WO2018079726A1 - Procédé de production de tétrafluoropropènes - Google Patents

Procédé de production de tétrafluoropropènes Download PDF

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WO2018079726A1
WO2018079726A1 PCT/JP2017/038955 JP2017038955W WO2018079726A1 WO 2018079726 A1 WO2018079726 A1 WO 2018079726A1 JP 2017038955 W JP2017038955 W JP 2017038955W WO 2018079726 A1 WO2018079726 A1 WO 2018079726A1
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catalyst
metal
reactor
fluoride
oxide
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PCT/JP2017/038955
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Japanese (ja)
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達也 鎌塚
優 竹内
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旭硝子株式会社
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    • 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
    • C07C21/00—Acyclic unsaturated compounds containing halogen atoms
    • C07C21/02—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds
    • C07C21/18—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B61/00—Other general methods

Definitions

  • the present invention relates to a method for producing tetrafluoropropene.
  • Patent Document 1 describes that 1214ya can be converted to 1224yd by contacting it with a catalyst layer of palladium-supported activated carbon at 80 to 90 ° C.
  • the conversion rate from 1214ya to 1224yd is about 20%, and furthermore, since an expensive palladium catalyst is used, it is disadvantageous for industrial production of 1224yd. .
  • 1,1-dichloro-2,2,3,3,3-pentafluoropropane (CCl 2 H—CF 2 —CF 3 , HCFC-225ca) is used in the presence of a phase transfer catalyst.
  • a method of producing the product through a step of dehydrofluorination by bringing it into contact with an alkali.
  • the waste liquid treatment is costly and is not an industrially advantageous method. Therefore, a method for producing fluorine-containing propene such as 1214ya and 1224yd by an industrially advantageous method is required.
  • the object of the present invention is to provide a method for producing tetrafluoropropene, which is a fluorine-containing propene such as 1214ya and 1224yd, in an industrially advantageous manner by using an easily available material.
  • the present invention provides a method for producing tetrafluoropropene having the following constitution.
  • General formula (1) CF 2 Cl—CFX—CClYZ (in general formula (1), one of X and Y is H and the other is F or Cl.
  • Z is H or Cl.
  • contact with the catalyst in the presence of hydrogen fluoride A method for producing tetrafluoropropene, wherein a tetrafluoropropene represented by the general formula (2): CF 3 CF ⁇ CClZ is obtained (in the general formula (2), Z is H or Cl).
  • [2] The method for producing tetrafluoropropene according to [1], wherein the catalyst includes at least one selected from a metal oxide, a partial halide of a metal oxide, and a metal halide.
  • the metal is an alkali metal, alkaline earth metal, Group 4 metal, Group 5 metal, Group 6 metal, Group 7 metal, Group 8 metal, Group 9 metal, Group 10 metal,
  • the metal is at least one selected from Li, Na, K, Cs, Mg, Ca, Sr, Ba, Al, Cr, Zr, Fe, Ni, Zn, Co, Mn, Sb, Nb, and Ta.
  • the metal oxide includes at least one selected from zinc oxide, chromium oxide, magnesium oxide, aluminum oxide, zinc-chromium composite oxide, chromium-magnesium composite oxide, and chromium-aluminum-magnesium composite oxide.
  • the method for producing tetrafluoropropene according to any one of [2] to [5] [7]
  • the metal oxide partial halide is a partial fluoride of zinc oxide, a partial fluoride of chromium oxide, or a partial fluoride of magnesium oxide.
  • the metal halide includes at least one selected from aluminum fluoride, chromium fluoride, lithium fluoride, potassium fluoride, magnesium fluoride, calcium fluoride, and zirconium fluoride, [2] to [5 ] The manufacturing method of tetrafluoropropene in any one of.
  • fluorine-containing propene such as 1214ya and 1224yd can be produced by an industrially advantageous method by using an easily available material.
  • the tetrafluoropropene production method of the present embodiment is obtained by contacting a fluorine-containing propane represented by the general formula (1): CF 2 Cl—CFX—CClYZ with a catalyst.
  • This is a method for obtaining a fluorinated propene represented by the general formula (2): CF 3 CF ⁇ CClZ.
  • one of X and Y is H, the other is F or Cl, and Z is H or Cl.
  • reaction represented by the above reaction formula [I] XY (HF or HCl) is once eliminated from the fluorine-containing propane (1) to produce a compound represented by the general formula CF 2 Cl—CF ⁇ CClZ. Then, it is considered that the allylic chlorine is fluorinated by reacting with the detached HF to produce the fluorinated propene (2).
  • 1224yd can be produced by contacting 234 cc and HCFC-234eb of the fluorinated propane (1) in which Z is H in the general formula (1) with a catalyst. Further, 1224yd can be produced by contacting HCFC-233bc and HCFC-233ea with a catalyst in the presence of hydrogen fluoride.
  • 1214ya can be produced by contacting 224ca and HCFC-224eb with a catalyst. 1214ya can be produced by contacting HCFC-223ba and HCFC-223eb with a catalyst in the presence of hydrogen fluoride.
  • Examples of the method for bringing the fluorinated propane (1) into contact with the catalyst include a method in which the raw material composition containing the fluorinated propane (1) and the catalyst are brought into contact with each other in the reactor.
  • the method of bringing the fluorine-containing propane (1) into contact with the catalyst in the presence of hydrogen fluoride can be performed by supplying hydrogen fluoride into a reactor in which the raw material composition and the catalyst are brought into contact.
  • the contact between the raw material composition and the catalyst may be performed in a liquid phase or in a gas phase.
  • the reaction in the gas phase is preferable because the reaction time can be shortened and the production of by-products can be suppressed.
  • the tetrafluoropropene production method of the present embodiment can be performed by either a batch method or a continuous method.
  • the method for producing tetrafluoropropene of the present embodiment is preferably a continuous method in terms of production efficiency.
  • the raw material composition contains fluorine-containing propane (1).
  • the fluorine-containing propane (1) contained in the raw material composition may be one type or two or more types.
  • the raw material composition may contain impurities other than fluorine-containing propane (1) in addition to fluorine-containing propane (1). Examples of impurities contained in the raw material composition include a raw material for producing the fluorine-containing propane (1) and a by-product generated in addition to the fluorine-containing propane (1) when the fluorine-containing propane (1) is produced.
  • the impurity is preferably a compound that is inert under the reaction conditions of the reaction represented by the above reaction formula [I].
  • the catalyst is a catalyst that promotes the reaction represented by the above reaction formula [I].
  • a catalyst may be used individually by 1 type and may use 2 or more types together.
  • a partial halide of a metal oxide is a compound in which a part of the metal oxide is halogenated (F, Cl, Br, I, etc.).
  • the metal halide is a compound composed of a metal and a halogen such as F, Cl, Br, or I.
  • the partial halide and metal halide of the metal oxide may contain only one kind of halogen or may contain two or more kinds of halogen.
  • the metal oxide partial halide is preferably a metal oxide partial fluoride in which the metal oxide is fluorinated.
  • the partial fluoride of the metal oxide may contain a halogen other than fluorine.
  • the metal halide is preferably a metal fluoride.
  • the metal fluoride may contain a halogen other than fluorine.
  • Metal oxides, partial halides of metal oxides, and metal halides that are catalysts include alkali metals, alkaline earth metals, Group 4 metals, Group 5 metals, and Group 6 metals that constitute the catalyst. Metal, Group 7 metal, Group 8 metal, Group 9 metal, Group 10 metal, Group 12 metal, Group 13 metal and Group 15 metal are preferred.
