Method for producing 1-chloro-2,3,3,3-tetrafluoropropene

Abstract

To provide a method for producing 1224yd at high yield.SOLUTION: According to a method for producing 1-chloro-2,3,3,3-tetrafluoropropene, in the presence of a Cu-containing support catalyst having a carrier and a Cu-containing catalyst supported on the carrier, 1,1-dichloro-2,3,3,3-tetrafluoropropene is allowed to react with hydrogen, to produce 1-chloro-2,3,3,3-tetrafluoropropene. The Cu-containing catalyst includes at least one selected from the group consisting of Cu catalyst and Cu-M catalyst. The Cu catalyst includes a monovalent Cu-bearing compound. The Cu-M catalyst includes a monovalent Cu-bearing compound, and a compound having at least one metal selected from the group consisting of Pd, Pt and Ni or at least one atom selected from the group consisting of Pd, Pt and Ni. The carrier has a BET specific surface area of 400 m2 / g or more.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a method for producing 1-chloro-2,3,3,3-tetrafluoropropene. [Background technology]

[0002] 1-Chloro-2,3,3,3-tetrafluoropropene (CF3CF=CHCl. HCFO-1224yd. Hereinafter, also referred to as 1224yd) can be used in a variety of applications, such as a cleaning agent, a refrigerant, a heat transfer medium, a blowing agent, and a solvent.

[0003] In this disclosure, for halogenated hydrocarbons, the abbreviation for the compound may be written in parentheses after the compound name. In this disclosure, the abbreviation may be used instead of the compound name as needed. The abbreviation may use only the number and lowercase alphabet portion following the hyphen (-) (for example, "HCFO-1224yd" becomes "1224yd").

[0004] The Examples section of Patent Document 1 discloses that 1,1-dichloro-2,3,3,3-tetrafluoropropene (CFCF=CCl, CFO-1214ya; hereinafter also referred to as 1214ya) is reacted with hydrogen using a Ni-Cu catalyst or a 0.5% Pd-8.5% Cu catalyst to obtain 1224yd. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] U.S. Patent No. 9,637,429 Summary of the Invention [Problem to be solved by the invention]

[0006] However, the product obtained by the method specifically described in Patent Document 1 contains many by-products and unreacted raw materials, and the yield of 1224 yd is low.

[0007] Therefore, an object of the present invention is to provide a method for producing 1224yd with a high yield. [Means for solving the problem]

[0008] As a result of extensive investigation, the present inventors have found that the above object can be achieved by employing the following configuration.

[0009] (1) A method for producing 1-chloro-2,3,3,3-tetrafluoropropene, comprising reacting 1,1-dichloro-2,3,3,3-tetrafluoropropene with hydrogen in the presence of a Cu-containing supported catalyst comprising a support and a Cu-containing catalyst supported on the support, to obtain 1-chloro-2,3,3,3-tetrafluoropropene, the Cu-containing catalyst comprises at least one selected from the group consisting of a Cu catalyst and a Cu-M catalyst; the Cu catalyst comprises a compound having monovalent Cu, the Cu-M catalyst comprises a compound having monovalent Cu and a compound having at least one metal selected from the group consisting of Pd, Pt, and Ni or at least one atom selected from the group consisting of Pd, Pt, and Ni; The BET specific surface area of the support is 400m 2 / g or more. (2) The method for producing 1-chloro-2,3,3,3-tetrafluoropropene according to (1), wherein the carrier comprises activated carbon. (3) The BET specific surface area of the support is 1000 m 2 / g or more, (1) or (2). (4) The method for producing 1-chloro-2,3,3,3-tetrafluoropropene according to any one of (1) to (3), wherein the amount of the Cu-containing catalyst supported is 1 to 20 parts by mass in terms of metal atoms per 100 parts by mass of the support. (5) The method for producing 1-chloro-2,3,3,3-tetrafluoropropene according to any one of (1) to (4), wherein the reaction temperature is 30 to 350°C. (6) The method for producing 1-chloro-2,3,3,3-tetrafluoropropene according to any one of (1) to (5), wherein the molar ratio of hydrogen to 1,1-dichloro-2,3,3,3-tetrafluoropropene is 0.1 to 50. (7) The Cu-containing catalyst is a Cu-M catalyst; The method for producing 1-chloro-2,3,3,3-tetrafluoropropene according to any one of (1) to (6), wherein the Cu-M catalyst contains CuCl. (8) The method for producing 1-chloro-2,3,3,3-tetrafluoropropene according to any one of (1) to (7), wherein the Cu-M catalyst contains at least one metal selected from the group consisting of Pd and Pt, or a compound having at least one atom selected from the group consisting of Pd and Pt. (9) The Cu-containing catalyst is a Cu catalyst; The method for producing 1-chloro-2,3,3,3-tetrafluoropropene according to any one of (1) to (6), wherein the Cu catalyst contains CuCl. [Effects of the Invention]

[0010] According to the present invention, a method for producing 1224 yd with a high yield can be provided. [Brief explanation of the drawings]

[0011] [Figure 1] FIG. 1 is a schematic diagram showing a reaction apparatus. DETAILED DESCRIPTION OF THE INVENTION

[0012] A numerical range expressed using "to" means a range that includes the numerical values before and after "to" as the lower and upper limits.

[0013] 1224yd exists as geometric isomers, Z and E, depending on the position of the substituent on the carbon-carbon double bond. In the present disclosure, unless otherwise specified, when a compound name or abbreviation is used, it refers to at least one selected from the group consisting of Z-isomer and E-isomer, specifically, Z-isomer or E-isomer, or a mixture containing Z-isomer and E-isomer in any ratio. When a compound name or abbreviation is followed by (E) or (Z), it indicates the (E) or (Z) isomer of the compound. For example, 1224yd(Z) indicates the Z isomer, and 1224yd(E) indicates the E isomer.

