WO2018047972A1 - Procédé de production de 1-chloro -2,3,3-trifluoropropène - Google Patents

Procédé de production de 1-chloro -2,3,3-trifluoropropène Download PDF

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WO2018047972A1
WO2018047972A1 PCT/JP2017/032837 JP2017032837W WO2018047972A1 WO 2018047972 A1 WO2018047972 A1 WO 2018047972A1 JP 2017032837 W JP2017032837 W JP 2017032837W WO 2018047972 A1 WO2018047972 A1 WO 2018047972A1
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chloro
trifluoropropene
metal
isomerization reaction
group
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PCT/JP2017/032837
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English (en)
Japanese (ja)
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厚史 藤森
允彦 中村
真理 村田
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旭硝子株式会社
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Priority to JP2018538502A priority Critical patent/JP7070419B2/ja
Priority to CN201780055755.3A priority patent/CN109689604A/zh
Publication of WO2018047972A1 publication Critical patent/WO2018047972A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/35—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction
    • C07C17/358—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction by isomerisation
    • 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 1-chloro-2,3,3-trifluoropropene.
  • Hydrochlorofluorocarbon has an adverse effect on the ozone layer, so its production is scheduled to be regulated.
  • HCFC is, for example, 3,3-dichloro-1,1,1,2,2-pentafluoropropane (HCFC-225ca) and 1,3-dichloro-1,1,2,2,3-pentafluoropropane ( HCFC-225cb) and the like, but with the HCFC regulations, the development of a compound that replaces the HCFC is desired.
  • HCFO-1233yd 1-chloro-2,3,3-trifluoropropene
  • 1233yd 1-chloro-2,3,3-trifluoropropene
  • 1233yd is a new compound that has a low global warming potential (GWP) and is useful for cleaning, solvent, refrigerant, blowing agent and aerosol applications.
  • GWP global warming potential
  • 1233yd has 1233yd E-form and Z-form as geometrical isomers, but depending on the use and compatibility with the components to be mixed, 1233yd Z-form or 1233yd E-form can be used alone or 1233yd
  • the Z form and the E form of 1233yd are also used as a mixture.
  • HCFC-244ca 3-chloro-1,1,2,2-tetrafluoropropane
  • HCFC-245ca A method for producing 1,1,2,2,3-pentafluoropropane (HCFC-245ca) is disclosed (for example, see Patent Document 1).
  • 1233yd is by-produced. Therefore, 1233yd can be obtained by recovering the composition obtained by the above reaction and separating 1233yd contained in the composition.
  • 1233yd produced by the above method is a mixture of 1233yd E-form and 1233yd Z-form, There is no disclosure about separation of E-form and Z-form of 1233yd. In addition, the above method does not adjust the composition of E-form and Z-form of 1233yd.
  • the present invention provides a production method capable of producing 1233yd having a predetermined composition by selectively reacting either E-form or Z-form of 1233yd with an industrially advantageous and efficient method. Objective.
  • the present invention provides a method for producing 1233yd having the following configuration.
  • the 1-chloro-2,3,3-trifluoropropene (E) in the raw material composition contained in a molar ratio different from the above is isomerized at the isomerization reaction temperature to give 1-chloro-2,3 , 3-trifluoropropene (Z), a process for producing 1-chloro-2,3,3-trifluoropropene (Z).
  • the molar ratio of the 1-chloro-2,3,3-trifluoropropene (Z) to the 1-chloro-2,3,3-trifluoropropene (E) (1- Chloro-2,3,3-trifluoropropene (Z) / 1-chloro-2,3,3-trifluoropropene (E)) is smaller than the equilibrium ratio (molar ratio) at the isomerization reaction temperature, 1]
  • the isomerization reaction is performed by bringing the raw material composition into contact with a metal catalyst. Production of 1-chloro-2,3,3-trifluoropropene (Z) according to [1] or [2] Method.
  • the metal constituting the metal catalyst is a Group 4 metal element, Group 6 metal element, Group 8 metal element, Group 9 metal element, Group 10 metal element, Group 11 metal element, Group 12 1-chloro-2,3,3-trifluoropropene (Z) according to [3] or [4], which is at least one element selected from the group consisting of group metal elements and group 13 metal elements Production method.