  • the metal constituting the catalyst may be one kind or two or more kinds.
  • Catalysts composed of two or more metals include metal oxides containing two or more metals, partial halides of metal oxides containing two or more metals, metal halides containing two or more metals, and the like It is a combination.
  • Li, Na, K, Cs, Mg, Ca, Sr, Ba, Al, Cr are used as a metal constituting the catalyst.
  • At least one selected from Zr, Fe, Ni, Co, Zn, Mn, Sb, Nb, and Ta is preferable, and at least one selected from Al, Zn, Cr, Mg, Ca, K, Zr, and Li is more preferable.
  • the metal oxide includes zinc oxide, chromium oxide, magnesium oxide, aluminum oxide, zinc-chromium composite oxide, chromium-magnesium.
  • Composite oxides and chromium / aluminum / magnesium composite oxides are preferable, and chromium oxide, aluminum oxide, zinc / chromium composite oxides, chromium / magnesium composite oxides, and chromium / aluminum / magnesium composite oxides are particularly preferable.
  • the metal oxide is preferably a partially fluorinated metal oxide partial fluoride, zinc oxide partial fluoride, chromium oxide partial fluoride, Magnesium oxide partial fluoride, aluminum oxide partial fluoride, zinc-chromium composite oxide partial fluoride, chromium-magnesium composite oxide partial fluoride, chromium-aluminum-magnesium composite oxide partial fluoride
  • chromium oxide partial fluoride, aluminum oxide partial fluoride, zinc-chromium composite oxide partial fluoride, chromium-magnesium composite oxide partial fluoride, chromium-aluminum-magnesium composite oxide partial fluoride Is particularly preferred.
  • the partial fluoride of the metal oxide may contain a halogen other than fluorine.
  • the metal halide is preferably a metal fluoride, more preferably aluminum fluoride, chromium fluoride, lithium fluoride, potassium fluoride, magnesium fluoride, calcium fluoride, or zirconium fluoride, and aluminum fluoride or chromium fluoride. Particularly preferred are potassium fluoride, calcium fluoride, and zirconium fluoride.
  • the metal fluoride may contain a halogen other than fluorine.
  • the catalyst is preferably used only with metal oxides, metal oxide partial halides or metal halides, which do not contain other catalysts. Further, the catalyst is preferably composed of a single compound of any one of the above metal oxides, partial halides of metal oxides or metal halides. For example, when zinc oxide is used as the catalyst, only zinc oxide is used. When zinc / chromium composite oxide or chromium / magnesium composite oxide is used as the catalyst, only zinc / chromium composite oxide or chromium / magnesium composite is used. More preferably, it is composed only of an oxide.
  • the catalyst is composed of a single compound of any one of the above metal oxides, partial halides of metal oxides, or metal halides, impurities and the like are included within the range not impairing the effects of the present invention. You may contain.
  • the catalyst may be used after being formed into catalyst pellets or may be used by being supported on a carrier.
  • the carrier include carbon materials such as activated carbon, carbon black, and carbon fiber, and oxide materials such as alumina, silica, titania, zirconia, alkali metal oxides, and alkaline earth metal oxides. Silica, zirconia, alkali metal oxides and alkaline earth metal oxides are preferred.
  • activated carbon, alumina, and zirconia are particularly preferable because they have a large specific surface area and can easily carry the catalyst.
  • the above-mentioned metal oxides, metal oxide partial halides and metal halides are crushed into powders, and the catalyst pellets are formed using a tableting machine or the like. Can do.
  • the catalyst pellet may have a diameter of about 3.0 mm and a height of about 4.0 mm, for example.
  • a binder such as carbon, cellulose, alumina, silica, etc., as required, is 100 parts by mass or less, preferably 50 parts by mass or less, more preferably 10 parts by mass with respect to 100 parts by mass of the catalyst. You may mix below.
  • catalyst pellets can be formed from a mixture of a catalyst and a binder by a tableting machine or the like.
  • the catalyst is preferably dried in advance in an inert atmosphere, for example, in a nitrogen stream.
  • the catalyst may be dried in the same manner as described above in a state of being accommodated in the reactor from the viewpoint of simplification of operation and improvement of working efficiency.
  • the catalyst is accommodated in the reactor as catalyst pellets or supported on a support, the catalyst is supported on the catalyst pellets or the support in advance in the reactor or before being stored in the reactor. It may be dried in a state.
  • the specific surface area of the catalyst or catalyst pellet depends on the type of each catalyst. Generally, the smaller the value, the lower the conversion rate, and the larger the value, the lower the selectivity and the faster the deterioration.
  • the specific surface area of the metal oxide catalyst and the metal oxide partial halide catalyst is preferably 10 to 400 m 2 / g, and the specific surface area of the metal halide catalyst is preferably 3 to 300 m 2 / g. .
  • the specific surface area of the metal oxide catalyst and the metal oxide partial halide catalyst is preferably 3 to 300 m 2 / g.
  • the specific surface area of the metal halide catalyst is preferably 3 to 300 m 2 / g.
  • the specific surface area of the binder is 20 to 1200 m 2. / G is preferable.
  • the specific surface area is a value measured by the BET method.
  • the catalyst is preferably activated in advance from the viewpoint of improving the reactivity.
  • the activation treatment method include a method in which the catalyst is brought into contact with the activation treatment agent with heating or without heating.
  • the activation treatment agent for example, hydrogen fluoride, hydrogen chloride, halogen-containing hydrocarbon, perhalogenated carbon, or the like can be used.
  • the perhalogenated carbon is a compound having a structure in which all hydrogen atoms bonded to carbon in the molecule of the hydrocarbon compound are substituted with halogen atoms.
  • 1 type may be used independently and 2 or more types may be used together.
  • a fluorine-containing hydrocarbon as an activation treating agent.
  • the perhalogenated carbon used as the activation treatment agent include carbon tetrachloride, trichlorofluoromethane (CFC-11), dichlorodifluoromethane (CFC-12), chlorotrifluoromethane (CFC-13), tetrafluoroethylene ( TFE), chlorotrifluoroethylene (CTFE) and the like are suitable.
  • the halogen-containing hydrocarbon used as the activation treatment agent chloroform, dichlorofluoromethane (HCFC-21), chlorodifluoromethane (HCFC-22), trifluoromethane (HFC-23), and the like are preferable.
  • fluorine-containing propane (1) such as 224ca, 234cc, etc. similar to what is contained in a raw material composition as an activation processing agent.
  • a catalyst made of a metal oxide is activated using the hydrogen fluoride, the fluorine-containing hydrocarbon, or the fluorine-containing perhalogenated carbon, so that a partial halide of the metal oxide ( (Partial fluoride) can be produced.
  • a reactivation treatment can be performed on the catalyst. That is, when the activity of the catalyst falls and the conversion rate to the fluorinated propene (2) is lowered, the catalyst can be reactivated. Thereby, the activity of the catalyst can be regenerated and the catalyst can be reused.
  • the reactivation treatment method examples include a method in which the catalyst is brought into contact with the activation treatment agent under heating or non-heating as in the activation treatment before use.
  • a treatment agent for reactivation treatment oxygen, chlorine, hydrogen fluoride, hydrogen chloride, halogen-containing hydrocarbon, perhalogenated carbon, or the like can be used.
  • the halogen-containing hydrocarbon and perhalogenated carbon include the same compounds as described above.
  • an inert gas such as nitrogen, carbon dioxide, or a rare gas (such as helium) is used to dilute the reactivation treatment agent from the viewpoint of suppressing side reactions and improving the durability of the catalyst. be able to.
