Method for producing hydrochlorofluorocarbons, method for producing 1-chloro-2,3,3-trifluoropropene, method for producing 1-chloro-2,3,3,4,4,5,5-heptafluoro-1-pentene

Abstract

The present invention provides a method for producing HCFC, the method being capable of producing HCFC at high selectivities. A method for producing hydrochlorofluorocarbon according to the present invention is characterized by producing a hydrochlorofluorocarbon given by formula (2) by the reaction, in the presence of a catalyst, of hydrogen chloride with a hydrofluorocarbon given by formula (1): X-L-Y formula (1), and X-L-Z formula (2), where X represents -CHaF(3-a), Y represents -CHbF(3-b), and Z represents -CHbClcF(3-b-c).

Description

[Technical field]

[0001] The present invention relates to a method for producing hydrochlorofluorocarbons, a method for producing 1-chloro-2,3,3-trifluoropropene, and a method for producing 1-chloro-2,3,3,4,4,5,5-heptafluoro-1-pentene. [Background technology]

[0002] In recent years, hydrochlorofluoroolefins (HCFOs) have been attracting attention as compounds that have a small impact on the global environment and can be used for various applications such as cleaning agents, refrigerants, working fluids, propellants, heat transfer media, foaming agents, solvents, etc. Among HCFOs, HCFOs in which a chlorine atom is bonded to the terminal carbon of a carbon-carbon double bond, such as 1-chloro-2,3,3,3-tetrafluoropropene (CF3-CF=CClH, HCFO-1224yd) and 1-chloro-2,3,3-trifluoropropene (CF2H-CF=CClH, HCFO-1233yd), are known to be highly non-flammable and excellent for the above applications. In this specification, the abbreviation of a halogenated hydrocarbon is written in parentheses after the compound name, but in this specification, the abbreviation is used instead of the compound name as necessary. In addition, only the number and lowercase alphabet following the hyphen (-) may be used as the abbreviation (for example, "1233yd" in "HCFO-1233yd"). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] International Publication No. 1990 / 008754 Summary of the Invention [Problem to be solved by the invention]

[0004] The present inventors have developed a compound having the specific structure (-CF2-CH b Cl c F (3-b-c)The researchers discovered that if a hydrochlorofluorocarbon (hereinafter, also referred to as "HCFC") having a chlorine atom bonded to the terminal carbon of the carbon-carbon double bond is used, then it is possible to efficiently synthesize an HCFO in which a chlorine atom is bonded to the terminal carbon of the carbon-carbon double bond. As a method for producing an HCFC having the above-mentioned specific structure, for example, Patent Document 1 describes a method in which an HCFC having a difluoromethylene group is reacted with hydrogen fluoride to fluorinate the HCFC. However, in the production method described in Patent Document 1, it is difficult to control the fluorination reaction, and it is difficult to selectively obtain an HCFC having the above-mentioned specific structure, so a method for obtaining the HCFC with higher selectivity has been desired. Thus, there is a demand for a more efficient method for producing HCFCs. In particular, from an industrial point of view, it is desirable to be able to produce HCFCs with high selectivity from hydrofluorocarbons, which are relatively easy to synthesize. An object of the present invention is to provide a method for producing HCFCs, which can produce HCFCs with high selectivity. Another object of the present invention is to provide a method for producing 1-chloro-2,3,3-trifluoropropene and a method for producing 1-chloro-2,3,3,4,4,5,5-heptafluoro-1-pentene. [Means for solving the problem]

[0005] As a result of intensive research into solving the above problems, the present inventors have found that the above problems can be solved by the following configuration.

[0006] (1) A method for producing a hydrochlorofluorocarbon, comprising reacting a hydrofluorocarbon represented by the formula (1) described below with hydrogen chloride in the presence of a catalyst to produce a hydrochlorofluorocarbon represented by the formula (2) described below. (2) The method according to (1), wherein the catalyst is a metal-containing catalyst. (3) The method according to (1) or (2), wherein the catalyst comprises at least one selected from a metal oxide, a partial halide of a metal oxide, and a metal halide, and each of the metal oxide, the partial halide of a metal oxide, and the metal halide comprises at least one selected from Cr and Al. (4) The method according to (3), wherein the catalyst comprises a partial halide of a metal oxide. (5) The method according to any one of (1) to (4), wherein L is -CF2-, -CF2CF2-, -CF2-CF2-CF2-, -CF2-CHF-CF2- or -CF2-CH2-CF2-. (6) The method according to any one of (1) to (5), wherein a is 1, b is 2, and c is 1. (7) The production method according to any one of (1) to (6), comprising reacting the hydrofluorocarbon represented by the formula (1) with hydrogen chloride in a gas phase. (8) The method according to any one of (1) to (7), wherein the reaction temperature is 100 to 450° C. (9) The process according to any one of (1) to (8), wherein the molar ratio of hydrogen chloride to the hydrofluorocarbon represented by the formula (1) is 0.5 to 2.0. (10) The production method according to any one of (1) to (9), in which a raw material composition containing a hydrofluorocarbon represented by formula (1) is reacted with hydrogen chloride, and the water content of the raw material composition is 5,000 ppm by mass or less. (11) The method according to (10), wherein the moisture content is 400 ppm by mass or less. (12) The hydrofluorocarbon represented by formula (1) is 1,1,2,2,3-pentafluoropropane, The process according to any one of (1) to (11), wherein the hydrochlorofluorocarbon represented by the formula (2) is 3-chloro-1,1,2,2-tetrafluoropropane. (13) A method for producing 1-chloro-2,3,3-trifluoropropene, comprising subjecting 3-chloro-1,1,2,2-tetrafluoropropane produced by the method according to (12) to a dehydrofluorination reaction to produce 1-chloro-2,3,3-trifluoropropene. (14) The hydrofluorocarbon represented by formula (1) is 1,1,2,2,3,3,4,4,5-nonafluoropentane, The process according to any one of (1) to (11), wherein the hydrochlorofluorocarbon represented by formula (2) is 5-chloro-1,1,2,2,3,3,4,4-octafluoropentane. (15) A method for producing 1-chloro-2,3,3,4,4,5,5-heptafluoro-1-pentene, comprising subjecting 5-chloro-1,1,2,2,3,3,4,4-octafluoropentane produced by the method according to (14) to a dehydrofluorination reaction to produce 1-chloro-2,3,3,4,4,5,5-heptafluoro-1-pentene. Effect of the Invention

[0007] According to the present invention, there is provided a method for producing HCFCs, which can produce HCFCs with high selectivity. Furthermore, according to the present invention, it is possible to provide a method for producing 1-chloro-2,3,3-trifluoropropene and a method for producing 1-chloro-2,3,3,4,4,5,5-heptafluoro-1-pentene. [Brief description of the drawings]

[0008] [Figure 1] FIG. 1 is a schematic diagram showing a reaction apparatus. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] The method for producing a hydrochlorofluorocarbon of the present invention (hereinafter also simply referred to as the "production method of the present invention") is a method for producing a hydrochlorofluorocarbon represented by formula (2) (hereinafter also referred to as "compound 2") by reacting a hydrofluorocarbon represented by formula (1) described below (hereinafter also referred to as "compound 1") with hydrogen chloride in the presence of a catalyst. In other words, the production method of the present invention is a method for producing compound 2 by contacting compound 1 with hydrogen chloride in the presence of a catalyst. In the following, first, the components used in the production method of the present invention will be described in detail, and then the procedure of the production method will be described in detail. Regarding the components, Compound 1 and Compound 2 will be described in detail first.