  • the 1-chloro-2,3,3-trifluoropropene (Z) in the raw material composition contained in a molar ratio different from) is isomerized at the isomerization reaction temperature to give 1-chloro-2,
  • the molar ratio of the 1-chloro-2,3,3-trifluoropropene (Z) to the 1-chloro-2,3,3-trifluoropropene (E) (1- Chloro-2,3,3-trifluoropropene (Z) / 1-chloro-2,3,3-trifluoropropene (E)) is greater than the equilibrium ratio (molar ratio) at the isomerization reaction temperature, 14] for producing 1-chloro-2,3,3-trifluoropropene (E).
  • the 1233yd Z form can be produced by selectively reacting the 1233yd E form with an industrially advantageous and efficient method.
  • the 1233yd E-isomer can be produced by selectively reacting the 1233yd Z-isomer with an industrially advantageous and efficient method.
  • a method for producing 1233yd which is one embodiment of the present invention, is 1-chloro-2,3,3-trifluoropropene (E) (HCFO-1233yd (E), hereinafter “ And 1-chloro-2,3,3-trifluoropropene (Z) (HCFO-1233yd (Z), hereinafter also referred to as “1233yd (Z)”) are isomerized.
  • a raw material composition containing a molar ratio different from the equilibrium ratio at temperature is prepared, and 1233yd (E) in the raw material composition is isomerized to produce 1233yd (Z).
  • the method for producing 1233yd which is another embodiment of the present invention, isomerizes 1233yd (Z) in the raw material composition to give 1233yd (E). It is a manufacturing method.
  • the isomerization reaction between 1233yd (E) and 1233yd (Z) represented by the above formulas [1] and [2] is an equilibrium reaction.
  • the isomerization reaction is performed under conditions where the isomerization reaction occurs (hereinafter also referred to as “isomerization conditions”).
  • the isomerization reaction represented by the above formula [1] or [2] is also simply referred to as “isomerization reaction” hereinafter.
  • 1233yd (Z) and 1233yd (E) are present at a predetermined molar ratio (equilibrium ratio).
  • the equilibrium ratio refers to the “molar ratio of 1233yd (Z) to 1233yd (E) in the equilibrium state of the isomerization reaction”, and [[1233yd (Z) in 1233yd in the equilibrium state] Number of moles) / (number of moles of 1233yd (E) in 1233yd)].
  • the equilibrium ratio varies depending on the reaction temperature (hereinafter also referred to as isomerization reaction temperature), pressure, and the like during the isomerization reaction.
  • the equilibrium ratio at an atmospheric pressure and an isomerization reaction temperature of 20 ° C. is about 97/3.
  • the equilibrium ratio at an atmospheric pressure and an isomerization reaction temperature of 230 ° C. is about 91/9.
  • “1233yd (Z) / 1233yd (E)” represents the molar ratio of 1233yd (Z) to 1233yd (E).
  • the abundance ratio (mol%) of 1233yd (Z) with respect to the sum of 1233yd (E) and 1233yd (Z) at each isomerization reaction temperature is shown in FIG. From the graph of FIG. 1, it can be seen that as the isomerization reaction temperature increases, the abundance ratio of 1233yd (Z) decreases and the equilibrium ratio decreases.
  • 1233yd (Z) can be produced by using a raw material composition in which 1233yd (Z) / 1233yd (E) is smaller than the equilibrium ratio at the isomerization reaction temperature. That is, by the isomerization reaction at the isomerization reaction temperature, the content ratio of 1233yd (Z) in the reaction product is increased as compared with the content ratio in the raw material composition to produce 1233yd (Z).
  • the content of 1233yd (Z) may be 80 mol% or more.
  • 1233yd (E) is produced by using a raw material composition in which 1233yd (Z) / 1233yd (E) is larger than the equilibrium ratio at the isomerization reaction temperature. it can. That is, by the isomerization reaction at the isomerization reaction temperature, the content ratio of 1233yd (Z) in the reaction product is decreased from the content ratio in the raw material composition, and 1233yd (E) is produced.
  • the reaction from 1233yd (E) to 1233yd (Z) and 1233yd (Z) are adjusted by adjusting 1233yd (Z) / 1233yd (E) in the raw material composition.
