WO2022163745A1 - Procédé de production de 3-chloro-1,1,2,2-tétrafluoropropane et procédé de production de 1-chloro-2,3,3-trifluoropropane - Google Patents

Procédé de production de 3-chloro-1,1,2,2-tétrafluoropropane et procédé de production de 1-chloro-2,3,3-trifluoropropane Download PDF

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WO2022163745A1
WO2022163745A1 PCT/JP2022/003032 JP2022003032W WO2022163745A1 WO 2022163745 A1 WO2022163745 A1 WO 2022163745A1 JP 2022003032 W JP2022003032 W JP 2022003032W WO 2022163745 A1 WO2022163745 A1 WO 2022163745A1
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reaction
tetrafluoropropane
production method
chloro
chlorine
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PCT/JP2022/003032
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English (en)
Japanese (ja)
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厚史 藤森
聡史 河口
英史 塩田
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Ａｇｃ株式会社
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Priority to JP2022578466A priority Critical patent/JPWO2022163745A1/ja
Priority to CN202280011803.XA priority patent/CN116802170A/zh
Publication of WO2022163745A1 publication Critical patent/WO2022163745A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
    • C07C17/10—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/25—Preparation of halogenated hydrocarbons by splitting-off hydrogen halides from halogenated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C19/00—Acyclic saturated compounds containing halogen atoms
    • C07C19/08—Acyclic saturated compounds containing halogen atoms containing fluorine
    • C07C19/10—Acyclic saturated compounds containing halogen atoms containing fluorine and chlorine
    • 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

Definitions

  • the present invention relates to a method for producing 3-chloro-1,1,2,2-tetrafluoropropane and a method for producing 1-chloro-2,3,3-trifluoropropene.
  • 3-chloro-1,1,2,2-tetrafluoropropane (CHF 2 —CF 2 —CH 2 Cl.
  • HCFC-244ca hereinafter also referred to as 244ca) is a new detergent, refrigerant, blowing agent, solvent, and aerosols, or their synthetic raw materials.
  • HCFO-1233yd hereinafter also referred to as 1233yd.
  • TFPO 2,2,3,3-tetrafluoropropanol
  • N,N-dimethylformamide is used as a chlorinating agent in the presence of
  • a method for the preparation of 244ca is described by reacting with thionyl chloride.
  • the method for producing 244ca described in Patent Document 2 uses thionyl chloride as a chlorinating agent, so that the reaction product contains by-products such as hydrogen chloride and sulfur dioxide, and is neutralized with a large amount of aqueous alkaline solution. Therefore, a method for producing 244ca suitable for industrial-scale mass production has been investigated.
  • An object of the present invention is to provide an industrially advantageous method for producing high-purity 244ca.
  • the solvent is carbon tetrachloride, 1,1,2-trichloro-1,2,2-trifluoroethane, 1-chloro-1,1,2,2-tetrafluoropropane, 1,3-dichloro -1,1,2,2-tetrafluoropropane, 1,3,3-trichloro-1,1,2,2-tetrafluoropropane, 1,3,3,3-tetrachloro-1,1,2, 2-tetrafluoropropane, 3-chloro-1,1,2,2-tetrafluoropropane, 1,1-dichloro-2,2,3,3-tetrafluoropropane, 1,1,1-trichloro-2, At least selected from the group consisting of 2,3,3-tetrafluoropropane, 1,3,3,4,4,6-hexachloro-1,1,2,2,5,5,6,6-octafluorohexane 1, the production method according to [9].
  • [16] 3-chloro-1,1,2,2-tetrafluoropropane obtained by the production method according to any one of [1] to [15] is subjected to dehydrofluorination in the presence of a base or a catalyst.
  • 1,3-dichloro-2,3,3-trifluoropropene is added to the 1-chloro-2,3,3-trifluoropropene in the reaction product obtained by the dehydrofluorination reaction;
  • the production method according to [16] containing 10% by mass or less.
  • chlorine refers to molecular state chlorine (Cl 2 ).
  • Pressure means gauge pressure unless otherwise stated.