[0010] Compound 1 is a compound represented by formula (1). Formula (1) XLY X is -CH a F (3-a) Represents. a represents 0 or 1.

[0011] Y is -CH b F (3-b) Represents. b represents 1 or 2. However, when a is 0, b represents 1 or 2, and when a is 1, b represents 2. That is, compound 1 includes CF3-L-CHF2, CF3-L-CH2F, and CHF2-L-CH2F.

[0012] L is -CF2-, -CF2CF2-, or a fluoroalkylene group having 3 to 6 carbon atoms in which at least a portion of the hydrogen atoms may be substituted with fluorine atoms, and all of the terminals of the fluoroalkylene group having 3 to 6 carbon atoms are -CF2-. In addition, the terminus of the above-mentioned fluoroalkylene group is -CF2-, means that -CF2- is located at both ends of the fluoroalkylene group. For example, the above-mentioned fluoroalkylene group having 3 carbon atoms includes -CF2-CF2-CF2-, -CF2-CH2-CF2-, and -CF2-CFH-CF2-. L is preferably -CF2-, -CF2CF2-, -CF2-CF2-CF2-, -CF2-CHF-CF2- and -CF2-CH2-CF2-, and more preferably a perfluoroalkylene group -CF2-, -CF2CF2- and -CF2-CF2-CF2-.

[0013] The compound produced from compound 1 is a compound represented by formula (2). Formula (2) XLZ Z is -CH b Cl c F (3-b-c) Represents. b represents 1 or 2. c represents 1 or 2. However, when b is 1, c represents 1 or 2, and when b is 2, c represents 1. That is, Z includes -CHClF, -CHCl2, and -CH2Cl.

[0014] The relationship between a, b, and c above is shown in the following Table 1. In Table 1, "X", "Y", and "Z" correspond to "X", "Y", and "Z" in the above-mentioned formula (1) and formula (2). In addition, the "X", "Y", and "Z" columns in Table 1 show the values ​​that a, b, and c can take, and the structure in each case. For example, "(a=0) CF3" means that when a is 0, X represents CF3.

[0015] [Table 1]

[0016] In the production method of the present invention, the fluorine atoms bonded to the carbon atoms located at the terminals of compound 1 can be replaced with chlorine atoms by reacting compound 1 with hydrogen chloride in the presence of a catalyst. At that time, the fluorine atoms substituted at the terminal carbon atoms having fewer fluorine atoms among the two terminals can be selectively replaced with chlorine atoms. In the production method of the present invention, when comparing X and Y in formula (1), Y has fewer fluorine atoms, and the replacement of fluorine atoms with chlorine atoms proceeds at the position of Y. In addition, the number of fluorine atoms substituted with chlorine atoms can be controlled by adjusting the reaction conditions, etc. For example, as shown in Table 1, when Y is CHF2, one fluorine atom is substituted with a chlorine atom to form CHClF, or two fluorine atoms are substituted with chlorine atoms to form CHCl2. More specifically, the relationships between a, b, and c described above represent the cases of modes 1 to 4 in Table 1. For example, in the case of "mode 4," the "X" and "Y" columns indicate that compound 1 is CHF2-L-CH2F, and the "X" and "Z" columns indicate that compound 2 is CHF2-L-CH2Cl. That is, in the production method of the present invention, a, b, and c can take the following four forms. (Aspect 1) a is 0, b is 1, and c is 1. (Aspect 2) a is 0, b is 1, and c is 2. (Aspect 3) a is 0, b is 2, and c is 1. (Aspect 4) a is 1, b is 2, and c is 1. The production method of the present invention can be particularly suitably used in a reaction in which only one of the fluorine atoms of compound 1 is replaced with a chlorine atom. For example, when 1,1,2,2,3-pentafluoropropane is used as compound 1, 3-chloro-1,1,2,2-tetrafluoropropane (HCFC-244ca) can be produced as compound 2. In addition, when 1,1,2,2,3,3,4,4,5-nonafluoropentane (HFC-449pccc) is used as compound 1, 5-chloro-1,1,2,2,3,3,4,4-octafluoropentane (HCFC-448occc) can be produced as compound 2.

[0017] In the production method of the present invention, as described above, compound 1 contributes to the reaction. A raw material composition containing compound 1 may be used as a raw material. Compound 1 may be of two or more types. The raw material composition may contain impurities in addition to compound 1. Examples of impurities include by-products other than compound 1 produced during the production of compound 1, raw materials for compound 1, and water. When the raw material composition contains the above-mentioned impurities, by-products produced from the impurities may be removed by known means such as distillation, extractive distillation, azeotropic distillation, membrane separation, two-phase separation, and adsorption. The impurities are preferably compounds that are inactive under the reaction conditions of the present invention.

[0018] The raw material composition is preferably dehydrated before use in the reaction in order to obtain a higher conversion rate of compound 1. In other words, it is preferable to use a raw material composition that has been subjected to a dehydration treatment in the reaction. The water content (moisture content) of the raw material composition used in the reaction is preferably 5000 ppm by mass or less, more preferably 2000 ppm by mass or less, further preferably 400 ppm by mass or less, and particularly preferably 200 ppm by mass or less. The lower limit is 0 ppm by mass. Here ppm stands for parts per million. The moisture content is measured using a Karl Fischer moisture meter. A trace moisture measuring device (manufactured by Mitsubishi Chemical Analytech Co., Ltd., Model CA-200) is used as the Karl Fischer moisture meter, and a liquefied gas vaporizer (manufactured by the same company, Model VG-200) is connected to the sample introduction section, and a preset amount of the raw material composition after the dehydration treatment is vaporized and automatically injected into the moisture meter.

[0019] In the raw material composition used in the reaction, compound 1 is contained as a main component. The main component means that the content of compound 1 is 50 mass% or more, preferably 60 mass% or more, and more preferably 75 mass% or more, based on the total mass of the raw material composition. The upper limit can be 100 mass%.

[0020] The method for dehydrating the raw material composition is not particularly limited, but examples thereof include distillation and a method using a dehydrating agent. When a dehydrating agent is used, the raw material composition is brought into contact with the dehydrating agent to reduce the water content in the raw material composition. Dehydrating agents include zeolites, molecular sieves, alumina, calcium chloride, magnesium sulfate, sodium sulfate, calcium sulfate, and potassium carbonate.

[0021] Hydrogen chloride is a gas at room temperature and pressure. Hydrogen chloride may be dissolved in water when used. In the reaction, it is preferable to use hydrogen chloride that has been subjected to a dehydration treatment.