  • any reaction can be allowed to proceed selectively.
  • the raw material composition contains 1233yd (E) and 1233yd (Z) at a molar ratio different from the equilibrium ratio (molar ratio) at the isomerization reaction temperature.
  • the raw material composition may contain impurities other than 1233yd (E) and 1233yd (Z) in addition to 1233yd (E) and 1233yd (Z). Impurities contained in the raw material composition are produced in addition to 1233yd (E) and 1233yd (Z) when manufacturing raw materials of 1233yd (E) and 1233yd (Z), and 1233yd (E) and 1233yd (Z). Such as by-products.
  • the impurity is preferably a compound which is inactive under conditions where 1233yd (E) or 1233yd (Z) undergoes an isomerization reaction.
  • 1233yd (E) and 1233yd (Z) can be manufactured by a known method.
  • 1233yd is obtained as a by-product when HCFC-244ca is reacted with hydrogen fluoride to produce HCFC-245ca.
  • 1233yd obtained by the above method may be used as it is as a raw material composition, or 1233yd is separated into E-form and Z-form of 1233yd by a known method such as distillation and prepared to a desired mixing ratio May be used as a raw material composition.
  • the product HCFC-245ca, the production raw material HCFC-244ca, and 1-chloro-3,3-difluoro by-produced in the production process Propin etc. are included. You may use this composition as a raw material composition as it is.
  • the manufacturing method of this embodiment can be either a batch method or a continuous distribution method.
  • the manufacturing method of the present embodiment is preferably a continuous distribution method in terms of manufacturing efficiency.
  • a desired compound can be produced by the isomerization reaction by subjecting the raw material composition satisfying the above conditions to an isomerization reaction under predetermined isomerization conditions. Further, the isomerization reaction is promoted by a method of bringing the raw material composition into contact with the metal catalyst in the reactor, a method of bringing the raw material composition into contact with the radical generator in the reactor, or a method of heating the raw material composition. be able to. According to these methods, the isomerization reaction can be rapidly advanced to achieve an equilibrium state. Therefore, the above method is suitable as an industrial method in which 1233yd (E) is isomerized to produce 1233yd (Z), or 1233yd (Z) is isomerized to produce 1233yd (E).
  • the isomerization reaction may be performed in a liquid phase or in a gas phase.
  • the reaction is carried out in the liquid phase
  • the reaction time can be shortened compared to the case where the reaction is carried out in the liquid phase, and 1,2,3-trichloro-3-fluoropropene (ClCHF), which is a byproduct, can be obtained.
  • ClCHF 1,2,3-trichloro-3-fluoropropene
  • the reactor used in the production method of the present embodiment is not particularly limited as long as it can withstand the temperature and pressure in the reactor described later.
  • a glass flask, an autoclave, a cylindrical vertical reactor is used. Can be used.
  • a material of the reactor glass, iron, nickel, iron, an alloy mainly containing nickel, or the like is used. Further, the reactor may be provided with an electric heater for heating the inside of the reactor.
  • the isomerization reaction is preferably performed using a metal catalyst.
  • a metal catalyst By using a metal catalyst, the reaction rate can be improved and the production efficiency can be improved.
  • the metal catalyst has a catalytic action for the isomerization reaction. Examples of the metal catalyst include metals (metal simple substance or alloy), metal oxides, metal halides, and the like.
  • a metal catalyst may be used individually by 1 type, and may use 2 or more types together.
  • metal oxides or metal halides are preferable because the isomerization reaction proceeds efficiently.
  • Examples of the metal constituting the metal catalyst include transition metal elements, Group 12 metal elements, Group 13 metal elements, Group 14 metal elements, and Group 15 metal elements. Among them, Group 4 metal element, Group 6 metal element, Group 8 metal element, Group 9 metal element, Group 10 metal element, Group 11 metal element, Group 12 metal element, Group 13 metal element, Group 14 metal element, Group 15 metal element are preferred, Group 4 metal element, Group 6 metal element, Group 8 metal element, Group 10 metal element, Group 11 metal element, Group 12 metal element, Group 13 metal elements are preferred.