  • a compound When a compound has isomers, it indicates one or a mixture of two or more selected from the isomers, unless otherwise specified. For example, when Z and E isomers are present, all mean Z isomers only, E isomers only, or mixtures of Z and E isomers in any proportion.
  • (E) or (Z) is attached to the end of a compound name or compound abbreviation, the (E) isomer or (Z) isomer of the respective compound is indicated. For example, 1233yd(Z) indicates the Z isomer and 1233yd(E) indicates the E isomer.
  • the method for producing 244ca of the present invention (hereinafter also simply referred to as the “production method of the present invention”) comprises 1,1,2,2-tetrafluoropropane (CHF 2 —CF 2 —CH 3 .HFC-254cb. , also referred to as 254cb) with chlorine.
  • the reaction for obtaining 244ca by the chlorination reaction of 254cb is the reaction represented by the following formula (1) (hereinafter also referred to as reaction (1)).
  • the production method of the present invention has the advantage that 244ca can be selectively obtained in the chlorination reaction of 254cb with almost no other chlorinated products.
  • 254cb is used as a raw material.
  • 254cb is a known compound known as a raw material or intermediate for producing fluorine-containing compounds.
  • Methods for obtaining 254cb are not particularly limited, and include known methods described in International Publication No. 2018/139654 and the like.
  • hydrogen is added to 1-chloro-1,1,2,2-tetrafluoropropane (CCIF 2 —CF 2 —CH 3 , HCFC-244cc, hereinafter also referred to as 244cc) in the presence of a catalyst, It can be produced by reacting at temperatures above 200°C.
  • a hydrogenation catalyst is used for the above reaction in which 244cc is reacted with hydrogen and reduced.
  • a palladium catalyst is preferred as the hydrogenation catalyst.
  • the palladium catalyst may be a catalyst composed of palladium, or a metal catalyst containing palladium, as well as simple palladium.
  • a palladium alloy catalyst is preferable as the metal catalyst containing palladium.
  • Palladium alloy catalysts include palladium/platinum alloy catalysts and palladium/rhodium alloy catalysts.
  • the palladium catalyst may be a metal catalyst containing palladium or a mixture with other metals.
  • a catalyst in which the palladium catalyst is supported on a carrier (hereinafter also referred to as a palladium-supported catalyst) may be used, or a composite catalyst in which the palladium catalyst and another metal are separately supported on a carrier may be used.
  • Examples of the carrier for the palladium-supported catalyst include activated carbon, metal oxides (alumina, zirconia, silica, etc.), and activated carbon is preferred from the viewpoint of activity, durability, and reaction selectivity.
  • Examples of activated carbon include those obtained from plant raw materials (wood, charcoal, fruit shells, coconut shells, etc.) and mineral raw materials (peat, lignite, coal, etc.). The activated carbon obtained is preferred, and coconut shell activated carbon is particularly preferred.
  • the reduction reaction for reacting 244cc with hydrogen is preferably carried out in the gas phase.
  • a reaction tube is filled with a catalyst-carrying carrier to form a catalyst layer, and 244 cc gas and hydrogen gas are passed through the catalyst layer.
  • the temperature of the catalyst layer during the reaction is above 200°C, preferably 210 to 350°C, more preferably 250 to 300°C.
  • the ratio of 244cc and hydrogen is adjusted accordingly.
  • a diluent gas such as nitrogen gas or rare gas may be added to the 244 cc gas and hydrogen gas for the reaction.
  • 254cb From the reaction product obtained by reacting 244cc with hydrogen, 254cb can be isolated by a normal separation method, for example, by distillation, and used as a raw material for the production method of the present invention.
  • 254cb which is the raw material for the production method of the present invention, may be a mixture with other compounds. That is, the starting material for the production method of the present invention should only contain 254cb, and for example, a mixture of 254cb and other compounds may be used as the starting material.
  • Other compounds that can be contained in the raw materials applied to the production method of the present invention include impurities such as raw materials for producing 254cb and by-products produced in addition to 254cb when producing 254cb.
  • impurities such as raw materials for producing 254cb and by-products produced in addition to 254cb when producing 254cb.
  • by-products generated from the impurities may be removed by known means such as distillation, extractive distillation, azeotropic distillation, membrane separation, two-layer separation, and adsorption.