  • the catalyst by bringing the reactivation treatment agent into contact with the catalyst layer together with the fluorine-containing propane (1), the catalyst can be reactivated in the reaction system, and the decrease in the activity of the catalyst can be suppressed.
  • the supply amount of the reactivation treatment agent is 100 mol% of the fluorinated propene (1) supplied to the reactor (however, when the composition containing the fluorinated propene (1) is used as a raw material, 0.001 to 1000 mol%) is preferred. From the viewpoint of enhancing the activation effect of the catalyst, 0.01 mol% or more is more preferable, 0.05% or more is more preferable, and 0.1% or more is particularly preferable. From the viewpoint of improving the volumetric efficiency of the reactor and reducing impurities derived from the reactivation treatment agent, it is more preferably ⁇ 100 mol%, further preferably ⁇ 10 mol%, and particularly preferably ⁇ 1 mol%.
  • the catalyst may be activated before being accommodated in the reactor.
  • the activation treatment is preferably performed in the state accommodated in the reactor. Therefore, it is preferable to perform the activation treatment by introducing the activation treatment agent into the reactor containing the catalyst.
  • the activation treatment agent may be introduced into the reactor at room temperature, but from the viewpoint of improving reactivity, it is preferable to adjust the temperature by heating or the like when introduced into the reactor.
  • the temperature in the reactor is preferably heated to 50 to 500 ° C.
  • the catalyst when the catalyst is used after being dried, it is preferable to carry out the activation treatment after the catalyst is dried.
  • the activation treatment is performed after the catalyst is dried, it is preferable that the catalyst is dried in a state of being accommodated in the reactor, and then the activation treatment is performed.
  • the raw material composition is composed of 234 cc, HCFC-234eb, HCFC-233bc and HCFC-233ea as fluorine-containing propane (1) as described above. Of these, at least one fluorine-containing propane (1) is contained. These fluorine-containing propanes (1) can be produced by a known method.
  • 234cc can be manufactured by the following method (A) and method (B).
  • a compound represented by formula (3) obtained in the first step and a compound represented by the general formula (3) obtained in the first step are hydrogenated to obtain 234 cc.
  • TFE is reacted with one or both of CCl 4 and CHCl 3 in the presence of a Lewis acid catalyst such as aluminum chloride, for example.
  • a Lewis acid catalyst such as aluminum chloride, for example.
  • 1,1,1,3-tetrachloro-2,2,3,3-tetrafluoropropane (Cl 3 C—CF 2 —CClF 2 , CFC-214cb; hereinafter also referred to as 214cb) and One or both of 224ca are obtained.
  • one or both of 214cb and 224ca can be hydrogenated in the presence of, for example, a palladium catalyst to obtain a composition containing 234 cc.
  • composition containing 234 cc obtained by the method (A) in addition to 234 cc, production raw materials TFE, 214 cb, 224 ca, CCl 4 , CHCl 3 , 1-chloro-1,1 by-produced in the production process , 2,2-tetrafluoropropane (CClF 2 —CF 2 —CH 3 , HCFC-244cc; hereinafter also referred to as 244cc).
  • the composition obtained by the method (A) may be used as a raw material composition as it is, and the purity of 234 cc is increased by known methods such as distillation, extractive distillation, azeotropic distillation, membrane separation, two-layer separation, and adsorption. May be used as a raw material composition.
  • 234 cc can be obtained by reacting TFE and CH 2 Cl 2 in the presence of a Lewis acid catalyst as described above.
  • a Lewis acid catalyst as described above.
  • 233 isomer trichlorotrifluoropropane
  • 234 isomerism Dichlorotetrafluoropropane
  • 235 chloropentafluoropropane
  • the composition obtained by the method (B) may be used as a raw material composition as it is, and the purity of 234 cc is increased by known methods such as distillation, extractive distillation, azeotropic distillation, membrane separation, two-layer separation, and adsorption. May be used as a raw material composition.
  • the production method of 1224yd of this embodiment can be carried out by a method in which a raw material composition containing 234 cc as a fluorinated propane (1) is allowed to flow through a reactor containing a catalyst for a predetermined time.
  • examples of the catalyst include metal oxides, metal oxide partial halides, metal halides, and the like.
  • a partial halide of a metal oxide is a compound in which a part of the metal oxide is halogenated (F, Cl, Br, I, etc.).
  • the metal halide is a compound composed of a metal and a halogen such as F, Cl, Br, or I.
  • the partial halide and metal halide of the metal oxide may contain only one kind of halogen or may contain two or more kinds of halogen.
  • the metal oxide partial halide is preferably a metal oxide partial fluoride in which the metal oxide is fluorinated.
  • the partial fluoride of the metal oxide may contain a halogen other than fluorine.
  • the metal halide is preferably a metal fluoride.
  • the metal fluoride may contain a halogen other than fluorine.
  • Metal oxides, partial halides of metal oxides, and metal halides that are catalysts include alkali metals, alkaline earth metals, Group 4 metals, Group 5 metals, and Group 6 metals that constitute the catalyst. Metal, Group 7 metal, Group 8 metal, Group 9 metal, Group 10 metal, Group 12 metal, Group 13 metal and Group 15 metal are preferred.
  • the metal constituting the catalyst may be one kind or two or more kinds.
  • Catalysts composed of two or more metals include metal oxides containing two or more metals, partial halides of metal oxides containing two or more metals, metal halides containing two or more metals, and the like It is a combination.
  • Li, Na, K, Cs, Mg, Ca, Sr, Ba, Al, Cr are used as a metal constituting the catalyst.
  • At least one selected from Zr, Fe, Ni, Co, Zn, Mn, Sb, Nb, and Ta is preferable, and at least one selected from Al, Zn, Cr, Mg, Ca, K, Zr, and Li is more preferable.
  • metal oxide zinc oxide, chromium oxide, magnesium oxide, aluminum oxide, zinc / chromium composite oxide, chromium / magnesium composite oxide, chromium / aluminum / magnesium composite oxide are used to improve the production efficiency of 1224yd.
  • the metal oxide is preferably a partially fluorinated metal oxide partial fluoride, zinc oxide partial fluoride, chromium oxide partial fluoride, Magnesium oxide partial fluoride, aluminum oxide partial fluoride, zinc-chromium composite oxide partial fluoride, chromium-magnesium composite oxide partial fluoride, chromium-aluminum-magnesium composite oxide partial fluoride
  • chromium oxide partial fluoride, aluminum oxide partial fluoride, zinc-chromium composite oxide partial fluoride, chromium-magnesium composite oxide partial fluoride, chromium-aluminum-magnesium composite oxide partial fluoride Is particularly preferred.
  • the partial fluoride of the metal oxide may contain a halogen other than fluorine.
  • the metal halide is preferably a metal fluoride, more preferably aluminum fluoride, chromium fluoride, lithium fluoride, potassium fluoride, magnesium fluoride, calcium fluoride, or zirconium fluoride, and aluminum fluoride or chromium fluoride. Particularly preferred are potassium fluoride, calcium fluoride, and zirconium fluoride.
  • the metal fluoride may contain a halogen other than fluorine.
  • a dilution gas is supplied to the reactor together with the raw material composition from the viewpoint of suppressing side reactions, ease of supply of starting materials to the reactor, and adjusting the flow rate. Is preferred. Further, there is an advantage that the durability of the catalyst is improved by using a dilution gas.
  • the dilution gas examples include nitrogen, carbon dioxide, rare gas (such as helium), water vapor, and a gas of an organic compound that is inactive in the reaction of the present embodiment.