  • the metal constituting the metal catalyst is a transition metal element, a Group 12 metal element, a Group 13 metal element, a Group 14 metal element, or a Group 15 metal element, specifically, titanium (Ti), zirconium (Zr), hafnium (Hf) (Group 4 metal element), niobium (Nb), tantalum (Ta) (Group 5 metal element), chromium (Cr), tungsten (W) (Group 6 metal element), Rhenium (Re) (Group 7 metal element), Iron (Fe), Ruthenium (Ru) (Group 8 metal element), Cobalt (Co), Rhodium (Rh) (Group 9 metal element), Nickel (Ni) , Palladium (Pd), platinum (Pt) (Group 10 metal element), copper (Cu) (Group 11 metal element), zinc (Zn) (Group 12 element), boron (B), aluminum (Al) , Gallium (Ga), indium (In (Group 13 metal element), tin (Sn) (Group 14 metal element), more preferably at least
  • the metal catalyst may be one of the above metals or an alloy of two or more metals.
  • the metal oxide may be one kind of the above-mentioned metal oxide or a complex oxide of two or more kinds of metals.
  • the metal halide may be a single halide of the above-described metal or a composite halide of two or more metals.
  • the metal catalyst may be supported on a carrier.
  • the carrier include an alumina carrier, a zirconia carrier, a silica carrier, a silica alumina carrier, a carbon carrier represented by activated carbon, a barium sulfate carrier, and a calcium carbonate carrier.
  • the activated carbon include activated carbon prepared from raw materials such as wood, charcoal, fruit glass, coconut shell, peat, lignite and coal.
  • the support is the same kind of compound as the metal catalyst, it may have a function as a metal catalyst.
  • the metal catalyst is preferably activated in advance from the viewpoint of improving the reactivity.
  • the activation treatment method include a method in which a metal catalyst is brought into contact with an activation treatment agent with heating or without heating.
  • an activation treatment agent for example, hydrogen fluoride, hydrogen chloride, fluorine-containing hydrocarbon, or the like can be used.
  • an activation processing agent 1 type may be used independently and 2 or more types may be used together. Among them, it is preferable to use a fluorinated hydrocarbon as the activation treatment agent.
  • fluorine-containing hydrocarbon used as the activation treatment agent examples include trichlorofluoromethane (CFC-11), dichlorodifluoromethane (CFC-12), chlorotrifluoromethane (CFC-13), and dichlorofluoromethane (HCFC-21). Chlorodifluoromethane (HCFC-22), trifluoromethane (HFC-23), tetrafluoroethylene (FO-1114) and the like are preferable.
  • 1233yd (E) or 1233yd (Z) in a raw material composition can also be used for an activation processing agent.
  • a reactivation treatment can be performed on the metal catalyst. That is, in the isomerization reaction, when the activity of the metal catalyst decreases and the conversion rate between the E-form and the Z-form of 1233yd decreases (when it takes a long time to reach the isomerization equilibrium). For this, it is preferable to reactivate the metal catalyst. Thereby, the activity of the metal catalyst can be regenerated and the metal catalyst can be reused.
  • Examples of the reactivation treatment method include a method of bringing a metal catalyst into contact with an activation treatment agent under heating or non-heating as in the activation treatment before use.
  • the treatment agent (reactivation treatment agent) for the reactivation treatment oxygen, hydrogen fluoride, hydrogen chloride, chlorine-containing / fluorine-containing hydrocarbons, or the like can be used.
  • Chlorine-containing and fluorine-containing hydrocarbons include compounds in which part of the hydrocarbon hydrogen is substituted with chlorine, fluorine-substituted compounds, chlorine and fluorine-substituted compounds, such as carbon tetrachloride, chloroform, Dichloromethane (HCC-30), chloromethane, vinyl chloride, CFC-11, CFC-12, CFC-13, HCFC-21, HCFC-22, HFC-23, FO-1114, 1233yd (E), 1233yd (Z) Etc.
  • an inert gas such as nitrogen, argon, or helium can be used to dilute the reactivation treatment agent from the viewpoint of suppressing side reactions and improving the durability of the metal catalyst.
  • the metal 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 metal 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 400 ° C.
  • a metal halide is preferable as the metal catalyst.
  • a metal halide containing at least one element selected from the group consisting of Al, Sb, Nb, Ta, W, Re, B, Sn, Ga, In, Zr, Hf, and Ti.