[0022] The catalyst in the production method of the present invention is preferably a metal-containing catalyst. Specific examples of the metal-containing catalyst include a simple metal, a metal oxide, a partial halide of a metal oxide, and a metal halide. The partial halide of the metal oxide is a compound in which a part of the metal oxide is halogenated (F, Cl, Br, I, etc.). The metal halide is a compound composed of a metal and a halogen. The partial halide of the metal oxide and the metal halide may contain only one type of halogen or may contain two or more types of halogen. Two or more types of catalysts may be used in combination.

[0023] The partial halide of a metal oxide is preferably a partial fluoride of a metal oxide in which the metal oxide is fluorinated. In this case, the partial fluoride of a metal oxide may contain a halogen other than fluorine. The metal halide is preferably a metal fluoride. The metal fluoride may contain a halogen other than fluorine.

[0024] The metal element contained in the above-mentioned simple metals, metal oxides, and metal halides is, from the viewpoint of improving reactivity, preferably at least one selected from Li, Na, K, Cs, Mg, Ca, Sr, Ba, Al, Cr, Zr, Fe, Ni, Co, Zn, Mn, Sb, Nb, and Ta, more preferably at least one selected from Al, Zn, Cr, Mg, Ca, K, Zr, and Li, and even more preferably at least one selected from Al, Zn, Cr, Mg, and Zr.

[0025] In particular, from the viewpoint of producing compound 2 with higher selectivity, it is preferable that the catalyst contains one or more selected from a metal oxide, a partial halide of a metal oxide, and a metal halide, and that the metal oxide, the partial halide of a metal oxide, and the metal halide each contain at least one metal element selected from Cr and Al (hereinafter also referred to as "metal A"). In other words, it is preferable that the catalyst contains one or more selected from a metal oxide containing metal A, a partial halide of a metal oxide containing metal A, and a metal halide containing metal A. The metal oxide, the partial halide of a metal oxide, and the metal halide may contain both Cr and Al. Among these, the catalyst more preferably contains a partial halide of a metal oxide containing metal A.

[0026] As the catalyst containing metal A, a metal oxide containing Cr, a partial halide of a metal oxide containing Cr, or a metal halide containing Cr is preferable, since the conversion rate of compound 1 is higher.

[0027] When a metal oxide, a partial halide of a metal oxide, or a metal halide containing metal A is used as a catalyst, the catalyst may contain a metal other than metal A for various purposes such as improving durability. Specific examples of other metals include Na, K, Mg, Ca, Zr, Fe, Zn, Ni, Co, and Mn. Among these, Na, K, Mg, Zn, or Mn is preferable, and Mg or Zn is more preferable, from the viewpoints of increasing the physical and chemical durability of the catalyst and enabling more efficient production of compound 2. In addition, when the catalyst contains a metal other than the metal A, the conversion rate of the compound 1 is more excellent. In terms of further improving the conversion rate, the other metal is preferably Na, K, Mg, Zn, or Mn, and more preferably Mg or Zn.

[0028] When the catalyst contains Cr, the Cr content is preferably 1% by mass or more, more preferably 5% by mass or more, and even more preferably 10% by mass or more, based on the total mass (100% by mass) of the metals contained in the catalyst, from the viewpoint of improving the conversion rate of compound 1. The upper limit is 100% by mass. When the catalyst contains Al, the content of Al is preferably 5% by mass or more, more preferably 20% by mass or more, and even more preferably 50% by mass or more, based on the total mass (100% by mass) of metals contained in the catalyst, from the viewpoint of improving the conversion rate of compound 1. The upper limit is 100% by mass. When the catalyst contains a metal other than metal A, the content of metal A is preferably 90 to 99.9 mass% and more preferably 95 to 99 mass% relative to the total mass of metals (100 mass%). On the other hand, the content of the metal other than metal A is preferably 0.1 to 10 mass% and more preferably 1 to 5 mass% relative to the total mass of metals (100 mass%).

[0029] The catalyst to be used in the reaction preferably has a low moisture content. Specifically, the catalyst is placed in a reactor, N2 is supplied to the reactor at 3.94 NmL / min per 1 g of catalyst, and the moisture content in the gas obtained from the reactor outlet is preferably 100 ppm by volume or less, more preferably 50 ppm by volume or less.

[0030] Specific examples of the catalyst include partially fluorinated chromium zinc composite oxide (partial fluoride of chromium zinc composite oxide), partially fluorinated chromium aluminum magnesium composite oxide (partial fluoride of chromium aluminum magnesium composite oxide), partially fluorinated alumina (partial fluoride of alumina), and partially fluorinated chromium oxide (partial fluoride of chromium oxide). Among these, partially fluorinated chromium zinc composite oxide (partial fluoride of chromium zinc composite oxide) and partially fluorinated chromium oxide (partial fluoride of chromium oxide) are preferred because of their excellent conversion rate of compound 1.

[0031] In order to improve the reactivity, the catalyst may be formed into pellets and used, or may be supported on a carrier and used. Examples of the carrier include carbon materials such as activated carbon, carbon black, and carbon fiber, and oxide materials such as alumina, silica, titania, zirconia, alkali metal oxides, and alkaline earth metal oxides, with activated carbon, alumina, silica, zirconia, alkali metal oxides, and alkaline earth metal oxides being preferred. Among these, activated carbon, alumina, and zirconia are more preferred because they have a large specific surface area and are easy to support the catalyst.

[0032] The catalyst may be formed into pellets by crushing the catalyst into powder and forming the powder into pellets using a tablet press or the like. As the pellet-shaped catalyst, for example, a cylindrical catalyst having a diameter of about 3.0 mm and a height of about 4.0 mm can be used. If necessary, a binder may be mixed with the catalyst. The amount of the binder used is preferably 100 parts by mass or less, more preferably 50 parts by mass or less, and even more preferably 10 parts by mass or less, relative to 100 parts by mass of the catalyst. In this case, the mixture of the catalyst and the binder can be molded into a pellet-shaped catalyst using a tablet press or the like. Specific examples of the binder include carbon, cellulose, alumina, and silica.

[0033] In order to improve the reactivity, the catalyst is preferably dried in advance in an inert atmosphere (e.g., in a nitrogen stream). From the viewpoint of simplification of the operation and improvement of the working efficiency, the catalyst may be dried in the same manner as above while being contained in the reactor. The catalyst may be dried before being placed in the reactor.

[0034] The specific surface area of ​​the catalyst depends on the type of catalyst, and generally, the smaller the specific surface area, the lower the conversion rate, and the larger the specific surface area, the lower the selectivity and the more likely the catalyst is to deteriorate quickly. For example, when the binder is not used, the specific surface area of ​​the metal oxide and the partial halide of the metal oxide is 10 to 400 m 2 / g, and the specific surface area of ​​the metal halide is preferably 3 to 300 m 2 / g is preferred. When the above binders are used, the specific surface area of ​​the binder also depends on the specific surface area, so it is not possible to make a general statement. For example, when a carbon binder with a high specific surface area is used, the specific surface area of ​​the mixture of the catalyst and the carbon binder is 20 to 1200 m. 2 / g is preferred. In this specification, the specific surface area is a value measured by the BET method.