[0014] The method for producing 1224yd of the present invention (hereinafter also simply referred to as "the production method of the present invention") is a method for producing 1224yd by reacting 1214ya with hydrogen in the presence of a predetermined Cu-containing supported catalyst.

[0015] The Cu-containing supported catalyst includes a support and a Cu-containing catalyst supported on the support. The Cu-containing catalyst includes at least one catalyst selected from the group consisting of a Cu catalyst and a Cu-M catalyst, the Cu catalyst including a compound having monovalent Cu, and the Cu-M catalyst including a compound having monovalent Cu and at least one metal selected from the group consisting of Pd, Pt, and Ni, or a compound having at least one atom selected from the group consisting of Pd, Pt, and Ni. In the following, first, the Cu catalyst and the Cu-M catalyst will be explained, and then the support will be explained.

[0016] (Cu catalyst) The Cu catalyst includes compounds having monovalent Cu (monovalent copper). The Cu catalyst refers to a catalyst containing only Cu as the catalytic metal element. Specific examples of compounds containing monovalent Cu include salt compounds containing monovalent Cu and oxides (copper oxides) containing monovalent Cu. Halides (copper halides) containing monovalent Cu are preferred, with monovalent Cu chloride (CuCl) being particularly preferred. The Cu catalyst may contain a compound having a Cu atom in addition to the above-mentioned compound having monovalent Cu. The compound having a Cu atom is a compound other than a compound having monovalent Cu, and is a compound having only Cu as the metal element that acts as a catalyst. Specific examples of compounds having a Cu atom include compounds represented by Cu (zerovalent Cu), CuCl2, CuF2, and Cu2X4. Each X independently represents a halogen ion (e.g., Cl - ), hydroxide ion, and nitrate ion. Specific examples of compounds represented by Cu2X4 include Cu2Cl(OH)3 and Cu2(NO3(OH)3). Of these, Cu is preferred as a compound having a Cu atom.

[0017] The Cu catalyst may contain trace amounts of metal elements other than Cu as impurities during production of the catalyst. Specifically, the total content of metal elements other than Cu may be 1000 mass ppm or less relative to the total mass of Cu atoms in the Cu catalyst. However, this does not apply to metal elements that are clearly not involved in this reaction, such as alkali metals and alkaline earth metals contained as ash in the activated carbon used as a carrier. This also applies to the Cu-M catalyst described below.

[0018] (Cu-M catalyst) The Cu-M catalyst contains a compound having monovalent Cu (hereinafter also referred to as the "first component") and a compound having at least one metal selected from the group consisting of Pd, Pt, and Ni, or at least one atom selected from the group consisting of Pd, Pt, and Ni (hereinafter collectively referred to as the "second component").

[0019] The first component has the same meaning as the compound containing monovalent Cu contained in the Cu catalyst, and the preferred range is also the same.

[0020] The second component may contain at least one metal element selected from the group consisting of Pd, Pt, and Ni as a metal element that acts as a catalyst, and compounds of the metal, oxide, and halide can be used. The valence of the second component may be either 0 or 1 or higher. The valence is preferably 2 to 6, more preferably 2 to 3, and particularly preferably 2.

[0021] Specific examples of the compound having at least one atom selected from the group consisting of Pd, Pt, and Ni include PdO, PdCl2, PtO, PtO2, PtCl2, PtCl4, HPtCl6, NiO, and NiCl2. As the second component, a compound having a Pd atom or a Pt atom is preferred, and a compound having a Pd atom is particularly preferred, in terms of being able to improve the yield of 1224 yd.

[0022] The first component and the second component may be present individually on the same support, or may be present as an alloy.

[0023] The Cu-M catalyst may contain components other than the first component and the second component, as long as the effects of the present invention are not impaired. Specific examples of components other than the first component and the second component include compounds having at least one metal or atom selected from the group consisting of Fe, Ru, Os, Co, Rh, Ir, Au, Bi, and Al.

[0024] In the Cu-M catalyst, the mass ratio (M / Cu) of at least one atom selected from the group consisting of Pd, Pt, and Ni (hereinafter, these are also collectively referred to as "M") to Cu atoms is preferably 1 / 40 or less, more preferably 1 / 60 or less, even more preferably 1 / 70 or less, particularly preferably 1 / 80 or less, and most preferably 1 / 100 or less, from the viewpoint of improving the 1224 yd yield, particularly selectivity. The lower limit is preferably 1 / 999 or more, more preferably 1 / 700 or more, and particularly preferably 1 / 500 or more, from the viewpoint of reaction yield.

[0025] As the Cu-M catalyst, a catalyst containing CuCl is preferred, and a catalyst containing CuCl and at least one metal selected from the group consisting of Pd and Pt, or a compound having at least one atom selected from the group consisting of Pd and Pt, is particularly preferred.

[0026] The Cu-containing catalyst is preferably a catalyst containing CuCl and at least one metal selected from the group consisting of Pd and Pt, or a compound having at least one atom selected from the group consisting of Pd and Pt, and more preferably a catalyst containing CuCl and a compound having Pd metal or a Pd atom.

[0027] (Carrier) The BET specific surface area of the support is 400m 2 / g or more, and 800m 2 / g or more is preferable, and 1000m 2 / g or more is more preferable, and 1200m 2 The upper limit is, for example, 3000 m 2 / g. The BET specific surface area means the nitrogen adsorption specific surface area measured using the BET method. The BET specific surface area is measured using an apparatus (e.g., "3Flex" manufactured by Micrometrics) that uses nitrogen gas as the measurement principle. The support is dried overnight at 130°C under vacuum using a vacuum drying apparatus (e.g., "Vacuum Low-Temperature Dryer" manufactured by EYELA), and then the BET specific surface area is measured.