  • metal halide examples include metal chlorides such as GaCl 2 , GaCl 3 , ZrCl 4 , BCl 3 , AlCl 3 , HfCl 4 , InCl 3 , TiCl 4 , or a part of these metal chlorides fluorinated.
  • metal chlorides such as GaCl 2 , GaCl 3 , ZrCl 4 , BCl 3 , AlCl 3 , HfCl 4 , InCl 3 , TiCl 4 , or a part of these metal chlorides fluorinated.
  • AlFCl 2 , AlF 2 Cl, TiCl 2 F 2 , TiClF 3 , ZrCl 2 F 2, ZrCl 2 F , ZrClF 2 and the like can be used.
  • metal bromides such as GaBr 3 , GaI 3 , HfBr 4 , InI 3 , TiBr 4 , metal iodides or metal bromides thereof, and a part of these metal bromides and metal iodides are chlorinated by the above-described activation treatment
  • Fluorinated ones can be used.
  • a compound in which a part of the metal chloride is fluorinated, such as AlFCl 2 and AlF 2 Cl is preferable because the isomerization reaction can proceed efficiently.
  • the addition amount of such a metal catalyst is preferably 1 to 100% by mass by external addition to the total amount (100% by mass) of 1233yd (E) and 1233yd (Z) in the raw material composition, It is more preferably 5 to 50% by mass, and further preferably 5 to 15% by mass. Within the above range, the isomerization reaction can proceed efficiently.
  • the reaction solvent is a compound that is inactive with respect to the metal catalyst and dissolves the starting material and the target product but does not dissolve the metal catalyst.
  • it is a compound that can be easily separated from the target product by distillation or the like.
  • a reaction solvent for example, an aprotic organic solvent having a boiling point of 60 ° C. to 200 ° C., specifically, carbon tetrachloride, chloroform and the like are preferable.
  • the reaction conditions when the isomerization reaction is performed in a liquid phase using a metal catalyst are preferably a reaction temperature of 0 to 150 ° C, more preferably 10 to 100 ° C, and more preferably 10 to 50 ° C. More preferably. Within the above range, the isomerization reaction can proceed efficiently.
  • the reaction time is usually preferably 0.5 to 200 hours, more preferably 1 to 100 hours, and even more preferably 1 to 10 hours from the viewpoint of production efficiency.
  • an isomerization reaction can be performed by making a raw material composition and a metal catalyst contact in a reactor. Specifically, for example, it can be carried out by accommodating a metal catalyst in a reactor, forming a reaction part, and circulating the raw material composition in the reaction part.
  • the metal catalyst may be accommodated in either a fixed bed type or a fluidized bed type. In the case of a fixed floor type, either a horizontal fixed floor type or a vertical fixed floor type may be used.
  • the metal catalyst may be a vertical fixed bed type. preferable.
  • the production method of the present embodiment is performed in a continuous flow system, and the raw material composition is brought into contact with the metal catalyst in the gas phase to carry out the isomerization reaction.
  • a single metal or a metal oxide as the metal catalyst.
  • Specific examples include iron, cobalt, nickel, palladium, chromium oxide (chromia), aluminum oxide (alumina), zinc oxide, iron fluoride, aluminum fluoride, aluminum chloride, chromium fluoride, and chromium chloride.
  • chromia chromium oxide
  • aluminum oxide alumina
  • zinc oxide iron fluoride, aluminum fluoride, aluminum chloride, chromium fluoride, and chromium chloride.
  • alumina and chromia are preferable because they are easily available and allow the isomerization reaction to proceed efficiently.
  • the dilution gas is supplied to the reactor together with the raw material composition from the viewpoints of suppressing side reactions, ease of supply of starting materials to the reactor, and adjusting the flow rate. It is preferable to supply to. Moreover, when performing isomerization reaction in presence of the above-mentioned metal catalyst, there exists an advantage of improving durability of a metal catalyst by using dilution gas.
  • the dilution gas examples include nitrogen, carbon dioxide, a rare gas (such as helium), and a gas of an organic compound that is inert in the isomerization reaction of the present embodiment.
  • Inactive organic compounds include saturated hydrocarbons such as methane, ethane, propane, butane, pentane, hexane, trifluoromethane (HFC-23), difluoromethane (HFC-32), pentafluoroethane (HFC-125).
