.
  • Table 4 The results are shown in Table 4.
  • D residue including 1,3,3,3-tetrafluoropropene, 1-chloro-3,3,3-trifluoropropene, 1,1,1,3,3-pentafluoropropane, water, etc.
  • E Residue including 1,3,3,3-tetrafluoropropene, 1-chloro-3,3,3-trifluoropropene, 1,1,1,3,3-pentafluoropropane, etc.
  • F Residue (residue after obtaining trans-1,3,3,3-tetrafluoropropene as a fraction by rectification) a Raw materials (1-chloro-3,3,3-trifluoropropene and hydrogen fluoride) b Bottomed liquid (unreacted organic matter such as 1-chloro-3,3,3-trifluoropropene and hydrogen fluoride) c Hydrogen fluoride and sulfuric acid d Hydrogen fluoride e Hydrochloric acid h1, h2 Entrained water

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PCT/JP2013/061591 2012-04-26 2013-04-19 Procédé de production en parallèle de trans-1,3,3,3-tétrafluoropropène et de 1,1,1,3,3-pentafluoropropane Ceased WO2013161692A1 (fr)

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US20180057433A1 (en) * 2016-08-31 2018-03-01 Honeywell International Inc. AZEOTROPIC OR AZEOTROPE-LIKE COMPOSITIONS OF 1,3,3-TRICHLORO-3-FLUORO-1-ENE (HCFO-1231zd) AND HYDROGEN FLUORIDE (HF)
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US10029964B2 (en) 2016-08-30 2018-07-24 Honeywell International Inc. Azeotropic or azeotrope-like compositions of 3,3,3-trifluoropropyne and water
WO2019240233A1 (fr) * 2018-06-13 2019-12-19 ダイキン工業株式会社 Procédé de production de difluoroéthylène
CN115945180A (zh) * 2023-02-28 2023-04-11 天津绿菱气体有限公司 一种精制六氟-1,3-丁二烯的吸附剂及其制备方法与应用

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CN107522592B (zh) * 2017-09-07 2020-06-02 浙江衢化氟化学有限公司 一种联产多种卤代烯烃和氟代烷烃的方法
CN113527038B (zh) * 2020-04-22 2023-10-27 浙江省化工研究院有限公司 制备顺式-1,3,3,3-四氟丙烯的方法
CN113501743B (zh) * 2021-08-19 2024-03-29 山东华安新材料有限公司 一种1,1,1,3,3-五氟丙烷的制备方法

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CN115945180A (zh) * 2023-02-28 2023-04-11 天津绿菱气体有限公司 一种精制六氟-1,3-丁二烯的吸附剂及其制备方法与应用

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