[0035] In addition, the catalyst is preferably subjected to an activation treatment in advance from the viewpoint of improving reactivity (particularly, from the viewpoint of improving the conversion rate of compound 1). As a method of activation treatment, a method of contacting the catalyst with an activation treatment agent under heating or without heating can be mentioned. As the activation treatment agent, a halogen-containing compound can be mentioned, specifically, hydrogen chloride, hydrogen fluoride, chlorocarbon, fluorocarbon, chlorofluorocarbon, hydrochlorocarbon, hydrofluorocarbon, hydrochlorofluorocarbon, chloroolefin, fluoroolefin, chlorofluoroolefin, hydrofluoroolefin, hydrochloroolefin, hydrochlorofluoroolefin, hydrochlorofluoroolefin, can be mentioned. In addition, compound 1, which is a raw material, can be used as the halogen-containing compound. By subjecting a metal oxide to the above-mentioned activation treatment, a partial halide of the metal oxide can be produced.

[0036] The catalyst may be subjected to activation treatment before being accommodated in the reactor, but it is preferable to perform the activation treatment while it is accommodated in the reactor, since the operation is simple and the work efficiency is good. Therefore, it is preferable to perform the activation treatment by introducing an activation treatment agent into the reactor containing the catalyst. The activation treatment agent may be introduced into the reactor at room temperature, but it is preferable to adjust the temperature by heating or the like when introducing it into the reactor, in order to efficiently perform the activation treatment. When introducing the activation treatment agent, an inert gas (dilution gas) may be introduced together. Specific examples of the dilution gas include nitrogen, carbon dioxide, helium, and argon. In order to increase the efficiency of the activation treatment, it is preferable to perform the activation treatment in a state where the inside of the reactor is heated. In this case, the temperature of the reactor when the activation treatment agent is supplied is preferably 50 to 500° C., more preferably 100 to 400° C., and further preferably 150 to 350° C. The residence time of the activation treatment agent is preferably 1 to 1000 seconds, and more preferably 2 to 500 seconds.

[0037] In addition to the above-mentioned activation treatment before the reaction, the catalyst can be reactivated. In particular, when the activity of the catalyst is reduced and the conversion rate of compound 1 is reduced, the catalyst can be reactivated. This allows the catalyst to be reactivated and reused.

[0038] The reactivation treatment method may be a method in which the catalyst is brought into contact with a treatment agent for reactivation treatment (reactivation treatment agent) under heating or without heating, similar to the activation treatment before use. Specific examples of the reactivation treatment agent include oxygen, chlorine, hydrogen fluoride, hydrogen chloride, halogen-containing hydrocarbons, and perhalogenated carbons. In addition, in the reactivation treatment, in order to suppress side reactions and improve the durability of the catalyst, an inert gas such as nitrogen, carbon dioxide, a rare gas (helium, etc.), or water vapor can be used to dilute the reactivation treatment agent.

[0039] When the activity of the catalyst has decreased to a level that makes it impossible to reactivate it, or when the production of compound 2 is stopped, the catalyst may be extracted from the reactor and refilled. When extracting the catalyst, it is preferable to purge the reactor with an inert gas in advance in order to remove organic matter and acidity remaining in the reactor or adhering to the catalyst. Specific examples of the inert gas used include nitrogen and helium. Purging with air may be undesirable because of the possibility of forming harmful substances such as hexavalent chromium in the catalyst.

[0040] In the above reaction (liquid phase reaction, gas phase reaction), the molar ratio of hydrogen chloride used to compound 1 used (molar amount of hydrogen chloride / molar amount of compound 1) is preferably 0.01 to 100, more preferably 0.1 to 10, further preferably 0.3 to 5, and particularly preferably 0.5 to 2, from the viewpoint of producing compound 2 with higher selectivity. From the viewpoint of suppressing the production of by-products and improving the volumetric efficiency of the reactor, it is more particularly preferably 0.75 to 1.5, and most preferably 0.8 to 1.2. In particular, when the molar ratio is 0.75 or more, the conversion rate of compound 1 is more excellent.

[0041] The above reaction is carried out in a reactor. The shape and structure of the reactor are not particularly limited. For example, in the case of a gas phase reaction described later, a cylindrical vertical reactor capable of being filled with a catalyst can be used. As the cylindrical vertical reactor, a multi-tube reactor is preferred. Specific examples of materials for the reactor include glass, iron, nickel, stainless steel, and alloys mainly composed of iron or nickel. The reactor may be provided with a heating unit therein, such as an electric heater, etc. The reactor may have a sheath tube into which a thermometer for measuring the temperature inside is inserted. When a multi-tubular reactor is used as the reactor, the pressure drop of each reaction tube is preferably within ±20%, more preferably within ±15%, and further preferably within ±10% of the average pressure drop of all reaction tubes. By adjusting the catalyst loading amount of each reaction tube to be constant, the difference in pressure drop between the reaction tubes can be reduced.

[0042] In the production method of the present invention, the reaction between compound 1 and hydrogen chloride may be either a liquid phase reaction or a gas phase reaction. The liquid phase reaction refers to reacting compound 1 with hydrogen chloride in a liquid state. The gas phase reaction refers to reacting compound 1 with hydrogen chloride in a gaseous state. The above reaction may be carried out in a batch manner, a semi-continuous manner, or a continuous flow manner.

[0043] The liquid phase reaction will now be described in detail. A specific procedure for the liquid phase reaction is, for example, a procedure in which hydrogen chloride is continuously or discontinuously supplied to a reactor in which a mixture of compound 1 in a liquid state and a catalyst is present, and compound 2 produced by the reaction is continuously or discontinuously withdrawn from the reactor. From the viewpoints of reaction yield and production efficiency, the reaction temperature in the liquid phase reaction is preferably 20°C or higher, more preferably 30°C or higher, and even more preferably 50°C or higher, and is preferably 250°C or lower, more preferably 200°C or lower, and even more preferably 150°C or lower. The reaction time in the liquid phase reaction is preferably 0.1 to 100 hours, more preferably 0.2 to 50 hours, and even more preferably 0.5 to 20 hours, from the viewpoints of reaction yield and production efficiency. The reaction time means the residence time of the raw materials in the reactor. The liquid phase reaction may be carried out in the presence of a solvent, if necessary. Specific examples of the solvent include CF3 (CF2) m Examples of the compound include linear perfluoroalkyl compounds having 5 to 8 carbon atoms represented by CF3 (wherein m is an integer of 3 to 6).

[0044] Next, the gas phase reaction will be described in detail. A specific procedure for the gas phase reaction includes continuously supplying the raw materials, compound 1 and hydrogen chloride, which have been heated to a gaseous state, into a reactor, and bringing the gaseous compound 1 and hydrogen chloride into contact with a catalyst packed in the reactor to obtain compound 2. A gas inert to the above reaction (dilution gas) may be supplied to the reactor because it is effective for adjusting the flow rate, suppressing by-products, suppressing catalyst deactivation, etc. Specific examples of the dilution gas include nitrogen, carbon dioxide, helium, and argon.