[0028] The carrier is preferably a carrier containing activated carbon, and activated carbon is particularly preferred. Specific examples of activated carbon include activated carbon prepared using wood, charcoal, fruit shells, coconut shells, peat, lignite, and coal as raw materials. Of these, activated carbon prepared using plants as raw materials is preferred, and coconut shell activated carbon is particularly preferred. As for the carrier shape, molded coal having a length of about 2 to 5 mm, crushed coal of about 4 to 50 mesh, or granular coal of 2 to 50 mesh is preferred, and from the viewpoint of the yield of 1224 yd, crushed coal of 4 to 20 mesh or granular coal of 4 to 20 mesh is more preferred, and crushed coal of 4 to 6 mesh or granular coal of 4 to 6 mesh is particularly preferred.

[0029] The support may be subjected to a treatment such as acid washing in order to enhance its ability to support the catalyst. Specific examples of methods for preparing a carrier carrying a Cu catalyst or a Cu-M catalyst include a precipitation method or an impregnation method, as described in Satterfield, "Heterogeneous Catalysts in Industrial Practice," 2nd ed. (McGraw-Hill, New York, 1991), pp. 87-112, with the impregnation method being particularly preferred.

[0030] In the Cu-containing supported catalyst, the amount of Cu-containing catalyst supported is preferably 0.5 to 50 parts by mass, more preferably 1 to 20 parts by mass, even more preferably 3 to 20 parts by mass, and particularly preferably 5 to 10 parts by mass, in terms of metal atoms, per 100 parts by mass of the support, in order to sufficiently increase the specific surface area of the Cu-containing catalyst and to achieve excellent catalytic activity. The Cu-M catalyst described above may be used as a mixture of the first component and the second component, each of which is supported individually on a carrier, or as a mixture of the first component and the second component, which is supported on a carrier.

[0031] In order to improve the activity of the Cu-containing supported catalyst, the Cu-containing supported catalyst may be subjected to a reduction treatment during the production process of the Cu-containing supported catalyst or before use. A specific example of the reduction treatment is a treatment in which the Cu-containing supported catalyst is brought into contact with hydrogen. The temperature of the reduction treatment is preferably 100° C. or higher, more preferably 150° C. or higher, and particularly preferably 180° C. or higher. The upper limit of the temperature is preferably less than 400° C., more preferably 370° C. or lower, even more preferably 350° C. or lower, particularly preferably 300° C. or lower, and most preferably 280° C. or lower. In particular, it is preferred that the Cu-containing supported catalyst is not subjected to the above reduction treatment, or that the Cu-containing supported catalyst is subjected to a reduction treatment in the above temperature range during the production process or before use.

[0032] 1214ya, which is the raw material for the production method of the present invention, can be produced by known methods. A specific example of a method for producing 1214ya is a method in which 1,1-dichloro-2,2,3,3,3-pentafluoropropane (HCFC-225ca) and 1,1,1-trichloro-2,3,3,3-tetrafluoropropane (HCFC-224db) are contacted with an aqueous alkali solution in the presence of a phase transfer catalyst to undergo dehydrofluorination or dehydrochlorination. Dichloropentafluoropropane (225) containing 225ca can be used in this reaction, and the phase transfer catalyst selectively dehydrofluorinates only 225ca in 225. After the reaction, 1214ya can be purified by known methods such as distillation. The purified 1214ya may contain impurities, such as 1,3-dichloro-1,2,3,3-tetrafluoropropene (1214yb), which is obtained by dehydrofluorination of 225 isomers other than 225ca. The content of impurities is preferably 1000 ppm by mass or less relative to the total mass of 1214ya. The lower limit is, for example, 0 ppm by mass. Commercially available 225 containing 225ca may be used. Examples of such commercially available products include Asahiklin AK225 (manufactured by AGC, a mixture of 48 mol% of 225ca and 52 mol% of 225cb). Tetrabutylammonium bromide (TBAB) is preferred as a phase transfer catalyst.

[0033] In the reaction of 1214ya with hydrogen in the production method of the present invention, the molar ratio of the molar amount of hydrogen used to the molar amount of 1214ya used (molar amount of hydrogen / molar amount of 1214ya) is preferably 0.1 to 50, more preferably 0.5 to 50, even more preferably 0.7 to 20, and particularly preferably 1 to 10, in order to increase the yield of 1224yd.

[0034] The above reaction is usually carried out using a reactor. The shape and structure of the reactor are not particularly limited. A specific example of the reactor is a cylindrical vertical reactor that can be filled with a Cu-containing supported catalyst in the case of a gas-phase reaction described below. The amount of catalyst packed into a cylindrical vertical reactor is determined by the gas linear velocity and contact time, and the optimal packing length varies depending on the amount of catalyst used. Generally, a cylindrical vertical reactor is packed to a depth of 10 to 500 cm.

[0035] In the case of a liquid-phase reaction, the content of the Cu-containing supported catalyst is preferably 0.1 to 20 mass% and particularly preferably 1 to 10 mass% relative to the total liquid volume in the reactor. When the content is 1 mass% or more, the reaction rate is excellent. Furthermore, when the content is 10 mass% or less, the catalyst separation step after the reaction and the stirring efficiency during the reaction are excellent. Specific examples of materials for the reactor include glass, iron, nickel, stainless steel, and alloys containing iron or nickel as the main component. The reactor may be provided with a heating unit such as an electric heater inside. The reactor may have a sheath tube into which a thermometer for measuring the temperature inside is inserted.

[0036] In the production method of the present invention, the reaction between 1214ya and hydrogen may be either a liquid phase reaction or a gas phase reaction. A liquid phase reaction means reacting 1214ya in liquid form with hydrogen. A gas-phase reaction means reacting 1214ya in gaseous form with hydrogen. As for the above, a gas phase reaction is preferred because a liquid phase reaction results in a high pressure inside the reactor. The reaction may be carried out in a batch mode, semi-continuous mode, or continuous flow mode.