  • Inactive organic compounds include saturated hydrocarbons such as methane, ethane, propane, butane, pentane and hexane, fluorohydrocarbons such as difluoromethane (HFC-32), hexafluoroethane (FC-216), and octafluoro.
  • fluorohydrocarbons such as difluoromethane (HFC-32), hexafluoroethane (FC-216), and octafluoro.
  • perfluorocarbons such as propane (FC-318).
  • the amount of the dilution gas is not particularly limited, but specifically, 1 to 10,000 mol%, preferably 10 to 5000 mol%, more preferably 30 to 100 mol% with respect to 100 mol% of the raw material composition supplied to the reactor. An amount of 1000 mol% is mentioned. Dilution gas may be used individually by 1 type, and may use 2 or more types together.
  • the raw material composition may be introduced into the reactor after preheating.
  • the preheating temperature at this time is preferably 20 to 500 ° C., and preferably 50 to 400 ° C., from the viewpoint of vaporizing 234 cc in the raw material composition and improving the reactivity.
  • the raw material composition and the dilution gas may be introduced into the reactor after preheating to the above-mentioned preferable temperature from the viewpoint of improving the reactivity.
  • the raw material composition and the dilution gas may be mixed after preheating to the above temperature, and then supplied to the reactor, or after mixing the raw material composition and the dilution gas, preheated and supplied to the reactor. Also good.
  • the reaction conditions when the contact between the raw material composition and the catalyst is carried out in the gas phase can be performed under reduced pressure or under increased pressure. From the viewpoint of easiness, it is preferable to carry out the reaction under reduced pressure, normal pressure, or slight pressure of 1.0 MPa or less.
  • reaction temperature The contact temperature (reaction temperature) between the raw material composition and the catalyst depends on the type of catalyst used, but the temperature in the reactor is 100 to 500 ° C., preferably 150 to 450 ° C. If the reaction temperature is equal to or higher than the lower limit value, the production reaction of 1224yd can be efficiently advanced. On the other hand, when the reaction temperature is equal to or lower than the upper limit value, generation of by-products due to decomposition of 1224yd can be suppressed.
  • the contact time (reaction time) of the raw material composition and the catalyst in the reactor is preferably 0.1 to 1000 seconds, and more preferably 1 to 100 seconds.
  • the contact time corresponds to the residence time of the raw material composition in the reactor, and can be controlled by adjusting the supply amount (flow rate) of the raw material composition to the reactor.
  • the reactor used in the method for producing 1224yd according to the present embodiment is not particularly limited as long as it can withstand the temperature and pressure in the reactor described above.
  • a glass flask, an autoclave, a cylindrical vertical reaction is used. Can be used.
  • the material of the reactor glass, iron, nickel, iron, an alloy containing nickel as a main component, or the like is used.
  • the reactor may be provided with an electric heater for heating the inside of the reactor.
  • FIG. 1 An example of a reaction apparatus used in the method for producing 1224yd of this embodiment is shown in FIG.
  • the reaction apparatus 20 shown in FIG. 1 has the reactor 1 provided with heating means, such as an electric heater.
  • a catalyst 2 is accommodated in the reactor 1.
  • the raw material composition supply line 3 and the dilution gas supply line 4 are connected to the reactor 1 as follows.
  • the installation of the heating means and the dilution gas supply line 4 in the reactor 1 is not essential, and is provided as necessary.
  • the raw material composition supply line 3 and the dilution gas supply line 4 may be provided with preheaters (not shown) each equipped with an electric heater or the like. In this case, the raw material composition and the dilution gas are each preheated to a predetermined temperature by the preheater and then supplied to the reactor 1.
  • the raw material composition supply line 3 and the dilution gas supply line 4 may be separately connected to the reactor 1, but as shown in FIG. 1, the raw material composition supply line 3 and the dilution gas supply By connecting the line 4 and connecting to the reactor 1 by the raw material composition / dilution gas supply line 5, a mixture of all components may be supplied to the reactor 1.
  • the raw material composition supply line 3 and / or the dilution gas supply line 4 includes a preheater, the raw material composition supply line 3 and the dilution gas supply line 4 are connected after passing through the preheater, and the raw material composition -What is necessary is just to connect with the reactor 1 by the dilution gas supply line 5.
  • the outlet line 6 is connected to the outlet of the reactor 1.
  • Each component of the crude gas after reaction obtained from the outlet line 6 may be analyzed and quantified by an analyzer such as gas chromatography (GC).
  • a cooling means 7 such as a water cooler is installed in the outlet line 6, and further, a steam and acidic liquid recovery tank 8, an alkali cleaning device 9, and a dehydration tower 10 are sequentially installed.
  • the crude gas passes through the outlet line 6 and is cooled by the cooling means 7, and then passes through the acidic liquid recovery tank 8, the alkali cleaning device 9, and the dehydration tower 10, thereby having strong acid content, moisture, and adsorptivity. It flows out from the exit of the dehydration tower 10 as an exit gas from which components have been removed.
  • 1224yd can be obtained as a component of the crude gas.
  • the crude gas containing these is directly introduced into the GC for analysis.
  • 1224yd can be obtained as a component of the outlet gas.
  • the above components other than 1224yd contained in the outlet gas can be removed to a desired extent by known means such as distillation, extractive distillation, azeotropic distillation, membrane separation, two-layer separation, adsorption and the like.
  • 1224yd can be manufactured by an industrially advantageous method by using 234 cc which is easily available as a raw material.
  • the raw material composition is composed of 224ca, HCFC-224eb, HCFC-223ba, and HCFC-223eb as fluorine-containing propane (1) as described above. Of these, at least one fluorine-containing propane (1) is contained. These fluorine-containing propanes (1) can be produced by a known method.
  • 224ca is obtained by the first step of the method (A) described above.
  • the composition obtained in the first step of method (A) includes TFE and TFE as production raw materials, CCl 4 and CHCl 3, and 214cb as a by-product. You may use this composition as a raw material composition as it is. Moreover, you may use what raised 224ca to desired purity by well-known methods, such as distillation, extractive distillation, azeotropic distillation, membrane separation, two-layer separation, adsorption
  • the production method of 1214ya of this embodiment can be performed by a method in which a raw material composition containing 224ca as a fluorinated propane (1) is allowed to flow through a reactor containing a catalyst for a predetermined time.
  • the same catalyst as the catalyst exemplified in the method for producing 1224yd can be used as the catalyst, and the metal oxide and the metal oxide partial halide are improved in that the production efficiency of 1214ya can be improved.
  • the metal oxide is more preferably zinc oxide, chromium oxide, magnesium oxide, aluminum oxide, zinc-chromium composite oxide, chromium-magnesium composite oxide, chromium-aluminum-magnesium composite oxide, chromium oxide, aluminum oxide, Zinc / chromium composite oxide, chromium / magnesium composite oxide, and chromium / aluminum / magnesium composite oxide are particularly preferable.
  • the metal oxide partial halide is more preferably a partially fluorinated metal oxide partial fluoride, zinc oxide partial fluoride, chromium oxide partial fluoride.
  • Magnesium oxide partial fluoride, aluminum oxide partial fluoride, zinc-chromium composite oxide partial fluoride, chromium-magnesium composite oxide partial fluoride, chromium-aluminum-magnesium composite oxide partial fluoride More preferably, chromium oxide partial fluoride, aluminum oxide partial fluoride, zinc-chromium composite oxide partial fluoride, chromium-magnesium composite oxide partial fluoride, chromium-aluminum-magnesium composite oxide partial fluorine
  • the compound is particularly preferred.