  • Fluoro such as tetrafluoroethane (HFC-134 or HFC-134a), trifluoroethane (HFC-143 or HFC-143a), difluoroethane (HFC-152 or HFC-152a), tetrafluoropropane (HFC-254eb etc.)
  • a hydrocarbon is mentioned.
  • the amount of the dilution gas is not particularly limited, but specifically, it is preferably 1 to 10000 mol%, more preferably 10 to 1000 mol%, relative to the raw material composition (100 mol%) supplied to the reactor. More preferred is an amount of 30 to 500 mol%, most preferably 50 to 150 mol%. 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 300 ° C., and is preferably 50 to 250 ° C. from the viewpoint of vaporizing 1233yd (E) and 1233yd (Z) in the raw material composition and improving the reactivity. Is more preferable.
  • the raw material composition and the dilution gas when used, it is preferable to introduce the raw material composition and the dilution gas into the reactor after preheating to the above-described 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. Good.
  • the reaction conditions when the isomerization reaction is carried out in the gas phase are about 1.0 MPa when the reaction pressure requires pressurization for the purpose of shortening the reaction time, for example.
  • the following pressurizing conditions and the internal pressure in the reactor can be a normal pressure to 1.0 MPa pressure condition. From the viewpoint of ease of industrial implementation, it is preferable to carry out the reaction at normal pressure or a slight pressure of 0.2 MPa or less. Normal pressure is atmospheric pressure.
  • the contact temperature (reaction temperature) between the raw material composition and the metal catalyst is preferably 0 to 500 ° C., more preferably 50 to 350 ° C., even more preferably 100 to 260 ° C., most preferably 150 to 250 ° C. preferable. If reaction temperature is more than the said lower limit, an isomerization reaction can be advanced efficiently. On the other hand, if reaction temperature is below the said upper limit, the production
  • the contact time (reaction time) between the raw material composition and the metal 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 isomerization reaction can be performed by bringing the raw material composition into contact with a radical generator.
  • the radical generator is activated by heat or light to generate radicals.
  • Examples of the method for bringing the raw material composition into contact with the radical generator to cause the isomerization reaction include a method in which the raw material composition is brought into contact with the radical generator activated by heat or light in a reactor. .
  • the isomerization reaction is preferably performed in the gas phase.
  • the radical generator may be activated by either heat or light, or both may be used in combination. Industrially, activation only by heat is preferable, a mixture of a raw material composition and a radical generator is supplied to a heated reactor, heat energy is applied to the mixture in the reactor, and the radical generator is generated by heat.
  • the method of activating is simple and preferable.
  • the radical generator When the radical generator is activated by light, the radical generator may be irradiated with light.
  • the irradiation light include ultraviolet rays and visible rays including light having a wavelength of 200 to 400 nm.
  • the light source used for such light irradiation include a high pressure mercury lamp, a low pressure mercury lamp, and a metal halide lamp.
  • a light source equipped with a jacket made of a corrosion-resistant material that transmits at least light having a wavelength necessary for the isomerization reaction and is inert to the components existing in the reaction system is used as the reaction component.
  • the jacket is preferably a jacket having a cooling means depending on the reaction temperature.
  • a radical is a chemical species such as an atom, molecule, or ion that has an unpaired electron. It can be a radical cation with a positive charge, a radical anion with a negative charge, a radical with a neutral charge, a biradical, a carbene, etc. Including. Specific examples include a fluorine radical, a chlorine radical, a bromine radical, an iodine radical, an oxygen radical, a hydrogen radical, a hydroxy radical, a nitroxy radical, a nitrogen radical, an alkyl radical, a difluorocarbene, or a carbon radical.
  • the radical generator that generates radicals as described above is a compound other than 1233yd (E) and 1233yd (Z) that generates radicals by application of external energy such as heat and light.
  • Specific examples of the radical generator include halogen gases such as chlorine and bromine, halogenated hydrocarbons, air, oxygen, ozone, hydrogen peroxide, and the like.
  • Halogenated hydrocarbons include some or all of hydrogen atoms bonded to carbon atoms in alkanes such as methane, ethane, propane, butane, pentane and hexane, and alkenes such as ethene, propene, butene, pentene and hexene.