[0037] The liquid phase reaction will now be described in detail. A specific procedure for the liquid phase reaction is, for example, to continuously or discontinuously supply hydrogen to a reactor in which a mixture of 1214ya and a catalyst exists in a liquid state, and continuously or discontinuously withdraw 1224yd produced by the reaction from the reactor.

[0038] In terms of the yield of 1224 yd, the reaction temperature in the liquid phase reaction is preferably 30°C or higher, more preferably 100°C or higher, and even more preferably higher than 160°C. Also, the reaction temperature is preferably 350°C or lower, more preferably 300°C or lower, and even more preferably lower than 225°C. The reaction time in the liquid phase reaction is preferably 0.1 to 100 hours, more preferably 0.5 to 50 hours, and particularly preferably 1 to 20 hours, from the viewpoint of the yield of 1224yd and production efficiency. The reaction time means the residence time of the raw materials (1224yd and hydrogen) in the reactor. The liquid phase reaction may be carried out in the presence of a solvent, if necessary. Examples of the solvent include CF3 (CF2) n Examples include linear perfluoroalkyl compounds having 5 to 8 carbon atoms represented by CF3 (wherein n is an integer of 3 to 6).

[0039] Next, the gas phase reaction will be described in detail. A specific procedure for the gas-phase reaction is to continuously supply the raw materials 1214ya heated to a gaseous state and hydrogen into a reactor, and then contact the Cu-containing supported catalyst filled in the reactor with the gaseous 1214ya and gaseous hydrogen to obtain 1224yd. A gas inert to the reaction (dilution gas) may be supplied to the reactor because it is effective for adjusting the flow rate, suppressing by-products, and suppressing catalyst deactivation. Specific examples of the dilution gas include nitrogen, carbon dioxide, helium, and argon. For example, when nitrogen is supplied to the reactor as the inert gas, the molar ratio of the molar amount of hydrogen to the molar amount of nitrogen is preferably greater than 0, more preferably 0.1 or greater, and even more preferably 0.2 or greater.

[0040] When a Cu catalyst is used, the reaction temperature in the gas phase reaction (temperature inside the reactor) is preferably 30 to 350°C, more preferably 100 to 350°C, even more preferably 160 to 350°C, particularly preferably 200 to 300°C, and most preferably 230 to 300°C, from the viewpoint of the yield of 1224 yd. When a Cu-M catalyst is used, the reaction temperature in the gas phase reaction (temperature inside the reactor) is preferably 30 to 350°C, more preferably 100 to 300°C, even more preferably 160 to 300°C, particularly preferably 200 to 300°C, and most preferably 230 to 300°C, from the viewpoint of the yield of 1224yd. On the other hand, the reaction temperature is preferably 200 to 280°C, more preferably 200 to 250°C, and particularly preferably 200 to 225°C, from the viewpoint of suppressing the production of by-products and improving the selectivity of 1224yd. The temperature inside the reactor can be controlled by adjusting the temperature and pressure of the 1214ya and hydrogen supplied to the reactor. If necessary, the inside of the reactor can be supplementarily heated by an electric heater, a microwave generator, or the like.

[0041] The reaction time in the gas phase reaction is preferably 0.1 to 1000 seconds, more preferably 1 to 800 seconds, even more preferably 5 to 600 seconds, and particularly preferably 10 to 500 seconds. By setting the reaction time to 0.1 to 1000 seconds, the reduction reaction of 1214ya proceeds sufficiently, resulting in a higher yield of 1224yd. The reaction time corresponds to the residence time of the raw materials 1214ya and hydrogen in the reactor, and can be controlled by adjusting the supply amounts (flow rates) of 1214ya and hydrogen to the reactor.

[0042] The pressure of the reaction system in the gas phase reaction (pressure inside the reactor) is preferably 0 to 2.0 MPa, more preferably 0 to 0.5 MPa. Negative pressure may also be used. From the viewpoint of ease of handling, the pressure inside the reactor is particularly preferably normal pressure (atmospheric pressure). In the present disclosure, unless otherwise specified, pressure refers to gauge pressure. The pressure inside the reactor in a liquid phase reaction is preferably a pressure at which the raw materials are present as liquids inside the reactor, more preferably a pressure higher than the vapor pressure of the raw materials at the reaction temperature, and particularly preferably 0.1 to 10 MPa.

[0043] In the production method of the present invention, 1224yd is obtained as a product. As described above, the obtained 1224yd may be the Z isomer alone, the E isomer alone, or a mixture of the Z isomer and the E isomer. When the resulting 1224yd is a mixture of Z and E isomers, the ratio of the mass of Z to E isomers (Z / E) is preferably 1 or more, more preferably 2 or more, even more preferably 5 or more, and particularly preferably 10 or more. The upper limit of this ratio is, for example, 100. 1224yd(Z) has higher chemical stability than 1224yd(E). Therefore, when the mass ratio (Z / E) is equal to or greater than the lower limit, 1224yd can be easily used in various applications, such as cleaning agents, refrigerants, heat transfer media, foaming agents, and solvents.

[0044] The product obtained by the production method of the present invention may contain impurities in addition to the target compound 1224yd. Specific examples of impurities include 2,3,3,3-tetrafluoropropene (CFCF=CH, HFO-1234yf, hereinafter also referred to as 1234yf), which is produced by further hydrogenation of 1214ya, and the over-reduced compounds 1,1,1-trifluoropropene (CFCH=CH, HFO-1243zf, hereinafter also referred to as 1243zf), and 1,1,1,2-tetrafluoropropane (254eb).

[0045] The total content of 1234yf, 1243zf, and 254eb in the product is preferably 10% by mass or less, and more preferably 5% by mass or less, based on the total mass of the product. The lower limit of the content is, for example, 0% by mass. The content of 1224yd in the product is preferably 45 mol% or more, more preferably 55 mol% or more, even more preferably 65 mol% or more, and particularly preferably 80 mol% or more, based on the total mass of the product. The upper limit of the content is, for example, 100 mol%. When the product contains impurities, a treatment may be carried out to separate 1224 yd from the obtained product by a known method such as distillation.