  • the impurity is preferably a compound that is inactive in the production method of the present invention.
  • 254cb is preferably contained as a main component in the raw materials used for the chlorination reaction.
  • the content of 254cb is preferably 50% by mass or more, more preferably 75% by mass or more, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more, relative to the total mass of the raw materials used in the chlorination reaction. 100 mass % is mentioned as an upper limit.
  • a reactor is used to bring 254cb into contact with chlorine to produce 244ca through a chlorination reaction.
  • 254cb obtained by the method described above can be used.
  • the method of obtaining 254cb is not limited to this.
  • the production method of the present invention can be carried out in either a liquid phase or a gas phase, and is preferably carried out in a liquid phase reaction because it is more advantageous for industrial implementation.
  • 1 ,3,3-trichloro-1,1,2,2-tetrafluoropropane (CCIF 2 —CF 2 —CHCl 2 , HCFC-224ca, hereinafter also referred to as 224ca), 1,3,3,3-tetrachloro -1,1,2,2-tetrafluoropropane (CClF 2 -CF 2 -CCl 3 ; HCFC-214cb; hereinafter also referred to as 214cb), 1,1,1-trichloro-2,2,3,3- tetrafluoropropane (CHF 2 —CF 2 —CCl 3 ; HCFC-224cb; hereinafter also referred to as 224cb), 1,3,3,4,4,6-hexachloro-1,1,2,2,5,5, Chlorinated products such as 6,6-octafluorohexane may be produced as a by-product.
  • a chlorinated product other than 244ca which is a by-product of the chlorination reaction of 254cb, can be subjected to a hydrogen reduction reaction to produce 244ca as the target product or 254cb as the raw material.
  • 254cb can be produced by reacting 244cc with hydrogen in the presence of a catalyst, which can be reused as a raw material.
  • 244ca can be produced by reacting 234cc or 234cb with hydrogen in the presence of a catalyst.
  • 244ca which is the product of the production method of the present invention, is a useful compound as a raw material for producing 1233yd.
  • 1233yd is a compound that can be used in a variety of applications as a detergent, refrigerant, blowing agent, solvent, or aerosol. If the raw material containing 244ca contains 234cc, by-products may be produced, which may cause the selectivity of 1233yd to decrease. Therefore, the chlorination reaction of 254cb is preferably carried out under conditions under which the amount of 234cc produced relative to the total amount of reaction products is small.
  • the content of 234cc is preferably 10% by mass or less, more preferably 5% by mass or less, relative to the total amount of 244ca and 234cc in the reaction product. It is preferably 3 mass % or less, more preferably 1 mass % or less. Within the above range, the production of by-products is suppressed during the production of 1233yd.
  • the shape and structure of the reactor are not particularly limited as long as it can introduce and react 254cb and chlorine.
  • Such reactors include glass reactors, SUS reactors, glass lined reactors, resin lined reactors, and the like.
  • the reactor is usually provided with a temperature control section for controlling the temperature inside the reactor. Any temperature control unit may be used as long as it can control the reaction temperature between 254cb and chlorine. An oil bath etc. are mentioned as such a thing.
  • the temperature control unit may be provided integrally with the reactor.
  • the production method of the present invention can be carried out in either the liquid phase or the gas phase, and the liquid phase reaction is preferred because it is more advantageous for industrial implementation.
  • the gas phase reaction means reacting gaseous 254cb with gaseous chlorine
  • the liquid phase reaction means reacting liquid 254cb with gaseous chlorine.
  • reaction conditions in the liquid phase in the production method of the present invention are first described in detail, and then the reaction conditions in the gas phase are described in detail.
  • the ratio of 254cb and chlorine for example, the ratio of 254cb and chlorine supplied to the reactor, is selected from the viewpoint of activating the reaction, suppressing the generation of by-products, and the selectivity of 244ca.
  • chlorine (Cl 2 ) is preferably 0.01 to 3 mol, more preferably 0.1 to 2 mol, even more preferably 0.2 to 1.6, relative to 1 mol of 254cb, 0.5 to 1.5 molar is most preferred.