[0045] The reaction temperature in the gas phase reaction (temperature inside the reactor) is preferably 100 to 450°C, more preferably 120 to 380°C, further preferably 140 to 360°C, and particularly preferably 160 to 340°C, in terms of enabling compound 2 to be produced more efficiently. When the reaction temperature is 100° C. or higher (preferably 180° C. or higher, more preferably 225° C. or higher), the conversion rate of compound 1 increases. When the reaction temperature is 450° C. or lower (preferably 360° C. or lower), the selectivity of compound 2 increases. The temperature in the reactor can be controlled by adjusting the temperature and pressure of the raw materials fed to the reactor. If necessary, the inside of the reactor can be supplementarily heated by an electric heater, a microwave generator, or the like.

[0046] The reaction time in the gas phase reaction is preferably from 0.1 to 1000 seconds, more preferably from 1 to 800 seconds, and even more preferably from 5 to 600 seconds. The above reaction time corresponds to the residence time of the raw materials in the reactor, and can be controlled by adjusting the supply amount (flow rate) of the raw materials to the reactor.

[0047] The pressure of the reaction system in the gas phase reaction (pressure in the reactor) is preferably 0 to 2.0 MPa, more preferably 0 to 1.5 MPa. It may be a negative pressure. From the viewpoint of handling, the pressure in the reactor is more preferably 0 to 1.0 MPa. In this specification, unless otherwise specified, the pressure indicates a gauge pressure.

[0048] The content of the by-product in the product is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total mass of the product. The lower limit of the content of the by-product is usually 0% by mass. Here, the product means a halogenated hydrocarbon produced by the reaction of compound 1 with hydrogen chloride. When the product contains impurities, a treatment may be carried out to separate compound 2 from the obtained product. Examples of the separation treatment include known methods such as distillation.

[0049] Next, a more detailed embodiment of the gas phase reaction will be described with reference to Figure 1. A reaction apparatus 20 shown in Figure 1 is an example of a reaction apparatus used for a gas phase reaction. The reaction apparatus 20 includes a reactor 1. The reactor 1 is connected to a supply line 2 for the compound 1, a supply line 3 for hydrogen chloride, 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 the compound 1 and the supply line 3 for the hydrogen chloride may be connected to the reactor 1 separately, or may be connected before the reactor 1 and then connected to the reactor 1. For example, as shown in FIG. 1, the supply line 2 for the compound 1, the supply line 3 for the hydrogen chloride, and the supply line 4 for the nitrogen are connected. As a result, a mixture of the compound 1, hydrogen chloride, and nitrogen is supplied to the reactor 1 via the mixture supply line 5.

[0050] In the reaction apparatus 20 shown in FIG. 1, the supply line 2 for the compound 1, the supply line 3 for the hydrogen chloride, and the supply line 4 for the nitrogen are provided with preheaters 2a, 3a, and 4a equipped with electric heaters, respectively. It is preferable that the compound 1, hydrogen chloride, and nitrogen 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 compound 1, hydrogen chloride, and nitrogen to be efficiently heated to a predetermined reaction temperature inside the reactor 1. The preheaters 2a, 3a, and 4a are not essential, but are preferably installed.

[0051] 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 taken out from the reactor 1 is treated after the outlet line 7 to remove acidic substances such as hydrogen chloride and hydrogen fluoride, water vapor, and water. The gas thus obtained is hereinafter referred to as "outlet gas." Each component in the outlet gas is analyzed and quantified by an analytical device 11 such as a gas chromatograph (GC).

[0052] The outlet gas contains compound 2. Compounds contained in the outlet gas other than compound 2 include compound 1, which is an unreacted raw material, hydrogen chloride, and hydrogen fluoride.

[0053] Components other than compound 2 contained in the outlet gas can be removed to a desired extent by known means such as distillation. In the reactor 20, unreacted raw materials can be separated from the reaction mixture or outlet gas discharged from the reactor 1 by distillation or the like and returned to the reactor as part of the raw materials. This can improve the productivity of the compound 2.

[0054] In the production method of the present invention, when compound 1 is 1,1,2,2,3-pentafluoropropane (245ca), 3-chloro-1,1,2,2-tetrafluoropropane (244ca) is obtained as compound 2. Below, we will explain in detail the case where 245ca is used as the raw material.

[0055] 245ca can be produced by known methods, for example, by the method described in WO 1994 / 27939.

[0056] When 244ca is produced by a gas-phase reaction using 245ca as a raw material, 244ca can be obtained as a component of the crude gas. In addition to 244ca, the crude gas may contain unreacted 245ca, 2-chloro-1,3,3-trifluoropropene (1233xe), 1-chloro-2,3,3-trifluoropropene (1233yd), 1,2-dichloro-3,3-difluoropropene (1232xd), 1,3-dichloro-2,3-difluoropropene (1232yd), 2,3-dichloro-1,3-difluoropropene (1232xe), 1,2,3-trichloro-3-fluoropropene (1231xd), 2,3,3-trichloro-1-fluoropropene (1231xe), 1,3,3-trichloro-2-fluoropropene (1231yd), 1,2,3,3-tetrachloropropene (1230xd), unreacted hydrogen chloride, hydrogen fluoride, etc. The components other than 244ca can be removed to a desired extent by known means such as distillation, extractive distillation, azeotropic distillation, membrane separation, two-phase separation, and adsorption.

[0057] In this specification, unless otherwise specified, when a compound name or abbreviation of a compound is used, it refers to at least one selected from Z-form and E-form, more specifically, it refers to Z-form or E-form, or a mixture of Z-form and E-form in any ratio. When (E) or (Z) is added after a compound name or abbreviation of a compound, it refers to the (E) form or (Z) form of the respective compound. For example, 1233yd(Z) refers to the Z form, and 1233yd(E) refers to the E form.

[0058] The resulting 244ca may be subjected to a dehydrofluorination reaction to produce 1233yd. The procedure for the dehydrofluorination reaction can be a known method such as that described in WO 2016 / 136744.

[0059] The dehydrofluorination reaction of 244ca may be either a liquid phase reaction or a gas phase reaction. The liquid phase reaction refers to the dehydrofluorination reaction of 244ca in a liquid state or dissolved in a liquid. The gas phase reaction refers to the dehydrofluorination reaction of 244ca in a gaseous state.

[0060] Furthermore, in the production method of the present invention, when compound 1 is HFC-449pccc, HCFC-448occc is obtained as compound 2. Below, we will explain in detail the case where 449pccc is used as the raw material.

[0061] 449pccc can be produced by known methods, for example, the method described in RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 5 No. 7 2002 pp. 1162-1165.

[0062] When 448occc is produced by a gas-phase reaction using 449pccc as a raw material, 448occc can be obtained as a component of the crude gas. In addition to 448occc, the crude gas also contains unreacted 449pccc, C5H2F (7-x) Cl (1+x) (where x represents 0 to 7.) etc. may be included. The components other than the 448 occc can be removed to a desired extent by known means such as distillation, extractive distillation, azeotropic distillation, membrane separation, two-phase separation, adsorption, and the like.