[0046] Next, a more detailed embodiment of the gas phase reaction will be described with reference to Figure 1. A reactor 20 shown in Figure 1 is an example of a reactor used for a gas phase reaction. The reaction device 20 includes a reactor 1. The reactor 1 is connected to a supply line 2 for 1214ya, a supply line 3 for hydrogen, and a supply line 4 for nitrogen as a diluent gas. The reactor 1 is preferably equipped with a heating unit such as an electric heater. The supply line 2 for 1214ya and the supply line 3 for hydrogen may be connected separately to the reactor 1, or may be connected upstream of the reactor 1 and then connected to the reactor 1. For example, as shown in Fig. 1, the supply line 2 for 1214ya, the supply line 3 for hydrogen, and the supply line 4 for nitrogen are connected. As a result, a mixture of 1214ya, hydrogen, and nitrogen is supplied to the reactor 1 via the mixture supply line 5.

[0047] In the reaction apparatus 20 shown in FIG. 1, the supply line 2 for 1214ya, the supply line 3 for hydrogen, and the supply line 4 for nitrogen are respectively provided with preheaters 2a, 3a, and 4a equipped with electric heaters or the like. It is preferable that 1214ya, hydrogen, and nitrogen to be supplied to the reactor 1 are preheated to a predetermined temperature by the preheaters 2a, 3a, and 4a, respectively, before being supplied to the reactor 1. This allows the temperature of 1214ya, hydrogen, and nitrogen to be efficiently raised to a predetermined reaction temperature inside the reactor 1. It is preferable that the preheaters 2a, 3a, and 4a are installed.

[0048] An outlet line 7 is connected to the outlet of the reactor 1 via a cooling unit 6 such as a heat exchanger. The outlet line 7 is further connected to a recovery tank 8 for water vapor and acidic liquid, an alkali washing device 9, and a dehydration tower 10 in this order. The reaction mixture removed from reactor 1 is treated through outlet line 7 and subsequent processes to remove acidic substances such as hydrogen chloride and hydrogen fluoride, water vapor, and water. The resulting gas is hereinafter referred to as the "outlet gas." Each component in the outlet gas is analyzed and quantified using an analytical device such as a gas chromatograph (GC).

[0049] For example, the outlet gas in a reduction reaction of 1214 ya contains 1224 yd. In this case, compounds other than 1224yd contained in the outlet gas include 1234yf, 1243zf, and 254eb in addition to the unreacted raw material 1214ya.

[0050] Components other than 1224yd contained in the outlet gas can be separated and removed by known means such as distillation to produce highly purified 1224yd.

[0051] In the reactor 20, unreacted 1214yd can be separated from the reaction mixture and outlet gas discharged from the reactor 1 by distillation or the like and returned to the reactor as part of the raw material, thereby improving the productivity of 1224yd. [Example]

[0052] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples. Examples 1 to 15 are working examples, and Example 16 is a comparative example.

[0053] Preparation of Cu-containing supported catalyst CuCl-PdCl2 supported catalyst (Pd / Cu=1 / 100) Copper (I) chloride and palladium (II) chloride were supported on activated carbon by impregnation. However, the catalyst preparation method is not limited to the impregnation method. Specific preparation procedures using the impregnation method are described below. Copper(I) chloride (15 g, manufactured by Nacalai Tesque), palladium(II) chloride (0.16 g, manufactured by Junsei Chemical Co., Ltd.), ion-exchanged water (300 g), 35% by mass hydrochloric acid (41 g, manufactured by Nacalai Tesque), and a sintered body having a BET specific surface area of 1230 m2 measured by the BET method were used. 2The mixture was mixed with 150 g of 4-6 mesh granular activated carbon (raw material: coconut shell) in a flask and allowed to stand for 12 hours. After this, hydrogen chloride and water were distilled off under reduced pressure at 60 °C using an evaporator. When the water content (water content) of the resulting supported catalyst reached 30 mass% or less, the catalyst was transferred to a reaction tube. The reaction tube was kept at 200 °C, and nitrogen gas was supplied at 16.7 mL / sec for 16 hours to dry the catalyst. This resulted in a CuCl-PdCl2-supported catalyst with a Pd to Cu mass ratio (Pd / Cu) of 1 / 100, calculated as metal atoms. The total amount of Cu and Pd supported, calculated as metal atoms, was 6 parts by mass per 100 parts by mass of activated carbon.

[0054] CuCl-PdCl2 supported catalyst (Pd / Cu=1 / 300) A CuCl-PdCl2-supported catalyst with a Pd / Cu mass ratio of 1 / 300 (metal atom equivalent) was obtained using the same procedure as in the CuCl-PdCl2-supported catalyst (Pd / Cu = 1 / 100) described above, except that the amount of palladium(II) chloride added was changed to 0.05 g. The total amount of Cu and Pd supported on activated carbon, calculated as metal atoms, was 6 parts by mass per 100 parts by mass of activated carbon.

[0055] CuCl-PdCl2 supported catalyst (Pd / Cu=1 / 600) A CuCl-PdCl2-supported catalyst with a Pd / Cu mass ratio of 1 / 600 (metal atom equivalent) was obtained using the same procedure as in the CuCl-PdCl2-supported catalyst (Pd / Cu = 1 / 100) described above, except that the amount of palladium(II) chloride added was changed to 0.03 g. The total amount of Cu and Pd supported on activated carbon, calculated as metal atoms, was 6 parts by mass per 100 parts by mass of activated carbon.