  • the reaction temperature (temperature inside the reactor) in the production method of the present invention is preferably -20 to 100°C, more preferably 5 to 60°C, when the reaction is carried out in the liquid phase. Within the above numerical range, the reaction can be activated and the production of by-products can be suppressed.
  • the chlorination reaction when carried out in a liquid phase reaction may be carried out in any of semi-continuous, batch, and continuous processes.
  • the reaction time the normal time adopted by each method can be applied, and it can be adjusted as appropriate according to the progress of the reaction. For example, 1 second to 100 hours is preferable, and 1 second to 10 hours is more preferable.
  • the reaction time is expressed as the contact time of 254cb and chlorine in the reactor.
  • the raw material may be supplied to the reactor by a method of supplying each component, a method of supplying each component as a mixture, or a combination of these methods.
  • the chlorine gas may be diluted with an inert gas such as nitrogen gas, if necessary.
  • the reaction time is the residence time of 254cb and chlorine in the reactor.
  • the raw materials are preferably fed into the reaction system individually or as a mixture of the components at a constant rate.
  • the raw material supply may be intermittent or continuous.
  • the chlorination reaction is carried out batchwise, it is preferable that the raw materials are fed together with a solvent and the like into a reactor prior to the reaction and subjected to the reaction.
  • the raw materials are continuously supplied and the reaction product is continuously withdrawn.
  • a method overflow method, etc. in which raw materials are continuously supplied into the reaction system from the bottom of a reactor charged with a solvent, and reaction products are continuously taken out from the top of the reactor.
  • the chlorination reaction When the chlorination reaction is performed continuously, it is preferable to feed the raw material and withdraw the product so that the raw material 254cb and chlorine stay in the reactor for 1 second to 100 hours, and the residence time is 1. Seconds to 50 hours are more preferred, and 1 second to 10 hours are particularly preferred.
  • the usual methods and apparatuses can be used in any of the semi-continuous, batch, and continuous methods, and the reaction is preferably carried out with stirring.
  • the reaction pressure in the production method of the present invention corresponds to the pressure inside the reactor.
  • the pressure in the reactor is preferably 0 to 1 MPa, more preferably 0.05 to 0.5 MPa, for efficient production.
  • the reaction is preferably carried out under pressurized conditions.
  • the production method of the present invention is preferably carried out under light irradiation.
  • the wavelength of light used for irradiation is preferably 200 to 750 nm, more preferably 250 to 730 nm. Light with a wavelength of 200 nm or more can sufficiently suppress the production reaction of by-products, and light with a wavelength of 750 nm or less allows the reaction to proceed sufficiently.
  • the light used for irradiation may include light with a wavelength of less than 200 nm or light with a wavelength of more than 750 nm.
  • light sources capable of efficiently irradiating light with a wavelength of 200 to 750 nm include, for example, fluorescent lamps, LED lights, incandescent lamps, high-pressure mercury lamps, and halogen lamps.
  • a light source that generates a large amount of heat is not preferable because it becomes difficult to keep the internal temperature of the reactor low. If the internal temperature is high, the internal pressure rises, and it is necessary to increase the pressure resistance of the reactor, which is disadvantageous in terms of cost. Also, if the internal temperature is high, side reactions tend to occur.
  • a fluorescent lamp or an LED light is preferable as a light source that generates little heat.
  • a jacketed light source is inserted into the reaction liquid and the raw material in the reaction liquid is irradiated with light from inside the reaction liquid.
  • the material of the jacket preferably transmits at least light of a wavelength useful for the above reaction, is inert to the components contained in the reaction solution, and is resistant to corrosion by these components.
  • the jacket preferably has cooling means depending on the reaction temperature.
  • 254cb and chlorine may be separately supplied to the reactor, or may be supplied in a premixed state.
  • a solvent may be used when the production method of the present invention is carried out in a liquid phase.
  • the solvent is a solvent capable of dissolving raw material components containing 254cb and chlorine, inert to the raw material components, and facilitating separation from the target product containing 244ca by distillation or the like. is preferred.
  • solvents examples include carbon tetrachloride and 1,1,2-trichloro-1,2,2-trifluoroethane.