  • a radical generator may be used individually by 1 type, and may use 2 or more types together.
  • radical generators oxygen, air, and chlorine are preferable because they are inexpensive and easily available.
  • chlorine is preferable because it easily generates radicals.
  • air or oxygen is suitable as the radical generator from the viewpoint of easy separation from the product.
  • the amount of the radical generator supplied to the reactor is very small. This is because the generation of radicals is chained. Moreover, addition of an excessive radical generator not only wastes auxiliary materials, but also causes a load on the separation process between the target substance or starting material after the reaction and the radical generator.
  • the isomerization reaction in the production method of 1233yd of this embodiment can be performed by changing the temperature of the raw material composition, for example, by heating.
  • the isomerization reaction can be performed by heating the raw material composition in the reactor.
  • the raw material composition may be supplied into a reactor heated by a heating furnace such as an electric furnace.
  • the isomerization reaction is preferably performed in the gas phase.
  • the reaction pressure is preferably normal pressure or a slight pressure of 0.2 MPa or less, as in the case of using a metal catalyst.
  • the heating temperature is preferably 400 to 1000 ° C, more preferably 400 to 900 ° C.
  • the residence time (reaction time) of the raw material composition in the reactor is preferably 0.001 to 1000 seconds, and more preferably 0.01 to 100 seconds. Increasing the reaction temperature within the above-mentioned preferred range or increasing the reaction time improves the conversion ratio between isomers, and 1233yd containing the isomer at an equilibrium ratio at the reaction temperature or a ratio close to the equilibrium ratio. Can be obtained.
  • reaction product In the production method of the present embodiment, 1233yd (E) or 1233yd (Z), which is the target product, can be obtained in the reaction product flowing out from the reactor.
  • the reaction product may contain by-products generated from impurities contained in the raw material composition, and by-products generated by decomposition of 1233yd (E) or 1233yd (Z).
  • the by-product is 1,2,3-trichloro-3-fluoropropene.
  • the reaction product includes both 1233yd (E) and 1233yd (Z).
  • 1233yd (E) and 1233yd (Z) in the reaction product have different boiling points, they can be separated by an ordinary distillation method. Therefore, the reaction product obtained above is subjected to acid washing, alkali washing, dehydration with an adsorbent such as synthetic zeolite, removal of by-products as necessary, and distillation to obtain high-purity 1233yd (E) and 1233yd (Z) can be obtained respectively.
  • the reaction product containing 1233yd (E) and 1233yd (Z) which has been washed as described above, is supplied to a distillation column for distillation, and 1233yd (E) is the main component from the top of the column. From the bottom of the distillate, distillate containing 1233yd (Z) can be obtained.
  • 1233yd (Z) / 1233yd (E) contained in the distillate obtained by distillation is smaller than the equilibrium ratio. Therefore, 1233yd (E) in the distillate can be converted to 1233yd (Z) by using this distillate as a raw material composition and carrying out an isomerization reaction in the same manner as described above.
  • the target product is 1233yd (E)
  • 1233yd (Z) / 1233yd (E) contained in the bottom product obtained by distillation becomes larger than the equilibrium ratio. Therefore, it is possible to convert 1233yd (Z) in the distillate into 1233yd (E) by using the bottom product as a raw material composition and carrying out an isomerization reaction in the same manner as described above.
  • the target product can be efficiently produced by repeatedly performing the isomerization reaction and distillation.
  • 1233yd (E) by subjecting the raw material composition to an isomerization reaction under predetermined isomerization conditions, 1233yd (E) can be isomerized in an industrially advantageous and efficient manner. 1233yd (Z) or 1233yd (Z) can be isomerized to produce 1233yd (E).
  • the liquid after the reaction was filtered to remove the metal catalyst, and 20 g of the reaction product was recovered as a liquid phase. Subsequently, the liquid phase of the obtained reaction product was analyzed using a gas chromatograph to determine the composition of the reaction product. The results are shown in Table 1 together with the reaction conditions.
  • Example 2 The isomerization reaction was carried out in the same procedure as in Example 1 except that the content ratio of E-form and Z-form of 1233yd in the raw material composition was changed. Table 2 shows the composition of the raw material composition, reaction conditions, and results.