  • the partial fluoride of the metal oxide may contain a halogen other than fluorine.
  • the metal halide is preferably a metal fluoride, more preferably aluminum fluoride, chromium fluoride, lithium fluoride, potassium fluoride, magnesium fluoride, calcium fluoride, or zirconium fluoride, and aluminum fluoride or chromium fluoride. Particularly preferred are potassium fluoride, calcium fluoride, and zirconium fluoride.
  • the metal fluoride may contain a halogen other than fluorine.
  • the raw material composition is preferably introduced into the reactor after preheating.
  • the preheating temperature at this time is preferably 20 to 500 ° C., and preferably 50 to 400 ° C., from the viewpoint of vaporizing 224ca in the raw material composition and improving the reactivity.
  • the reaction conditions when the contact between the raw material composition and the catalyst is carried out in the gas phase can be carried out under reduced pressure or under increased pressure. From the viewpoint of easiness, it is preferable to carry out the reaction under reduced pressure, normal pressure, or slight pressurization of 1.0 MPa or less.
  • reaction temperature The contact temperature (reaction temperature) between the raw material composition and the catalyst depends on the type of the catalyst, but the temperature in the reactor is 100 to 500 ° C., preferably 150 to 450 ° C. If the reaction temperature is equal to or higher than the lower limit value, the production reaction of 1214ya can proceed efficiently. On the other hand, when the reaction temperature is equal to or lower than the upper limit value, generation of by-products due to decomposition of 1214ya can be suppressed.
  • the contact time (reaction time) between the raw material composition and the catalyst in the reactor is preferably 0.1 to 1000 seconds, and more preferably 1 to 100 seconds.
  • the contact time corresponds to the residence time of the raw material composition in the reactor, and can be controlled by adjusting the supply amount (flow rate) of the raw material composition to the reactor.
  • preferable conditions other than the above such as a reactor, a reaction apparatus, a dilution gas, and the like, are the same as the method of producing 1224yd in the gas phase using 234cc described above.
  • 1214ya can be obtained as a component of the outlet gas.
  • Components other than 1214ya contained in the outlet gas can be removed to a desired extent by known means such as distillation, extractive distillation, azeotropic distillation, membrane separation, two-layer separation, and adsorption.
  • 1214ya can be manufactured by an industrially advantageous method by using 224ca which is easily available as a raw material.
  • anhydrous aluminum chloride 25 g, 0.19 mol
  • CHCl 3 500 g, 4.19 mol
  • 224ca 100 g, 0.45 mol
  • reaction solution was cooled to room temperature and analyzed by gas chromatography.
  • the conversion of CHCl 3 was 33% and the selectivity of 224ca was 84%.
  • 102 g of molecular sieve 4A was added and stirred overnight to dehydrate.
  • 224ca (230 g, 1.05 mol) was manufactured by distilling and purifying the crude product obtained by separating the stirred crude liquid by filtration.
  • a gas phase reactor made of SUS316, diameter 25 mm, length 30 cm
  • activated carbon pellets 15 g supporting palladium at a ratio of 2.0 mass%
  • the temperature was raised to 130 ° C. while flowing nitrogen (N 2 ) gas (500 NmL / min).
  • N 2 nitrogen
  • the catalyst was dried until the moisture in the crude gas after passing through the reactor became 20 ppm or less.
  • the supply of nitrogen was stopped, the reaction tube was heated to 200 ° C. while supplying hydrogen (180 mL / min), and then 224ca (0.44 g / min) was supplied.
  • the crude gas from the reaction tube was washed with water, and then acid and moisture were removed through an alkali washing tower and molecular sieve 5A, and then collected in a cold trap.
  • the conversion rate of 224ca was 98%, and 234cc was obtained with a selectivity of 24% and 244cc with a selectivity of 70%.
  • a total of 500 g (2.27 mol) of 224ca was reacted above to give 298 g of crude product.
  • the obtained crude product was subjected to normal pressure rectification in a 25-stage rectification column to obtain 234 cc (74 g, 0.4 mol).
  • Catalyst Preparation Example 1 Aluminum fluoride (AlF 3 , manufactured by Junsei Kagaku) was molded into pellets having a diameter of 3 mm and a height of 4 mm with a tableting machine. The pellets were charged into the reactor, and the temperature in the reactor was raised to 350 ° C. while flowing nitrogen (N 2 ) gas (500 NmL / min). While maintaining the inside of the reactor at atmospheric pressure (1 atm) and 350 ° C., the catalyst was dried until the moisture in the gas obtained from the outlet of the reactor became 20 ppm or less, whereby Catalyst 1 was obtained.
  • N 2 nitrogen
  • the crude gas after the reaction was washed with water and then passed through an alkali washing tower and a molecular sieve 4A to wash with water and dry to obtain an outlet gas. Moreover, each component of the crude gas after reaction was analyzed using gas chromatography.
  • the result of analyzing the crude gas one hour after the start of the supply to the 234 cc reactor was determined based on the reaction conditions (type of catalyst used, residence time of 234 cc in the reactor (reaction time), reactor temperature (reaction). Table 1 together with (temperature) and 234 cc supply flow rate).
  • Example 2 (Examples 2 and 3)
  • the flow rate of 234 cc supplied to the reactor in Example 1 was changed to 0.127 g / min, and the flow rate of nitrogen was changed to 15.33 NmL / min.
  • Example 3 the flow rate of 234 cc supplied to the reactor in Example 1 was changed to 0.380 g / min, and the flow rate of nitrogen was changed to 45.9 NmL / min. Except for these, the experiment was performed under the same conditions as in Example 1. The results are shown in Table 1 together with the reaction conditions.
  • Chromium fluoride (CrF 3 , manufactured by Kanakuma Chemical) was formed into pellets having a diameter of 3 mm and a height of 4 mm with a tableting machine. The pellets were charged into the reactor, and the temperature in the reactor was raised to 350 ° C. while flowing nitrogen (N 2 ) gas (500 NmL / min). While maintaining the inside of the reactor at atmospheric pressure (1 atm) and 350 ° C., the catalyst was dried until the moisture in the gas obtained from the outlet of the reactor became 20 ppm or less, whereby Catalyst 2 was obtained.
  • N 2 nitrogen
  • Example 4 The inside of the reactor containing the catalyst 2 prepared in Catalyst Preparation Example 2 was maintained at 300 ° C., and 234 cc was supplied to the reactor at a flow rate of 0.054 g / min and nitrogen was 6.49 NmL / min. After the reaction, the crude gas was washed with water, passed through an alkali washing tower and molecular sieve 4A, and washed with water and dried. Table 1 shows the results of analyzing the crude gas 1 hour after the start of supply to the 234 cc reactor using gas chromatography, together with the reaction conditions.
  • Example 5 In Example 5, the temperature of the reactor in Example 4 was maintained at 350 ° C., the flow rate of 234 cc supplied to the reactor was changed to 0.049 g / min, and the flow rate of nitrogen was changed to 5.97 mL / min. In Example 6, the temperature of the reactor was maintained at 400 ° C. in Example 4, the flow rate of 234 cc supplied to the reactor was changed to 0.046 g / min, and the flow rate of nitrogen was changed to 5.53 NmL / min.
  • Example 7 the temperature of the reactor in Example 4 was maintained at 450 ° C., the flow rate of 234 cc supplied to the reactor was changed to 0.042 g / min, and the flow rate of nitrogen was changed to 5.15 NmL / min. Except for these, the experiment was performed under the same conditions as in Example 4. The results are shown in Table 1 together with the reaction conditions.