  • 244ca may also be used as a solvent, and by-products 244cc, 234cc, 224ca, 214cb, 234cb, 224cb, 1,3,3,4,4,6-hexachloro-1,1,2,2,5,5 , 6,6-octafluorohexane may be used as a solvent.
  • the solvent one type of these compounds may be used alone, or two or more types may be used in combination.
  • the solvent is preferably carbon tetrachloride, which is low-cost and easy to separate from the target product, and 244ca, which does not require separation.
  • the amount of the solvent is not particularly limited as long as it can dissolve the generated 244ca, preferably 1 to 4000% by mass, more preferably 50 to 3000% by mass with respect to the raw material 254cb.
  • a gas inert to the above reaction may be supplied to the reactor because it is effective in adjusting the flow rate, suppressing by-products, suppressing deactivation of the catalyst, and the like.
  • diluent gas include nitrogen gas, carbon dioxide gas, helium gas, and argon gas.
  • the ratio of 254cb and chlorine for example, the ratio of 254cb and chlorine supplied to the reactor, is selected from the viewpoint of activating the reaction, suppressing the generation of by-products, and the selectivity of 244ca.
  • chlorine (Cl 2 ) is preferably 0.01 to 3 mol, more preferably 0.1 to 2 mol, even more preferably 0.2 to 1.6, relative to 1 mol of 254cb, 0.5 to 1.5 molar is most preferred.
  • the reaction time is preferably 1 second to 1 hour
  • the reaction pressure is preferably 0 to 1 MPa
  • the reaction temperature is preferably 50 to 200°C from the viewpoint of reactivity.
  • the wavelength of light used for irradiation is preferably 200 to 750 nm.
  • the reaction product obtained by performing the chlorination reaction in the liquid phase reaction or the gas phase reaction contains the target product 244ca, unreacted raw materials, solvents, by-products such as chlorinated products that are not the target product, and the like. .
  • a conventional separation method can be employed. For example, after removing chlorine by washing with an alkali, distillation removes the solvent and by-products. and the like.
  • 244ca can be purified to a higher purity by distillation, and 244ca with a desired purity can be obtained by repeating the distillation.
  • the content of 234cc is preferably 10% by mass or less with respect to the total amount of 244ca and 234cc in the reaction product, and 5 mass % or less, more preferably 3 mass % or less, and particularly preferably 1 mass % or less.
  • 244ca is separated by distillation, when a component with a boiling point lower than that of 244ca forms an azeotropic or pseudo-azeotropic composition with water, 244ca is distilled by entraining water with the low boiling point component. , can be recovered without water.
  • Specific examples of components having a boiling point lower than 244ca include 244cc, 254cb, fluoromethane, difluoromethane, 1,1,1,2-tetrafluoroethane, fluoroethane, 1,2-difluoroethane, 1233yd(E), and the like. be done.
  • (Production of 1233 yd) 244ca is a useful compound as a starting material for producing 1233yd.
  • 1233yd is a compound that can be used in a variety of applications as a detergent, refrigerant, blowing agent, solvent, or aerosol.
  • 1233yd can be produced by subjecting 244ca to a dehydrofluorination reaction.
  • a method for producing 1233yd includes a method for producing 1233yd by subjecting 244ca obtained by the production method of the present invention to a dehydrofluorination reaction in the presence of either a base or a catalyst.
  • Known methods such as International Publication No. 2016/136744 can be used as the procedure for the dehydrofluorination reaction.
  • the base used in the dehydrofluorination reaction of 244ca includes metal hydroxides, metal oxides, and metal carbonates. Among them, metal hydroxides are preferable from the viewpoint of reaction time and reaction yield. Potassium hydroxide or sodium hydroxide is particularly preferred.
  • a phase transfer catalyst is preferably used as the catalyst used in the dehydrofluorination reaction of 244ca. Examples of the phase transfer catalyst include quaternary ammonium salts, quaternary phosphonium salts, quaternary arsonium salts, sulfonium salts, crown ethers, etc. Among them, quaternary ammonium salts are preferred. is particularly preferably tetra-n-butylammonium chloride (TBAC), tetra-n-butylammonium bromide (TBAB), methyltri-n-octylammonium chloride (TOMAC).