[0063] The resulting 448occc may be dehydrofluorinated to produce 1-chloro-2,3,3,4,4,5,5-heptafluoro-1-pentene (HCFO-1437dycc). In particular, it is preferable to produce (Z)-1-chloro-2,3,3,4,4,5,5-heptafluoro-1-pentene (HCFO-1437dycc(Z)). The procedure for the dehydrofluorination reaction may be a known method such as that described in Zhurnal Organicheskoi Khimii (Russia), 1988, Vol. 24, No. 8, pp. 1626-1633.

[0064] The dehydrofluorination reaction of 448occc may be either a liquid phase reaction or a gas phase reaction. The liquid phase reaction refers to the dehydrofluorination reaction of 448occc in a liquid state or dissolved in a liquid. The gas phase reaction refers to the dehydrofluorination reaction of 448occc in a gaseous state. EXAMPLES

[0065] The present invention will be described in more detail below with reference to examples, but the present invention is not limited thereto. Examples 1 to 19 described below correspond to working examples.

[0066] <Gas chromatograph conditions> In the production of the following various compounds, the composition of the obtained products was analyzed using a gas chromatograph (GC). The column used was a DB-1301 (length 60 m × inner diameter 250 μm × thickness 1 μm, manufactured by Agilent Technologies, Inc.).

[0067] <Catalyst preparation> The catalyst used in the reactions described below was prepared as follows. The reaction apparatus used in each preparation example was the same as the reaction apparatus 20 described with reference to Fig. 1. The reaction apparatus 1 was a tubular reaction apparatus made of SUS304 having an inner diameter of 16.1 mm and a length of 15 cm.

[0068] (Catalyst Preparation Example 1) 38.1 g of chromium zinc composite oxide (PRICAT62-3M, Johnson Matthey) was filled into the reactor, and the temperature inside the reactor was raised to 300°C while flowing nitrogen (N2) at 150 Nml / min. While maintaining the inside of the reactor at atmospheric pressure, the catalyst filled therein was dried until the moisture content in the gas obtained from the reactor outlet was 5 ppm by volume or less. Thereafter, the reactor was heated to 350°C, and trifluoromethane (HFC-23) was supplied at a flow rate of 21.9 Nml / min and N2 at a flow rate of 43.7 NmL / min for 16 hours, to prepare a partially fluorinated chromium zinc composite oxide in the reactor. The obtained catalyst corresponds to a partial fluoride of a metal oxide. The Cr content in the chromium-zinc composite oxide (PRICAT62-3M) was 97.0 mass % relative to the total mass of metals contained in the catalyst, and the Zn content was 2.9 mass % relative to the total mass of metals contained in the catalyst.

[0069] (Catalyst Preparation Example 2) A partially fluorinated chromium aluminum magnesium composite oxide was obtained in the same manner as in (Catalyst Preparation Example 1), except that the chromium zinc composite oxide (PRICAT62-3M, Johnson Matthey) was replaced with 33.6 g of chromium aluminum magnesium composite oxide (N401AG, JGC Catalysts and Chemicals). The obtained catalyst corresponds to a partial fluoride of a metal oxide. The Cr content in the above chromium aluminum magnesium composite oxide (N401AG) was 20.3 mass% relative to the total mass of metals contained in the catalyst, the Al content was 76.6 mass% relative to the total mass of metals contained in the catalyst, and the Mg content was 3.0 mass% relative to the total mass of metals contained in the catalyst.

[0070] (Catalyst Preparation Example 3) A fluorination treatment was carried out in the same manner as in (Catalyst Preparation Example 1), except that the chromium-zinc composite oxide (PRICAT62-3M, Johnson Matthey) was replaced with 25.5 g of alumina (N612N, JGC Catalysts and Chemicals), to obtain partially fluorinated alumina. The obtained catalyst corresponds to a partial fluoride of a metal oxide.

[0071] (Catalyst Preparation Example 4) A partially fluorinated chromium-zinc composite oxide was prepared in the same manner as in (Catalyst Preparation Example 1), except that the temperature of the reactor was changed from 350°C to 320°C.

[0072] (Catalyst Preparation Example 5) 1100g of Cr(NO3)3·9H2O was dissolved in 2.5L of water, and 2000g of 28% by mass of ammonium hydroxide solution was added. The above-obtained aqueous solution was added to 4L of heated water while stirring the water, obtaining hydroxide precipitate. The precipitate was then filtered, and the obtained solid was washed with pure water and dried, and the obtained product was crushed to obtain oxide powder. The obtained oxide powder was mixed with 3% by mass of graphite, formed into a cylindrical shape with a diameter of 5mm and a height of 5mm using a tableting machine, and calcined in nitrogen at 420℃ for 5 hours to prepare chromium oxide. A partially fluorinated chromium oxide was obtained in the same manner as in (Catalyst Preparation Example 1), except that the chromium-zinc composite oxide (PRICAT62-3M, Johnson Matthey) was replaced with 36.6 g of the chromium oxide obtained above.

[0073] (Catalyst Preparation Example 6) A reactor was filled with 38.1 g of chromium zinc composite oxide (PRICAT62-3M, Johnson Matthey), and the temperature inside the reactor was raised to 300° C. while flowing nitrogen (N2) at 150 Nml / min. While maintaining the inside of the reactor at atmospheric pressure, the filled catalyst was dried until the moisture content in the gas obtained from the reactor outlet became 5 ppm by volume or less.

[0074] <Example 1> The reactor temperature was set to 250°C while N2 was circulated at a flow rate of 15.6 NmL / min through the reactor containing the catalyst prepared in Catalyst Preparation Example 1. After the reactor temperature stabilized, 245ca was fed to the reactor at a flow rate of 0.047 g / min and hydrogen chloride was fed to the reactor at a flow rate of 0.013 g / min. The crude gas at the reactor outlet was washed with water, then passed through an alkali washing section and molecular sieve 4A to remove acids and obtain a dried product. In addition, each component of the crude gas at the reactor outlet was analyzed by gas chromatography. The analysis results of the crude gas 10 hours after the start of the feeding of 245ca and hydrogen chloride are shown in Table 2. The 245ca used was one that had been subjected to a dehydration treatment. Specifically, 100 g of molecular sieve 4A (manufactured by Junsei Chemical Co., Ltd.) was placed as a dehydrating agent in a sealed container filled with raw material composition 1 (content of 245ca in raw material composition 1: 99.9 mass% or more) (1 kg) containing 245ca, and the container was left to stand for 3 days to perform dehydration treatment, and the raw material composition 2 after the dehydration treatment was used as the 245ca. The water content of the raw material composition 2 was 20 ppm by mass. The moisture content was measured using a Karl Fischer moisture meter. A trace moisture measuring device (manufactured by Mitsubishi Chemical Analytech Co., Ltd., Model CA-200) was used as the Karl Fischer moisture meter, and a liquefied gas vaporizer (manufactured by the same company, Model VG-200) was connected to the sample introduction section, and a preset amount of the raw material composition 2 was vaporized and automatically injected into the moisture meter.