  • Example 8 The inside of the reactor containing the catalyst 3 prepared in Catalyst Preparation Example 3 was maintained at 350 ° C., and 234 cc was supplied to the reactor at a flow rate of 0.049 g / min and nitrogen was 5.97 NmL / min. After the reaction, the crude gas was washed with water, passed through an alkali washing tower and molecular sieve 4A, and washed with water and dried. Table 1 shows the results of analyzing the crude gas 1 hour after the start of supply to the 234 cc reactor using gas chromatography, together with the reaction conditions.
  • Example 9 In Example 9, in Example 8, the temperature of the reactor was maintained at 400 ° C., the flow rate of 234 cc supplied to the reactor was changed to 0.046 g / min, and the flow rate of nitrogen was changed to 5.53 mL / min. Except for these, the experiment was performed under the same conditions as in Example 8. The results are shown in Table 1 together with the reaction conditions.
  • Example 10 The inside of the reactor containing the catalyst 4 prepared in Catalyst Preparation Example 4 was maintained at 350 ° C., and 234 cc was supplied to the reactor at a flow rate of 0.049 g / min and nitrogen was 5.97 NmL / min. After the reaction, the crude gas was washed with water and then washed with water and dried by passing through an alkali washing tower and molecular sieve 3A. Table 1 shows the results of analyzing the crude gas 1 hour after the start of supply to the 234 cc reactor using gas chromatography, together with the reaction conditions.
  • Catalyst Preparation Example 5 Magnesium fluoride (MgF 2 , manufactured by Junsei Kagaku) was molded into pellets having a diameter of 3 mm and a height of 4 mm with a tableting machine. The pellets were charged into the reactor, and the temperature in the reactor was raised to 350 ° C. while flowing nitrogen (N 2 ) gas (500 NmL / min). While maintaining the inside of the reactor at atmospheric pressure (1 atm) and 350 ° C., the catalyst was dried until the water content in the gas obtained from the outlet of the reactor became 20 ppm or less, whereby Catalyst 5 was obtained.
  • N 2 nitrogen
  • Example 11 The inside of the reactor containing the catalyst 5 prepared in Catalyst Preparation Example 5 was maintained at 350 ° C., and 234 cc was supplied to the reactor at a flow rate of 0.049 g / min and nitrogen was 5.97 NmL / min. After the reaction, the crude gas was washed with water, passed through an alkali washing tower and molecular sieve 4A, and washed with water and dried. Table 1 shows the results of analyzing the crude gas 1 hour after the start of supply to the 234 cc reactor using gas chromatography, together with the reaction conditions.
  • Example 12 In Example 12, the temperature of the reactor in Example 11 was maintained at 400 ° C., the flow rate of 234 cc supplied to the reactor was changed to 0.046 g / min, and the flow rate of nitrogen was changed to 5.60 NmL / min.
  • Example 13 in Example 11, the temperature of the reactor was maintained at 420 ° C., the flow rate of 234 cc supplied to the reactor was changed to 0.044 g / min, and the flow rate of nitrogen was changed to 5.37 NmL / min. Except for these, the experiment was performed under the same conditions as in Example 11. The results are shown in Table 1 together with the reaction conditions.
  • Catalyst Preparation Example 6 Calcium fluoride (CaF 2 , manufactured by Wako Pure Chemical Industries, Ltd.) was molded into pellets having a diameter of 3 mm and a height of 4 mm with a tableting machine. The pellets were charged into the reactor, and the temperature in the reactor was raised to 350 ° C. while flowing nitrogen (N 2 ) gas (500 NmL / min). While maintaining the inside of the reactor at atmospheric pressure (1 atm) and 350 ° C., the catalyst was dried until the moisture in the gas obtained from the outlet of the reactor became 20 ppm or less, whereby Catalyst 6 was obtained.
  • N 2 nitrogen
  • Example 14 The inside of the reactor containing the catalyst 6 prepared in Catalyst Preparation Example 6 was maintained at 350 ° C., and 234 cc was supplied to the reactor at a flow rate of 0.049 g / min and nitrogen was 5.97 NmL / min. After the reaction, the crude gas was washed with water, passed through an alkali washing tower and molecular sieve 4A, and washed with water and dried. Table 1 shows the results of analyzing the crude gas 1 hour after the start of supply to the 234 cc reactor using gas chromatography, together with the reaction conditions.
  • Example 15 In Example 15, in Example 14, the temperature of the reactor was maintained at 370 ° C., the flow rate of 234 cc supplied to the reactor was changed to 0.048 g / min, and the flow rate of nitrogen was changed to 5.79 NmL / min. Except for these, the experiment was performed under the same conditions as in Example 14. The results are shown in Table 1 together with the reaction conditions.
  • Catalyst Preparation Example 7 Zirconium fluoride (ZrF 4 , manufactured by Acros) was formed into pellets having a diameter of 3 mm and a height of 4 mm with a tableting machine. The pellets were charged into the reactor, and the temperature in the reactor was raised to 350 ° C. while flowing nitrogen (N 2 ) gas (500 NmL / min). While maintaining the inside of the reactor at atmospheric pressure (1 atm) and 350 ° C., the catalyst was dried until the moisture in the gas obtained from the outlet of the reactor became 20 ppm or less, whereby Catalyst 7 was obtained.
  • N 2 nitrogen
  • Example 16 The inside of the reactor containing the catalyst 7 prepared in Catalyst Preparation Example 7 was maintained at 350 ° C., and 234 cc was supplied to the reactor at a flow rate of 0.049 g / min and nitrogen was 5.97 NmL / min. After the reaction, the crude gas was washed with water, passed through an alkali washing tower and molecular sieve 4A, and washed with water and dried. Table 1 shows the results of analyzing the crude gas 1 hour after the start of supply to the 234 cc reactor using gas chromatography, together with the reaction conditions.
  • Example 17 In Example 17, in Example 16, the temperature of the reactor was maintained at 400 ° C., the flow rate of 234 cc supplied to the reactor was changed to 0.046 g / min, and the flow rate of nitrogen was changed to 5.53 NmL / min. Except for these, the experiment was performed under the same conditions as in Example 16. The results are shown in Table 1 together with the reaction conditions.
  • Catalyst Preparation Example 8 Graphite (manufactured by Nacalai Tesque) as a carbon binder is mixed with aluminum fluoride (AlF 3 , manufactured by Junsei Kagaku) so that the graphite is 3 parts by mass with respect to 100 parts by mass of aluminum fluoride, and the diameter is 3 mm with a tableting machine. And formed into pellets having a height of 4 mm. The pellets were charged into the reactor, and the temperature in the reactor was raised to 350 ° C. while flowing nitrogen (N 2 ) gas (500 NmL / min). While maintaining the inside of the reactor at atmospheric pressure (1 atm) and 350 ° C., the catalyst was dried until the moisture in the gas obtained from the outlet of the reactor became 20 ppm or less, whereby Catalyst 8 was obtained.
  • AlF 3 aluminum fluoride
  • Example 18 The inside of the reactor containing the catalyst 8 prepared in Catalyst Preparation Example 8 was maintained at 350 ° C., and 234 cc was supplied to the reactor at a flow rate of 0.127 g / min and nitrogen was 15.33 NmL / min. After the reaction, the crude gas was washed with water, passed through an alkali washing tower and molecular sieve 4A, and washed with water and dried. Table 1 shows the results of analyzing the crude gas 1 hour after the start of supply to the 234 cc reactor using gas chromatography, together with the reaction conditions.