  • TBAC tetra-n-butylammonium chloride
  • TBAB
  • the dehydrofluorination reaction of 244ca may be carried out in either a liquid phase reaction or a gas phase reaction.
  • the liquid-phase reaction is a dehydrofluorination reaction of 244ca in a liquid state or dissolved in a liquid.
  • the gas phase reaction refers to a dehydrofluorination reaction of 244ca in a gaseous state.
  • 1233yd when 1233yd is produced using a reaction raw material containing 244ca, which has a low 234cc content, the amount of by-products of 1223yd can be reduced, so the steps required for purifying 1233yd can be simplified and economical. is also advantageous. Since 1223yd is azeotropic with 1233yd, it is a compound that is difficult to separate from 1233yd by distillation, but according to the above method, 1233yd with a purity of 90% or more can be provided by an industrially advantageous method.
  • the content of 1223yd is preferably 10% by mass or less, more preferably 5% by mass or less, and further 3% by mass or less with respect to the total amount of 1233yd and 1223yd.
  • 1% by mass or less is particularly preferable, and 0.5% by mass or less is most preferable.
  • unreacted 244ca, by-products, etc. may be included in the reaction products.
  • a separation and purification method such as general distillation. Examples thereof include a separation and purification method by distillation or the like, a water washing treatment by washing with water, and a solid adsorption treatment by contacting with a solid adsorbent.
  • separation from 1233yd is possible by combining these.
  • solid adsorbents include activated carbon, zeolite, silica, and alumina. Two or more kinds of solid adsorbents may be used in combination. Zeolites are preferred because they have high adsorption properties for by-products and the like.
  • Examples 1 to 6 are examples of liquid phase reaction
  • Example 7 is an example of gas phase reaction
  • Example 8 is an example of a method for producing 1233yd.
  • 254cb for example, according to the method described in WO 2018/139654, using a reactor equipped with a U-shaped reaction tube having a catalyst layer filled with a catalyst-supporting carrier and a salt bath in which it is immersed, can be manufactured.
  • 244 cc was supplied together with hydrogen to a palladium catalyst-supporting activated carbon in which 2.0 parts by mass of palladium was supported with respect to 100 parts by mass of activated carbon as a catalyst-supporting carrier, and reacted.
  • the recovered reaction composition contained 244cc, 263eb, 263ca, etc. 254cb was obtained by distillation from the reaction composition.
  • Example 1 244ca was produced by chlorinating 254cb obtained in the above production example.
  • a stainless steel autoclave (internal volume: 2.0 liters) equipped with a jacket and a quartz tube that transmits light from a light source was cooled to 20°C.
  • a wavelength Chlorine gas was introduced into the reactor at a flow rate of 7.1 g per hour while irradiating with visible light of 200 to 750 nm.
  • the reaction pressure at this time was 0.0 to 0.2 MPaG.
  • the above flow rate of chlorine gas was introduced for 5 hours, ie, 0.5 moles of chlorine per mole of 254cb was introduced.
  • reaction liquid was mixed with a 20% by mass aqueous solution of potassium hydrogen carbonate for neutralization, and then a liquid separation operation was performed. After standing, the reaction composition 1 was recovered from the separated lower layer and subjected to GC analysis.
  • Example 2 The same reactor used in Example 1 was maintained at 20° C., and 1530 g of carbon tetrachloride (CCl 4 ) as a solvent and 116 g of 254cb were charged into the reactor. Thereafter, chlorine gas was supplied into the reactor at a flow rate of 14.2 g per hour while irradiating visible light with a wavelength of 200 to 750 nm from an LED lamp (LHT42N-G-E39 manufactured by Mitsubishi Electric Corporation, output 40 W). The reaction pressure at this time was 0.0 to 0.2 MPaG. The above flow rate of chlorine gas was introduced for 2.5 hours, ie, 0.5 moles of chlorine per mole of 254cb was introduced.