[0056] 《CuCl-PtCl2 supported catalyst (Pt / Cu=1 / 40)》 Copper chloride (I) and platinum chloride (II) were supported on activated carbon by impregnation. However, the catalyst preparation method is not limited to the impregnation method. Specific preparation procedures using the impregnation method are described below. Copper(I) chloride (15 g, manufactured by Nacalai Tesque), platinum(II) chloride (0.34 g, manufactured by Junsei Chemical Co., Ltd.), 35% by mass hydrochloric acid (320 g, manufactured by Nacalai Tesque), and a sintered body having a BET specific surface area of 1230 m2 measured by the BET method were used. 2 The mixture was mixed with 150 g of 4-6 mesh granular activated carbon in a flask and allowed to stand for 12 hours. After this, hydrogen chloride and water were distilled off under reduced pressure at 60°C using an evaporator. When the water content (water content) of the resulting supported catalyst reached 30% by mass or less, the catalyst was transferred to a reaction tube. The reaction tube was kept at 200°C, and nitrogen gas was supplied at 16.7 mL / sec for 16 hours to dry the catalyst. This resulted in a CuCl-PtCl2-supported catalyst with a Pt / Cu mass ratio (Pt / Cu) of 1 / 40, calculated as metal atoms. The total amount of Cu and Pt supported, calculated as metal atoms, was 6 parts by mass per 100 parts by mass of activated carbon.

[0057] 《CuCl-PtCl2 supported catalyst (Pt / Cu=1 / 70)》 A CuCl-PtCl2-supported catalyst was obtained using the same procedure as in the Cu-Pt catalyst (Pt / Cu = 1 / 40) above, except that the amount of platinum(II) chloride added was changed to 0.19 g. The mass ratio of Pt to Cu (Pt / Cu) was 1 / 70, calculated as metal atoms. The total amount of Cu and Pt supported, calculated as metal atoms, was 6 parts by mass per 100 parts by mass of activated carbon.

[0058] 《CuCl-PtCl2 supported catalyst (Pt / Cu=1 / 100)》 A CuCl-PtCl2-supported catalyst was obtained using the same procedure as in the above "Cu-Pt catalyst (Pt / Cu = 1 / 40)" except that the amount of platinum(II) chloride added was changed to 0.14 g. The mass ratio of Pt to Cu (Pt / Cu) was 1 / 100, calculated as metal atoms. The total amount of Cu and Pt supported, calculated as metal atoms, was 6 parts by mass per 100 parts by mass of activated carbon.

[0059] 《CuCl-H2PtCl6 supported catalyst (Pt / Cu=1 / 40)》 Copper(I) chloride and hexachloroplatinic(VI) acid hexahydrate were supported on activated carbon by impregnation. However, the catalyst preparation method is not limited to the impregnation method. Specific preparation procedures using the impregnation method are described below. Copper(I) chloride (15 g, manufactured by Nacalai Tesque), hexachloroplatinic(VI) acid hexahydrate (0.67 g, manufactured by Junsei Chemical Co., Ltd.), ion-exchanged water (75 g), 35% by mass hydrochloric acid (190 g, manufactured by Nacalai Tesque), and a 1000-kJ / kg sieve with a specific surface area of 1230 m2 measured by the BET method were used. 2 The mixture was mixed in a flask with 150 g of 4-6 mesh granular activated carbon and left to stand for 12 hours. After this, hydrogen chloride and water were distilled off under reduced pressure at 60°C using an evaporator. When the water content (water content) of the resulting supported catalyst reached 30% by mass or less, the catalyst was transferred to a reaction tube. The reaction tube was kept at 200°C, and nitrogen gas was supplied at 16.7 mL / sec for 16 hours to dry the catalyst. This resulted in a CuCl-H2PtCl6-supported catalyst with a Pt / Cu mass ratio (Pt / Cu) of 1 / 40, calculated as metal atoms. The total amount of Cu and Pt supported, calculated as metal atoms, was 6 parts by mass per 100 parts by mass of activated carbon.

[0060] CuCl-PdCl2 supported catalyst (Pd / Cu=1 / 100, BET:1243) Copper (I) chloride and palladium (II) chloride were supported on activated carbon by impregnation. However, the catalyst preparation method is not limited to the impregnation method. Specific preparation procedures using the impregnation method are described below. Copper(I) chloride (15 g, manufactured by Nacalai Tesque), palladium(II) chloride (0.16 g, manufactured by Junsei Chemical Co., Ltd.), ion-exchanged water (300 g), 35% by mass hydrochloric acid (41 g, manufactured by Nacalai Tesque), and a sintered body having a BET specific surface area of 1243 m2 measured by the BET method were used. 2The catalyst was mixed with 150 g of 4-6 mesh granular activated carbon (raw material: coconut shell) in a flask and allowed to stand for 12 hours. After this, hydrogen chloride and water were distilled off under reduced pressure at 60 °C using an evaporator. When the water content (water content) of the resulting supported catalyst reached 30% by mass or less, the catalyst was transferred to a reaction tube. The reaction tube was kept at 200 °C, and nitrogen gas was supplied at 16.7 mL / s for 16 hours to dry the catalyst. This resulted in a CuCl-PdCl2-supported catalyst (Pd / Cu = 1 / 100, BET: 1243) with a Pd to Cu mass ratio (Pd / Cu) of 1 / 100 (metal atom equivalent). The total amount of Cu and Pd supported, calculated as metal atoms, was 6 parts by mass per 100 parts by mass of activated carbon.