[0075] <Example 2> As shown in Table 2, the same procedure as in Example 1 was followed to obtain the product, except that the feed amounts of hydrogen chloride and N2 were changed.

[0076] <Example 3> As shown in Table 2, the same procedure as in Example 1 was followed to obtain products, except that the type of catalyst was changed.

[0077] <Example 8> As shown in Table 2, the same procedure as in Example 1 was followed to obtain the product, except that the feed amounts of hydrogen chloride and N2 were changed.

[0078] <Example 9> As shown in Table 2, the product was obtained by following the same procedure as in Example 1, except that the reaction temperature and the supply amounts of 245ca, hydrogen chloride and N2 were changed.

[0079] <Example 10> As shown in Table 2, the product was obtained by following the same procedure as in Example 1, except that the reaction temperature and the supply amounts of 245ca, hydrogen chloride and N2 were changed.

[0080] <Example 11> As shown in Table 2, the products were obtained according to the same procedure as in Example 1, except that the feed amounts of 245ca, hydrogen chloride and N2 were changed.

[0081] <Example 12> The reactor temperature was set to 330°C while N2 was circulated at a flow rate of 81.5 NmL / min through the reactor containing the catalyst prepared in Catalyst Preparation Example 4. After the reactor temperature stabilized, 245ca was supplied to the reactor at a flow rate of 0.244 g / min and hydrogen chloride was supplied at a flow rate of 0.066 g / min. The crude gas at the reactor outlet was washed with water, then passed through an alkali washing section and molecular sieve 4A to remove acids and obtain a dried product. In addition, each component of the crude gas at the reactor outlet was analyzed by gas chromatography. The analysis results of the crude gas 10 hours after the start of the supply of 245ca and hydrogen chloride are shown in Table 2. The 245ca used was subjected to the same dehydration treatment as in Example 1.

[0082] <Example 13> As shown in Table 2, the product was obtained by following the same procedure as in Example 12, except that the reaction temperature and the supply amounts of 245ca, hydrogen chloride and N2 were changed.

[0083] <Example 14> As shown in Table 2, the product was obtained by following the same procedure as in Example 12, except that the reaction temperature and the supply amounts of 245ca, hydrogen chloride and N2 were changed.

[0084] <Example 15> A product was obtained in the same manner as in Example 1, except that the catalyst was changed to the catalyst prepared in (Catalyst Preparation Example 5).

[0085] <Example 16> The reactor temperature was set to 300°C while N2 was circulated at a flow rate of 85.7 NmL / min through the reactor containing the catalyst prepared in Catalyst Preparation Example 6. After the reactor temperature stabilized, 245ca was fed to the reactor at a flow rate of 0.256 g / min and hydrogen chloride was fed to the reactor at a flow rate of 0.070 g / min. The crude gas at the reactor outlet was washed with water, then passed through an alkali washing section and molecular sieve 4A to remove acids and obtain a dried product. In addition, each component of the crude gas at the reactor outlet was analyzed by gas chromatography. The analysis results of the crude gas 5 hours after the start of the supply of 245ca and hydrogen chloride are shown in Table 2.

[0086] <Example 17> As shown in Table 2, the product was obtained by following the same procedure as in Example 16, except that the reaction temperature and the feed amounts of 245ca, hydrogen chloride and N2 were changed.

[0087] In Table 2, the conversion rate represents the ratio (unit: %) of the molar amount of 245ca consumed in the reaction to the molar amount of 245ca used in the reaction. The 244ca selectivity represents the ratio (unit: %) of the molar amount of 244ca in the product to the molar amount of 245ca consumed in the reaction. The 1233yd(Z) selectivity represents the ratio (unit: %) of the molar amount of 1233yd(Z) in the product to the molar amount of 245ca consumed in the reaction. The selectivity for other components represents the ratio (unit: %) of the molar amount of components other than the above-mentioned components in the product to the molar amount of 245ca consumed in the reaction. In Examples 1 to 3, 8 to 10, and 14 to 15, the reaction pressure (pressure in the reactor) was 0 MPaG, and the residence time was 30 seconds. In Examples 11 to 13, and 16 to 17, the reaction pressure (pressure in the reactor) was 0 MPaG, and the residence time was 5 seconds. In Example 4 described later, the reaction pressure (pressure in the reactor) was 0 MPaG, and the residence time was 30 seconds.

[0088] [Table 2]

[0089] As shown in Table 2, according to the production process of the present invention, HCFC could be produced with high selectivity. When the catalyst obtained in Catalyst Preparation Example 3 was used instead of the catalyst obtained in Catalyst Preparation Example 1 in Example 1, the specified HCFC could be obtained (Example 4). However, the conversion rate was lower than that of Example 3, and the selectivity was also somewhat inferior, at about 70%. Comparing Examples 1 to 4, it was confirmed that the catalyst containing Cr was more effective.

[0090] From a comparison between Example 1 and Example 8, it was confirmed that when the molar ratio of hydrogen chloride to compound 1 was 0.75 or more, the conversion rate was better. From a comparison between Example 1 and Examples 9 and 10, it was confirmed that the conversion rate was superior when the reaction temperature was 180° C. (preferably 225° C.) or higher. Comparing Examples 11 to 14, it was confirmed that when the reaction temperature was 360° C. or lower, the selectivity was superior. A comparison of Example 12 with Examples 16 and 17 confirmed that the conversion rate was superior when an activation treatment was performed (in other words, when a partial halide of a metal oxide was used).

[0091] <Example 5> The reactor temperature was set to 250°C while N2 was circulated at a flow rate of 15.6 NmL / min through the reactor containing the catalyst prepared in Catalyst Preparation Example 1. After the reactor temperature stabilized, 449pccc was fed to the reactor at a flow rate of 0.082 g / min and hydrogen chloride was fed to the reactor at a flow rate of 0.013 g / min. The crude gas at the reactor outlet was washed with water, then passed through an alkali washing section and a molecular sieve 4A to remove acids and obtain a dried product. In addition, each component of the crude gas at the reactor outlet was analyzed by gas chromatography. Analysis of the crude gas 10 hours after the start of the supply of 449pccc and hydrogen chloride revealed that the conversion of 449pccc was 63.4%, the selectivity of 448occc was 94.8%, and the selectivity of 1437dycc(Z) was 0.1%. The conversion rate mentioned above indicates the ratio (unit: %) of the molar amount of 449pccc consumed in the reaction to the molar amount of 449pccc used in the reaction. The 448occc selectivity represents the ratio (unit: %) of the molar amount of 448occc in the product to the molar amount of 449pccc consumed in the reaction. The 1437dycc(Z) selectivity represents the ratio (unit: %) of the molar amount of 1437dycc(Z) in the product to the molar amount of 449pccc consumed in the reaction.