  • Zinc / chromium composite oxide catalyst (Cr 2 O 3 : 95% by mass, ZnO: 5% by mass, AG-25, manufactured by Sakai Chemical Co., Ltd.) was charged into the reactor, and nitrogen (N 2 ) gas (500 NmL / min) The temperature in the reactor was raised to 250 ° C. While maintaining the reactor at atmospheric pressure (1 atm) and 250 ° C., the catalyst was dried until the moisture in the gas obtained from the outlet of the reactor was 20 ppm or less.
  • the catalyst 9 is a partially fluorinated product of a zinc / chromium composite oxide catalyst obtained by fluorinating a zinc / chromium composite oxide catalyst.
  • Example 19 While maintaining the reactor containing the catalyst 9 prepared in Catalyst Preparation Example 9 at 250 ° C., 234 cc was supplied to the reactor at a flow rate of 0.059 g / min and nitrogen was 7.11 NmL / min.
  • Table 2 shows the results of analysis of the crude gas 1 hour after the start of supply to the 234 cc reactor using gas chromatography.
  • Example 20 In Example 20, the temperature of the reactor in Example 19 was maintained at 200 ° C., the flow rate of 234 cc supplied to the reactor was changed to 0.065 g / min, and the flow rate of nitrogen was changed to 7.87 mL / min. In Example 21, the temperature of the reactor in Example 19 was maintained at 200 ° C., the flow rate of 234 cc supplied to the reactor was changed to 0.125 g / min, and the flow rate of nitrogen was changed to 15.14 NmL / min.
  • Example 22 in Example 19, the temperature of the reactor was maintained at 200 ° C., the flow rate of 234 cc supplied to the reactor was changed to 0.313 g / min, and the flow rate of nitrogen was changed to 37.85 NmL / min. Except for these, the experiment was performed under the same conditions as in Example 19. The results are shown in Table 2 together with the reaction conditions.
  • Catalyst Preparation Example 10 A zinc / chromium composite oxide catalyst (Cr 2 O 3 : 95% by mass, ZnO: 5% by mass, AG-25, manufactured by Sakai Chemical Co., Ltd.) similar to that in Catalyst Preparation Example 9 was charged into a reactor, and nitrogen (N 2 The temperature inside the reactor was raised to 250 ° C. while flowing gas (500 NmL / min). While maintaining the reactor at atmospheric pressure (1 atm) and 250 ° C., the catalyst was dried until the moisture in the gas obtained from the outlet of the reactor was 20 ppm or less.
  • the catalyst 10 is a partially fluorinated product of a zinc / chromium composite oxide catalyst obtained by fluorinating a zinc / chromium composite oxide catalyst.
  • Example 23 While maintaining the reactor containing the catalyst 10 prepared in Catalyst Preparation Example 10 at 250 ° C., 234 cc was supplied to the reactor at a flow rate of 0.059 g / min and nitrogen was 7.11 NmL / min.
  • Table 2 shows the results of analysis of the crude gas 1 hour after the start of supply to the 234 cc reactor using gas chromatography.
  • Example 24 In Example 24, in Example 23, the temperature of the reactor was maintained at 300 ° C., the flow rate of 234 cc supplied to the reactor was changed to 0.054 g / min, and the flow rate of nitrogen was changed to 6.49 NmL / min. In Example 25, the temperature of the reactor in Example 23 was maintained at 350 ° C., the flow rate of 234 cc supplied to the reactor was changed to 0.049 g / min, and the flow rate of nitrogen was changed to 5.97 NmL / min. Except for these, the experiment was performed under the same conditions as in Example 23. The results are shown in Table 2 together with the reaction conditions.
  • Catalyst Preparation Example 11 A zinc / chromium composite oxide catalyst (Cr 2 O 3 : 95% by mass, ZnO: 5% by mass, AG-25, manufactured by Sakai Chemical Co., Ltd.) similar to that in Catalyst Preparation Example 9 was charged into a reactor, and nitrogen (N 2 The temperature inside the reactor was raised to 250 ° C. while flowing gas (500 NmL / min). While maintaining the reactor at atmospheric pressure (1 atm) and 250 ° C., the catalyst was dried until the moisture in the gas obtained from the outlet of the reactor was 20 ppm or less.
  • the catalyst 11 is a partially fluorinated product of a zinc / chromium composite oxide catalyst obtained by fluorinating a zinc / chromium composite oxide catalyst.
  • Example 26 The reactor containing the catalyst 11 prepared in Catalyst Preparation Example 11 was maintained at 200 ° C., and 234 cc was supplied to the reactor at a flow rate of 0.065 g / min and nitrogen was 7.87 NmL / min.
  • Table 2 shows the results of analysis of the crude gas 1 hour after the start of supply to the 234 cc reactor using gas chromatography.
  • Example 27 In Example 27, the temperature of the reactor was maintained at 250 ° C. in Example 26, the flow rate of 234 cc supplied to the reactor was changed to 0.059 g / min, and the flow rate of nitrogen was changed to 7.11 NmL / min. In Example 28, the temperature of the reactor was maintained at 300 ° C. in Example 26, the flow rate of 234 cc supplied to the reactor was changed to 0.054 g / min, and the flow rate of nitrogen was changed to 6.49 NmL / min. Except for these, the experiment was performed under the same conditions as in Example 26. The results are shown in Table 2 together with the reaction conditions.
  • Catalyst Preparation Example 12 A chromium-magnesium composite oxide catalyst (Cr 2 O 3 : 95% by mass, MgO: 5% by mass, AG-16, manufactured by Sakai Chemical Co., Ltd.) was charged into the reactor, and nitrogen (N 2 ) gas (500 NmL / min) The temperature in the reactor was raised to 250 ° C. While maintaining the reactor at atmospheric pressure (1 atm) and 250 ° C., the catalyst was dried until the moisture in the gas obtained from the outlet of the reactor was 20 ppm or less.
  • N 2 nitrogen
  • the catalyst 12 is a partially fluorinated product of a chromium / magnesium composite oxide catalyst obtained by fluorinating a chromium / magnesium composite oxide catalyst.
  • Example 29 The reactor containing the catalyst 12 prepared in Catalyst Preparation Example 12 was maintained at 250 ° C., and 234 cc was supplied to the reactor at a flow rate of 0.059 g / min and nitrogen was 7.11 NmL / min.
  • Table 2 shows the results of analysis of the crude gas 1 hour after the start of supply to the 234 cc reactor using gas chromatography.
  • Example 30 In Example 30, in Example 29, the temperature of the reactor was maintained at 300 ° C., the flow rate of 234 cc supplied to the reactor was changed to 0.054 g / min, and the flow rate of nitrogen was changed to 6.49 NmL / min. In Example 31, in Example 29, the temperature of the reactor was maintained at 350 ° C., the flow rate of 234 cc supplied to the reactor was changed to 0.049 g / min, and the flow rate of nitrogen was changed to 5.97 NmL / min. Except for these, the experiment was performed under the same conditions as in Example 29. The results are shown in Table 2 together with the reaction conditions.
  • Catalyst Preparation Example 13 A chromium / aluminum / magnesium composite oxide catalyst (Cr 2 O 3 : 63 mass%, Al 2 O 3 : 13 mass%, MgO: 2 mass%, N401AG, manufactured by JGC Catalysts & Chemicals Co., Ltd.) was charged into the reactor, and nitrogen was added. The temperature inside the reactor was raised to 250 ° C. while flowing (N 2 ) gas (500 NmL / min). While maintaining the reactor at atmospheric pressure (1 atm) and 250 ° C., the catalyst was dried until the moisture in the gas obtained from the outlet of the reactor was 20 ppm or less.