[0061] CuCl-PdCl2 supported catalyst (Pd / Cu=1 / 100, BET:953) Copper (I) chloride and palladium (II) chloride were supported on activated carbon by impregnation. However, the catalyst preparation method is not limited to the impregnation method. Specific preparation procedures using the impregnation method are described below. Copper(I) chloride (15 g, manufactured by Nacalai Tesque), palladium(II) chloride (0.16 g, manufactured by Junsei Chemical Co., Ltd.), ion-exchanged water (300 g), 35% by mass hydrochloric acid (41 g, manufactured by Nacalai Tesque), and a sintered body having a BET specific surface area of 953 m2 measured by the BET method were used. 2 The catalyst was mixed with 150 g of 4-6 mesh granular activated carbon (raw material: coconut shell) in a flask and allowed to stand for 12 hours. After this, hydrogen chloride and water were distilled off under reduced pressure at 60 °C using an evaporator. When the water content (water content) of the resulting supported catalyst reached 30% by mass or less, the catalyst was transferred to a reaction tube. The reaction tube was kept at 200 °C, and nitrogen gas was supplied at 16.7 mL / s for 16 hours to dry the catalyst. This resulted in a CuCl-PdCl2-supported catalyst (Pd / Cu = 1 / 100, BET: 953) with a Pd to Cu mass ratio (Pd / Cu) of 1 / 100 (metal atom equivalent). The total amount of Cu and Pd supported, in terms of metal atoms, was 6 parts by mass per 100 parts by mass of activated carbon.

[0062] CuCl-PdCl2 supported catalyst (Pd / Cu=1 / 100, BET:323) Copper (I) chloride and palladium (II) chloride were supported on activated carbon by impregnation. However, the catalyst preparation method is not limited to the impregnation method. Specific preparation procedures using the impregnation method are described below. Copper(I) chloride (15 g, manufactured by Nacalai Tesque), palladium(II) chloride (0.16 g, manufactured by Junsei Chemical Co., Ltd.), ion-exchanged water (300 g), 35% by mass hydrochloric acid (41 g, manufactured by Nacalai Tesque), and a sintered body having a BET specific surface area of 323 m2 measured by the BET method were used. 2 The catalyst was mixed with 150 g of 4-6 mesh granular activated carbon (raw material: coconut shell) in a flask and allowed to stand for 12 hours. After this, hydrogen chloride and water were distilled off under reduced pressure at 60 °C using an evaporator. When the water content (water content) of the resulting supported catalyst reached 30% by mass or less, the catalyst was transferred to a reaction tube. The reaction tube was kept at 200 °C, and nitrogen gas was supplied at 16.7 mL / s for 16 hours to dry the catalyst. This resulted in a CuCl-PdCl2-supported catalyst (Pd / Cu = 1 / 100, BET: 323) with a Pd to Cu mass ratio (Pd / Cu) of 1 / 100 (metal atom equivalent). The total amount of Cu and Pd supported, in terms of metal atoms, was 6 parts by mass per 100 parts by mass of activated carbon.

[0063] <reaction> Example 1 1, 1214ya was reacted with hydrogen to obtain 1224yd, as described below. In Examples 1 to 11 and 14 to 15, the supported catalysts were used without undergoing pretreatment to reduce CuCl and PdCl2 in the supported catalysts, as described below. A reaction tube made of SUS304 and having an inner diameter of 35.3 mm was used as reactor 1, which was installed in an electric furnace. A thermometer was inserted into the sheath of the reaction tube to measure the internal temperature. The reaction tube was packed with a CuCl-PdCl2 supported catalyst (Pd / Cu=1 / 100) prepared by the above method to a length of 30 cm. The temperature inside the reaction tube was controlled at 180°C. 1214 ya, hydrogen, and nitrogen were continuously supplied to the reactor 1 from stainless steel tube supply lines 2, 3, and 4, respectively. Electric furnaces with an internal temperature of 200°C were used as preheaters 2a, 3a, and 4a. The supply rates of 1214 ya, hydrogen, and nitrogen were controlled to be 25 mol%, 25 mol%, and 50 mol%, respectively, and supplied to the reactor 1. The flow rate (amount supplied per unit time) of the mixed gas (1214 ya, hydrogen and nitrogen) was controlled so that the residence time of the mixed gas inside the reactor 1 was 120 seconds. The pressure inside the reactor 1 was the same as atmospheric pressure.

[0064] The composition of the resulting product (outlet gas) was analyzed using a gas chromatograph (GC). The column used was a DB-1301 (length 60 m x inner diameter 250 μm x thickness 1 μm, manufactured by Agilent Technologies). The ratio (unit: %) of the molar amount of 1224 yd in the product to the molar amount of 1214 yd fed to the reactor was calculated and defined as the "1224 yd yield." The higher this value, the higher the yield of 1224 yd.

[0065] Example 2 The reaction was carried out in the same manner as in Example 1, except that the reaction temperature was changed to 250°C.

[0066] Example 3 The reaction was carried out in the same manner as in Example 1, except that a CuCl-PdCl2 supported catalyst (Pd / Cu=1 / 300) was used instead of the CuCl-PdCl2 supported catalyst (Pd / Cu=1 / 100) and the reaction temperature was changed to 220°C.

[0067] Example 4 The reaction was carried out in the same manner as in Example 3, except that the reaction temperature was changed to 250°C.

[0068] Example 5 The reaction was carried out in the same manner as in Example 1, except that a CuCl-PdCl2 supported catalyst (Pd / Cu=1 / 600) was used instead of the CuCl-PdCl2 supported catalyst (Pd / Cu=1 / 100) and the reaction temperature was changed to 220°C.

[0069] Example 6 The reaction was carried out in the same manner as in Example 5, except that the reaction temperature was changed to 250°C.

[0070] Example 7 The reaction was carried out in the same manner as in Example 1, except that a CuCl-PtCl2 supported catalyst (Pt / Cu=1 / 40) was used instead of the CuCl-PdCl2 supported catalyst (Pd / Cu=1 / 100) and the reaction temperature was changed to 220°C.

[0071] Example 8 The reaction was carried out in the same manner as in Example 1, except that a CuCl-H2PtCl6 supported catalyst (Pt / Cu=1 / 40) was used instead of the CuCl-PdCl2 supported catalyst (Pd / Cu=1 / 100) and the reaction temperature was changed to 220°C.

[0072] Example 9 The reaction was carried out in the same manner as in Example 8, except that the reaction temperature was changed to 250°C.