[0092] <Example 6> In a 2-liter four-neck flask equipped with a stirrer and a Dimroth condenser, 251.31 g of 244ca obtained in Example 1 and 2.51 g of tetra-n-butylammonium chloride (TBAC) were placed, and the flask was heated to 50°C. The reaction temperature was maintained at 50°C, and 631.55 g of a 34% by mass aqueous solution of potassium hydroxide (KOH) was added dropwise over 5 minutes. Stirring was then continued for 30 hours, and the organic layer was collected. The organic layer collected above was washed with water, and then distilled to obtain purified 1233yd containing 1233yd (E) and 1233yd (Z). The selectivity of 1233yd (E) was 8.9%, and the selectivity of 1233yd (Z) was 91.0%.

[0093] <Example 7> In a 0.2-liter four-neck flask equipped with a stirrer and a Dimroth condenser, 100.7 g of the 448occc obtained in Example 5 and 1.0 g of tetra-n-butylammonium bromide (TBAB) as a phase transfer catalyst were placed, and the flask was cooled to 10°C. The reaction temperature was maintained at 10°C, and 153.9 g of a 34 mass% aqueous potassium hydroxide (KOH) solution was added dropwise over 30 minutes. Stirring was then continued for 38 hours. The resulting reaction solution was separated into an organic phase and an aqueous phase, and the organic phase was collected. The collected organic phase was purified to obtain 78.6 g of an isomer mixture of 1437dycc(Z) and 1437dycc(E) with a purity of 99.5%. The mass ratio of 1437dycc(Z) to 1437dycc(E) in the isomer mixture (1437dycc(Z) / 1437dycc(E)) was 99 / 1.

[0094] <Example 17> As shown in Table 3, a product was obtained according to the same procedure as in Example 1, except that the water content of raw material composition 2 was 198 ppm by mass.

[0095] <Example 18> As shown in Table 3, a product was obtained according to the same procedure as in Example 1, except that the water content of raw material composition 2 was 395 ppm by mass.

[0096] <Example 19> As shown in Table 3, a product was obtained according to the same procedure as in Example 1, except that the water content of the raw material composition 2 was 1995 ppm by mass.

[0097] In Table 3, the column "Moisture content [ppm by mass]" indicates the moisture content of raw material composition 2.

[0098] [Table 3]

[0099] As shown in Table 3, it was confirmed that the production method of the present invention is effective when the water content of raw material composition 2 is 2000 ppm by mass or less (preferably 400 ppm by mass or less, and more preferably 200 ppm by mass or less). The entire contents of the specification, claims, abstract and drawings of Japanese Patent Application No. 2019-084111, filed on April 25, 2019, are hereby incorporated by reference as the disclosure of the specification of the present invention. [Explanation of symbols]

[0100] 1: Reactor 2: Compound 1 supply line 2a: Preheater 3: Hydrogen chloride supply line 3a: Preheater 4: Nitrogen supply line 4a: Preheater 5: Mixture supply line 6: Cooling section 7: Exit Line 8: Steam and acid liquid collection tank 9: Alkaline cleaning equipment 10: Dehydration tower 11: Analyzer 20: Reactor

Claims

1. A method for producing a hydrochlorofluorocarbon, comprising reacting a hydrofluorocarbon represented by formula (1) with hydrogen chloride in the presence of a catalyst to produce a hydrochlorofluorocarbon represented by formula (2). Formula (1) Formula (2) X-L-Z X is -CH ａ F （３－ａ） Represents. Y is -CH ｂ F （３－ｂ） Represents. Z is -CH ｂ C ｃ F （３－ｂ－ｃ） Represents. L is -CF ２ -, -CF ２ CF ２ -, or a fluoroalkylene group having 3 to 6 carbon atoms in which at least some of the hydrogen atoms may be substituted with fluorine atoms, and the terminals of the fluoroalkylene group having 3 to 6 carbon atoms are all -CF ２ -It is. a represents 0 or 1. b represents 1 or 2. c represents 1 or 2. However, when a is 0, b represents 1 or 2, and when a is 1, b represents 2. When b is 1, c is 1 or 2; when b is 2, c is 1.

2. The process of claim 1 , wherein the catalyst is a metal-containing catalyst.

3. the catalyst comprises at least one selected from a metal oxide, a partial halide of a metal oxide, and a metal halide; 3. The method according to claim 1, wherein the metal oxide, the partial halide of the metal oxide, and the metal halide each contain at least one element selected from the group consisting of Cr and Al.

4. The process of claim 3 , wherein the catalyst comprises a partial halide of the metal oxide.

5. The L is -CF ２ -, -CF ２ CF ２ -, -CF ２ -CF ２ -CF ２ -, -CF ２ -CHF-CF ２ -or-CF ２ -CH ２ -CF ２ The method according to any one of claims 1 to 4, wherein

6. The method according to any one of claims 1 to 5, wherein a is 1, b is 2, and c is 1.

7. The method according to any one of claims 1 to 6, wherein the hydrofluorocarbon represented by the formula (1) and the hydrogen chloride are reacted in a gas phase.

8. The process according to any one of claims 1 to 7, wherein the reaction temperature is from 100 to 450°C.

9. The method according to any one of claims 1 to 8, wherein the molar ratio of the hydrogen chloride to the hydrofluorocarbon represented by the formula (1) is 0.5 to 2.

0.

10. The reaction is carried out using a raw material composition containing a hydrofluorocarbon represented by the formula (1) and hydrogen chloride, The method according to any one of claims 1 to 9, wherein the raw material composition has a moisture content of 5000 ppm by mass or less.

11. The method according to claim 10, wherein the moisture content is 400 ppm by mass or less.

12. The hydrofluorocarbon represented by the formula (1) is 1,1,2,2,3-pentafluoropropane, The method according to any one of claims 1 to 11, wherein the hydrochlorofluorocarbon represented by the formula (2) is 3-chloro-1,1,2,2-tetrafluoropropane.

13. A method for producing 1-chloro-2,3,3-trifluoropropene, comprising reacting 1,1,2,2,3-pentafluoropropane with hydrogen chloride in the presence of a catalyst to produce 3-chloro-1,1,2,2-tetrafluoropropane, and then subjecting the produced 3-chloro-1,1,2,2-tetrafluoropropane to a dehydrofluorination reaction to produce 1-chloro-2,3,3-trifluoropropene.

14. The hydrofluorocarbon represented by the formula (1) is 1,1,2,2,3,3,4,4,5-nonafluoropentane, The method according to any one of claims 1 to 11, wherein the hydrochlorofluorocarbon represented by the formula (2) is 5-chloro-1,1,2,2,3,3,4,4-octafluoropentane.

15. A method for producing 1-chloro-2,3,3,4,4,5,5-heptafluoro-1-pentene, comprising reacting 1,1,2,2,3,3,4,4,5-nonafluoropentane with hydrogen chloride in the presence of a catalyst to produce 5-chloro-1,1,2,2,3,3,4,4-octafluoropentane, and then subjecting the produced 5-chloro-1,1,2,2,3,3,4,4-octafluoropentane to a dehydrofluorination reaction to produce 1-chloro-2,3,3,4,4,5,5-heptafluoro-1-pentene.

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