  • CCl 4 carbon tetrachloride
  • reaction liquid was mixed with a 20% by mass aqueous solution of potassium hydrogen carbonate for neutralization, and then a liquid separation operation was performed. After standing, the reaction composition 2 was recovered from the separated lower layer and subjected to GC analysis.
  • Example 3 The same reactor as used in Example 1 was kept at 20° C., 1530 g of carbon tetrachloride (CCl 4 ) and 116 g of 254cb were placed therein, and then an LED lamp (Mitsubishi Electric LHT42N-G-E39, output 40 W ), while irradiating visible light with a wavelength of 200 to 750 nm, chlorine gas was introduced into the reactor at a flow rate of 3.6 g per hour. The reaction pressure at this time was 0.0 to 0.2 MPaG. The above flow rate of chlorine gas was introduced for 10 hours, that is, chlorine was introduced at a rate of 0.5 mol per 1 mol of 254cb, and light irradiation was continued until the temperature in the reactor became constant at 20°C.
  • CCl 4 carbon tetrachloride
  • 254cb 254cb
  • reaction liquid was mixed with a 20% by mass aqueous solution of potassium hydrogen carbonate for neutralization, and then a liquid separation operation was performed. After standing, the reaction composition 3 was recovered from the separated lower layer and subjected to GC analysis.
  • Example 4 The same reactor as used in Example 1 was kept at 50° C., 1530 g of carbon tetrachloride (CCl 4 ) and 116 g of 254cb were placed therein, and then an LED lamp (Mitsubishi Electric LHT42N-G-E39, output 40 W ), while irradiating visible light with a wavelength of 200 to 750 nm, chlorine gas was introduced into the reactor at a flow rate of 7.1 g per hour. The reaction pressure at this time was 0.0 to 0.2 MPaG. The above flow rate of chlorine gas was introduced for 5 hours, ie, 0.5 moles of chlorine per mole of 254cb was introduced.
  • CCl 4 carbon tetrachloride
  • 254cb 254cb
  • reaction liquid was mixed with a 20% by mass aqueous solution of potassium hydrogen carbonate for neutralization, and then a liquid separation operation was performed. After standing, the reaction composition 4 was recovered from the separated lower layer and subjected to GC analysis.
  • Example 5 The same reactor as used in Example 1 was kept at 0° C., 1530 g of carbon tetrachloride (CCl 4 ) and 116 g of 254cb were charged therein, and then an LED lamp (Mitsubishi Electric LHT42N-G-E39, output 40 W ), while irradiating visible light with a wavelength of 200 to 750 nm, chlorine gas was introduced into the reactor at a flow rate of 7.1 g per hour. The reaction pressure at this time was 0.0 to 0.2 MPaG. The above flow rate of chlorine gas was introduced for 5 hours, ie, 0.5 moles of chlorine per mole of 254cb was introduced.
  • CCl 4 carbon tetrachloride
  • 254cb 254cb
  • reaction liquid was mixed with a 20% by mass aqueous solution of potassium hydrogen carbonate for neutralization, and then a liquid separation operation was performed. After standing, the reaction composition 5 was recovered from the separated lower layer and subjected to GC analysis.
  • Example 6 A solenoid valve was provided at the bottom of the reactor used in Example 1 to keep the internal temperature of the reactor at 20° C., and 1530 g of carbon tetrachloride (CCl 4 ) was put therein. After that, from an LED lamp (Mitsubishi Electric LHT42N-G-E39, output 40W), while irradiating visible light with a wavelength of 200 to 750 nm, 254cb is 11.6 g per hour, and chlorine gas is added at a flow rate of 3.6 g per hour. introduced inside. The reaction pressure at this time was 0.0 to 0.2 MPaG. A reaction crude liquid was withdrawn through an electromagnetic valve provided at the bottom of the reactor to keep the reactor liquid level constant. Light irradiation was continued for 10 hours at the above flow rate.
  • LED lamp Mitsubishi Electric LHT42N-G-E39, output 40W
  • reaction liquid was mixed with a 20% by mass aqueous solution of potassium hydrogen carbonate for neutralization, and then a liquid separation operation was performed. After standing still, the reaction composition 6 was recovered from the separated lower layer and subjected to GC analysis.