  • the metal catalyst was activated as follows. That is, pellet-shaped activated alumina (diameter 3 mm, height 3 mm, specific surface area 160 m 2 / g, manufactured by JGC Catalysts & Chemicals Co., Ltd., product name N612N) is 2.54 cm in inner diameter and 100 cm long inconel (registered trademark) 600 reaction tube. (Reactor) was filled and immersed in a salt bath. The salt bath was heated to 250 ° C., and a 2/1 (molar ratio) mixed gas of nitrogen / HCFC-22 (CHClF 2 ) was passed through the reactor for 10 hours to activate the metal catalyst.
  • pellet-shaped activated alumina (diameter 3 mm, height 3 mm, specific surface area 160 m 2 / g, manufactured by JGC Catalysts & Chemicals Co., Ltd., product name N612N) is 2.54 cm in inner diameter and 100 cm long inconel (registered trademark) 600 reaction
  • the salt bath temperature (reaction temperature) was set to 230 ° C. in Example 3 and 280 ° C. in Example 4. Further, the supply of HCFC-22 was stopped, and the same raw material composition and nitrogen mixed gas as in Example 1 were supplied into the reactor in a contact time (reaction time) of 20 seconds.
  • the raw material composition was circulated in the reactor under the conditions shown in Table 3 to cause an isomerization reaction.
  • the composition of the reaction product was analyzed by analyzing the gas composition at the outlet of the reactor with a gas chromatograph. Table 3 shows the composition of the raw material composition, reaction conditions, and analysis results.
  • Example 5 The isomerization reaction was carried out under the same conditions as in Example 3 except that the reaction temperature was changed to 400 ° C. without using a metal catalyst. Table 3 shows the composition of the raw material composition, reaction conditions, and analysis results.
  • Example 6 The isomerization reaction was carried out in the same procedure as in Example 3 except that the content ratio of E-form and Z-form of 1233yd in the raw material composition was changed.
  • Table 4 shows the composition of the raw material composition, reaction conditions, and analysis results.
  • Example 8 The isomerization reaction was performed in the same procedure as in Example 7 except that the composition of the raw material composition was changed.
  • Table 6 shows the composition of the raw material composition, reaction conditions, and analysis results.
  • Example 9 In the same manner as in Example 3, the activated alumina obtained above was used as the metal catalyst. Further, in the same manner as in Example 3, the reaction temperature was set to 230 ° C. in Example 9 and 280 ° C. in Example 10, and a mixed gas of a raw material composition having the composition shown in Table 7 and nitrogen was supplied to the reactor. . The raw material composition was circulated in the reactor under the conditions shown in Table 7 to cause an isomerization reaction. The composition of the reaction product was analyzed by analyzing the gas composition at the outlet of the reactor with a gas chromatograph. Table 7 shows the composition of the raw material composition, reaction conditions, and analysis results.
  • Example 11 The isomerization reaction was performed in the same procedure as in Example 9 except that the reaction temperature was changed to 400 ° C. without using a metal catalyst.
  • Table 7 shows the composition of the raw material composition, reaction conditions, and analysis results.
  • Example 12 The isomerization reaction was performed in the same procedure as in Example 9 except that the composition of the raw material composition was changed.
  • Table 8 shows the composition of the raw material composition, reaction conditions, and analysis results.
  • 1233yd (Z) or 1233yd (E) can be produced by subjecting the raw material composition to an isomerization reaction under predetermined isomerization conditions to cause an isomerization reaction.

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

Abstract

L'invention concerne un procédé de production dans lequel l'un ou l'autre de 1233yd (E) ou 1233yd (Z) peut être sélectivement mis en réaction de manière industriellement avantageuse et efficace. Le procédé de production 1233yd comprend, dans une composition de matière première contenant 1233yd (E) et 1233yd (Z) dans un rapport molaire différent du rapport d'équilibre dans la température de réaction d'isomérisation, soumettre le 1233yd (E) à une réaction d'isomérisation pour produire 1233yd (Z), ou soumettre le 1233yd (Z) à une réaction d'isomérisation pour produire 1233yd (E).
PCT/JP2017/032837 2016-09-12 2017-09-12 Procédé de production de 1-chloro -2,3,3-trifluoropropène WO2018047972A1 (fr)

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