  • the catalyst 13 is a partially fluorinated product of a chromium / aluminum / magnesium composite oxide catalyst obtained by fluorinating a chromium / aluminum / magnesium composite oxide catalyst.
  • Example 32 The reactor containing the catalyst 13 prepared in Catalyst Preparation Example 13 was maintained at 250 ° C., and 234 cc was supplied to the reactor at a flow rate of 0.059 g / min and nitrogen was 7.11 NmL / min.
  • Table 2 shows the results of analysis of the crude gas 1 hour after the start of supply to the 234 cc reactor using gas chromatography.
  • Example 33 In Example 33, the temperature of the reactor in Example 32 was maintained at 300 ° C., the flow rate of 234 cc supplied to the reactor was changed to 0.054 g / min, and the flow rate of nitrogen was changed to 6.49 NmL / min. Except for these, the experiment was performed under the same conditions as in Example 32. The results are shown in Table 2 together with the reaction conditions.
  • Catalyst Preparation Example 14 Alumina (Al 2 O 3 , N612N, manufactured by JGC Catalysts & Chemicals) was charged into the reactor, and the temperature in the reactor was increased to 250 ° C. while flowing nitrogen (N 2 ) gas (500 NmL / min). While maintaining the reactor at atmospheric pressure (1 atm) and 250 ° C., the catalyst was dried until the moisture in the gas obtained from the outlet of the reactor was 20 ppm or less.
  • N 2 nitrogen
  • the catalyst 14 is a partially fluorinated product of aluminum oxide in which aluminum oxide (alumina) is fluorinated.
  • Example 34 The reactor containing the catalyst 14 prepared in Catalyst Preparation Example 14 was maintained at 250 ° C., and 234 cc was supplied to the reactor at a flow rate of 0.059 g / min and nitrogen was 7.11 NmL / min.
  • Table 2 shows the results of analysis of the crude gas 1 hour after the start of supply to the 234 cc reactor using gas chromatography.
  • Example 35 In Example 35, the temperature of the reactor in Example 34 was maintained at 300 ° C., the flow rate of 234 cc supplied to the reactor was changed to 0.054 g / min, and the flow rate of nitrogen was changed to 6.49 NmL / min. Except for these, the experiment was conducted under the same conditions as in Example 34. The results are shown in Table 2 together with the reaction conditions.
  • Catalyst Preparation Example 15 Alumina (Al 2 O 3 , N612N, manufactured by JGC Catalysts & Chemicals) was charged into the reactor, and the temperature in the reactor was increased to 350 ° C. while flowing nitrogen (N 2 ) gas (500 NmL / min). While maintaining the reactor at atmospheric pressure (1 atm) and 350 ° C., the catalyst was dried until the moisture in the gas obtained from the outlet of the reactor became 20 ppm or less.
  • N 2 nitrogen
  • the catalyst 15 is a partially fluorinated aluminum oxide obtained by fluorinating aluminum oxide (alumina).
  • Example 36 The reactor containing the catalyst 15 prepared in Catalyst Preparation Example 15 was maintained at 250 ° C., and 234 cc was supplied to the reactor at a flow rate of 0.181 g / min and nitrogen was 21.91 NmL / min.
  • Table 2 shows the results of analysis of the crude gas 1 hour after the start of supply to the 234 cc reactor using gas chromatography.
  • Example 38 In Example 38, 224ca and nitrogen were supplied into the reactor heated and maintained at 320 ° C. in Example 37. The flow rate of 224ca was changed to 0.062 g / min, and the flow rate of nitrogen was changed to 6.27 NmL / min.
  • Example 39 224ca and nitrogen were supplied into the reactor heated and maintained at 350 ° C. in Example 37. The flow rate of 224ca was changed to 0.113 g / min, and the flow rate of nitrogen was changed to 11.50 NmL / min. Except for these, the experiment was performed under the same conditions as in Example 37. The results are shown in Table 3 together with the reaction conditions.
  • Example 40 While maintaining the inside of the reactor containing the catalyst 10 prepared in Catalyst Preparation Example 10 at 250 ° C., 224ca is 0.070 g / min, nitrogen is 7.11 NmL / min (224ca / nitrogen molar ratio is 1/1).
  • the crude gas was washed with water, passed through an alkali washing tower and molecular sieve 4A, and washed with water and dried.
  • the crude gas 1 hour after the start of feeding to the reactor of 224ca was analyzed using gas chromatography. The results are shown in Table 3 together with the reaction conditions.
  • Example 41 In Example 41, 224ca and nitrogen were supplied into the reactor heated and maintained at 300 ° C. in Example 40. The flow rate of 224ca was changed to 0.064 g / min, and the flow rate of nitrogen was changed to 6.49 NmL / min. Except for these, the experiment was performed under the same conditions as in Example 40. The results are shown in Table 3 together with the reaction conditions.
  • Tables 1 and 2 show that 1224yd can be produced by bringing 234 cc into contact with the catalyst.
  • Table 3 also shows that 1214ya can be produced by contacting 224ca with the catalyst.

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Abstract

L'invention concerne un procédé de production de tétrafluoropropènes. En utilisant des matériaux facilement disponibles, le procédé de production permet de produire des propènes contenant du fluor tels que 1214ya et 1224yd d'une manière industriellement avantageuse. Un procédé de production de tétrafluoropropènes dans lequel un tétrafluoropropène représenté par la formule générale (2) (CF 3 CF = CClZ, dans laquelle Z représente H ou Cl) est obtenu par la mise en contact d'un propane contenant du fluor représenté par la formule générale (1) (CF 2 Cl-CFX-CClYZ, dans laquelle l'un de X et Y est H et l'autre est F ou Cl, et Z est H ou Cl) avec un catalyseur (à condition que, lorsque l'un de X et Y dans la formule générale (1) est H et l'autre est Cl, le propane contenant du fluor est mis en contact avec le catalyseur en présence du fluorure d'hydrogène).
PCT/JP2017/038955 2016-10-28 2017-10-27 Procédé de production de tétrafluoropropènes WO2018079726A1 (fr)

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JP2020023454A (ja) * 2018-08-07 2020-02-13 Ａｇｃ株式会社 １−クロロ−２，３，３−トリフルオロプロペンの製造方法
CN115322071A (zh) * 2022-10-17 2022-11-11 山东东岳化工有限公司 以1,1,1,2,3-五氟丙烷为原料联产制备三氟丙烯和四氟丙烯的方法
WO2023171273A1 (fr) * 2022-03-09 2023-09-14 株式会社クレハ Procédé de fabrication d'alcène halogéné

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JP2020023454A (ja) * 2018-08-07 2020-02-13 Ａｇｃ株式会社 １−クロロ−２，３，３−トリフルオロプロペンの製造方法
JP7151259B2 (ja) 2018-08-07 2022-10-12 Ａｇｃ株式会社 １－クロロ－２，３，３－トリフルオロプロペンの製造方法
WO2023171273A1 (fr) * 2022-03-09 2023-09-14 株式会社クレハ Procédé de fabrication d'alcène halogéné
CN115322071A (zh) * 2022-10-17 2022-11-11 山东东岳化工有限公司 以1,1,1,2,3-五氟丙烷为原料联产制备三氟丙烯和四氟丙烯的方法
CN115322071B (zh) * 2022-10-17 2023-01-31 山东东岳化工有限公司 以1,1,1,2,3-五氟丙烷为原料联产制备三氟丙烯和四氟丙烯的方法

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