  • the reaction conditions of Examples 1-6 and the GC analysis results of the resulting reaction compositions are shown in Table 1.
  • the conversion rate of 254cb is the ratio of the amount of 254cb consumed in the reaction to the amount of 254cb supplied to the reactor, and is a molar conversion value (unit: mol %).
  • the selectivity of each compound is the ratio of each compound to the total amount of the reaction composition, and is a molar conversion value (unit: mol %).
  • the target 244 ca can be obtained with high selectivity.
  • Example 7 A gas phase reactor (manufactured by Swagelok) consisting of a cylindrical reaction tube made of SUS316 with an inner diameter of 21.4 mm and a length of 50 cm was filled with activated carbon as a catalyst to a height of 40 cm, and the reactor was heated in an electric furnace. The temperature was kept at 100°C. 254cb was fed to the gas phase reactor from a cylinder maintained at a temperature of 50°C via a mass flow controller and a preheater. The temperature in the line from the cylinder through the mass flow controller to the preheater was kept at 50°C to prevent the 254cb from condensing.
  • the gas phase reactor was supplied with a contact time of 20 seconds and a molar ratio of chlorine/254cb of 1:1 to obtain a generated gas.
  • the conversion rate of 254cb was 93.2%
  • the selectivities of 244ca and 234cc were 80.9% and 5.9%, respectively
  • 244cc, 234cb, 224ca The selectivities for 224cb and 214cb were 1.5%, 4.4%, 1.5%, 2.9% and 2.9%, respectively.
  • Example 8 989.40 g of the raw material composition containing 244ca obtained in Example 6 above as a main component, tetra-n-butylammonium bromide (TBAB)9. 89 g was charged and the flask was heated to 50°C. While maintaining the reaction temperature at 50° C., 1396.01 g of a 40% by mass potassium hydroxide (KOH) aqueous solution was added dropwise over 30 minutes. After that, stirring was continued for 52 hours, and the organic layer was recovered.
  • the reaction time in this example is the total time of the time required for the dropping and the time for stirring after the dropping, that is, 52.5 hours.
  • Table 2 shows the results of analysis using a gas chromatogram after washing the recovered organic layer with water.
  • 244ca can be efficiently produced with high purity by reacting 254cb with chlorine.
  • the production method of the present invention is a method that allows a large-volume reaction without using special operations or reactors, and by this method, 244ca can be mass-produced on an industrial scale.
  • the entire contents of the specification, claims and abstract of Japanese Patent Application No. 2021-013256 filed on January 29, 2021 are cited here and incorporated as disclosure of the specification of the present invention. It is.

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Abstract

L'invention concerne un procédé efficace de production de 244ca avec une pureté élevée.　Ce procédé de production de 3-chloro-1,1,2,2-tétrafluoropropane consiste à faire réagir du 1,1,2,2-tétrafluoropropane avec du chlore pour obtenir du 3-chloro -1,1,2,2-tétrafluoropropane.
PCT/JP2022/003032 2021-01-29 2022-01-27 Procédé de production de 3-chloro-1,1,2,2-tétrafluoropropane et procédé de production de 1-chloro-2,3,3-trifluoropropane WO2022163745A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02300142A (ja) * 1989-02-02 1990-12-12 Asahi Glass Co Ltd 塩素化テトラフルオロプロパン類の製造方法
JP2016164152A (ja) * 2015-02-27 2016-09-08 ダイキン工業株式会社 １−クロロ−２，３，３−トリフルオロプロペンの製造方法
WO2017018412A1 (fr) * 2015-07-27 2017-02-02 旭硝子株式会社 Procédé de production de 1-chloro-2,3,3-trifluoropropène

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02300142A (ja) * 1989-02-02 1990-12-12 Asahi Glass Co Ltd 塩素化テトラフルオロプロパン類の製造方法
JP2016164152A (ja) * 2015-02-27 2016-09-08 ダイキン工業株式会社 １−クロロ−２，３，３−トリフルオロプロペンの製造方法
WO2017018412A1 (fr) * 2015-07-27 2017-02-02 旭硝子株式会社 Procédé de production de 1-chloro-2,3,3-trifluoropropène

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