[0073] Example 10 The reaction was carried out in the same manner as in Example 1, except that a CuCl-PtCl2 supported catalyst (Pt / Cu=1 / 70) was used instead of the CuCl-PdCl2 supported catalyst (Pd / Cu=1 / 100) and the reaction temperature was changed to 250°C.

[0074] Example 11 The reaction was carried out in the same manner as in Example 1, except that a CuCl-PtCl2 supported catalyst (Pt / Cu=1 / 100) was used instead of the CuCl-PdCl2 supported catalyst (Pd / Cu=1 / 100) and the reaction temperature was changed to 250°C.

[0075] Example 12 Before starting the continuous supply of 1214yd, the reaction tube was kept at 180°C, hydrogen gas was supplied at 1.67 mL / sec for 16 hours, a pretreatment was performed to reduce the CuCl-PdCl2 supported catalyst (Pd / Cu=1 / 100), and the reaction temperature was changed to 220°C. Except for this, the reaction was carried out in the same manner as in Example 1. Regarding the selectivity of the obtained 1224yd, the 1224yd(Z) selectivity was 64.6%, and the 1224yd(E) selectivity was 30.6%.

[0076] Example 13 The reaction was carried out in the same manner as in Example 12, except that in the pretreatment for reducing the CuCl-PdCl2 supported catalyst (Pd / Cu=1 / 100), the reaction tube was maintained at 330°C. Regarding the selectivity of the obtained 1224yd, the 1224yd(Z) selectivity was 53.3%, and the 1224yd(E) selectivity was 39.4%.

[0077] Example 14 The reaction was carried out in the same manner as in Example 1, except that a CuCl-PdCl supported catalyst (Pd / Cu=1 / 100, BET: 1243) was used instead of the CuCl-PdCl supported catalyst (Pd / Cu=1 / 100) and the reaction temperature was changed to 220°C.

[0078] Example 15 The reaction was carried out in the same manner as in Example 1, except that a CuCl-PdCl supported catalyst (Pd / Cu=1 / 100, BET:953) was used instead of the CuCl-PdCl supported catalyst (Pd / Cu=1 / 100) and the reaction temperature was changed to 220°C.

[0079] Example 16 The reaction was carried out in the same manner as in Example 1, except that a CuCl-PdCl supported catalyst (Pd / Cu=1 / 100, BET:323) was used instead of the CuCl-PdCl supported catalyst (Pd / Cu=1 / 100) and the reaction temperature was changed to 220°C.

[0080] The evaluation results are shown in the table. In the table, "1214ya conversion rate" represents the ratio of the molar amount of converted 1214ya to the molar amount of 1214ya supplied to the reactor. In the table, "1224yd selectivity," "1234yf selectivity," and "1243zf selectivity" respectively represent the ratio of the molar amount of each compound obtained to the molar amount of converted 1214ya.

[0081] [Table 1]

[0082] [Table 2]

[0083] As shown in the table, the production method of the present invention improved the yield by 1,224 yd. Comparison between Example 1 and Example 2 shows that when the reaction temperature was 230° C. or higher, the yield of 1224 yd was further improved. Furthermore, a similar comparison revealed that when the reaction temperature was 200 to 225°C, the selectivity for 1224yd was further improved. A comparison between Example 2 and Example 11 shows that when the Cu-M catalyst contained a compound having monovalent Cu and a compound having Pd metal or a Pd atom, the yield of 1224 yd was improved. A comparison between Example 12 and Example 13 shows that when the pretreatment temperature for reducing the Cu-containing supported catalyst was 300° C. or lower, the yield of 1224 yd was improved. Comparing Example 15 with Example 1 or Example 14, it is clear that the BET specific surface area is 1000 m 2 / g or more, the yield of 1224 yd was improved. Comparing Example 1 and Example 16, the BET specific surface area is 400m 2 / g or more, the yield of 1224 yd was improved. [Explanation of symbols]

[0084] 1: Reactor 2:1214ya supply line 2a: Preheater 3: Hydrogen supply line 3a: Preheater 4: Nitrogen supply line 4a: Preheater 5: Mixture supply line 6: Cooling section 7: Exit Line 8: Water vapor and acid liquid collection tank 9: Alkaline cleaning device 10: Dehydration tower 20: Reactor

Claims

1. A method for producing 1-chloro-2,3,3,3-tetrafluoropropene, comprising reacting 1,1-dichloro-2,3,3,3-tetrafluoropropene with hydrogen in the presence of a Cu-containing supported catalyst comprising a support and a Cu-containing catalyst supported on the support, to obtain 1-chloro-2,3,3,3-tetrafluoropropene, the Cu-containing catalyst comprises a Cu-M catalyst; the Cu-M catalyst comprises CuCl and at least one metal selected from the group consisting of Pd and Pt or a compound having at least one atom selected from the group consisting of Pd and Pt; The BET specific surface area of the carrier is 400 m ２ / g or more.

2. The method for producing 1-chloro-2,3,3,3-tetrafluoropropene according to claim 1, wherein the carrier comprises activated carbon.

3. The BET specific surface area of the carrier is 1000 m ２ The method for producing 1-chloro-2,3,3,3-tetrafluoropropene according to claim 1 or 2, wherein the 1-chloro-2,3,3,3-tetrafluoropropene content is 1 / g or more.

4. The method for producing 1-chloro-2,3,3,3-tetrafluoropropene according to any one of claims 1 to 3, wherein the amount of the Cu-containing catalyst supported is 1 to 20 parts by mass in terms of metal atoms per 100 parts by mass of the support.

5. The method for producing 1-chloro-2,3,3,3-tetrafluoropropene according to any one of claims 1 to 4, wherein the reaction temperature is 30 to 350°C.

6. The method for producing 1-chloro-2,3,3,3-tetrafluoropropene according to any one of claims 1 to 5, wherein a molar ratio of the hydrogen to the 1,1-dichloro-2,3,3,3-tetrafluoropropene is 0.1 to 50.

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