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 an HCFC by which an HCFC is able to be produced with high selectivity. A method for producing a hydrochlorofluorocarbon according to the present invention is characterized by producing a hydrochlorofluorocarbon having 3-8 carbon atoms by reacting a hydrofluorocarbon having 3-8 carbon atoms and a chlorine-containing compound having one or two carbon atoms with each other in the presence of a catalyst that contains a compound having at least one substance selected from among Cr and Al.

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] One candidate for a raw material for efficiently synthesizing HCFOs is hydrochlorofluorocarbon (hereinafter, also referred to as "HCFC"). As a method for producing a desired HCFC, 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 to selectively obtain the desired HCFC, and a method for obtaining the desired 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 saturated hydrofluorocarbon having 3 to 8 carbon atoms with a chlorine-containing compound having 1 or 2 carbon atoms in the presence of a catalyst containing a metal compound having at least one metal element selected from Cr and Al to produce a saturated hydrochlorofluorocarbon having 3 to 8 carbon atoms. (2) The method according to (1), wherein the metal compound is a metal oxide, a partial halide of a metal oxide, or a metal halide. (3) The hydrofluorocarbon is a compound represented by the formula (1) described below, The method according to (1) or (2), wherein the hydrochlorofluorocarbon is a compound represented by formula (2) described below. (4) The method according to any one of (1) to (3), wherein L is an alkylene group having 1 to 3 carbon atoms in which some hydrogen atoms may be substituted with fluorine atoms. (5) The method according to any one of (1) to (4), wherein a is 1, b is 2, and c is 1. (6) The process according to any one of (1) to (5), wherein the chlorine-containing compound is carbon tetrachloride, chloroform, dichloromethane, trichloroethylene, or tetrachloroethylene. (7) The method according to any one of (1) to (6), wherein the hydrofluorocarbon and the chlorine-containing compound are reacted 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 hydrofluorocarbon is 1,1,2,2,3-pentafluoropropane; The method according to any one of (1) to (8), wherein the hydrochlorofluorocarbon is 3-chloro-1,1,2,2-tetrafluoropropane. (10) 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 (9) to a dehydrofluorination reaction to produce 1-chloro-2,3,3-trifluoropropene. (11) The hydrofluorocarbon is 1,1,2,2,3,3,4,4,5-nonafluoropentane; The method according to any one of (1) to (8), wherein the hydrochlorofluorocarbon is 5-chloro-1,1,2,2,3,3,4,4-octafluoropentane. (12) 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 (11) 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 having 3 to 8 carbon atoms (hereinafter also referred to as "compound 2") by reacting a hydrofluorocarbon having 3 to 8 carbon atoms (hereinafter also referred to as "compound 1") with a chlorine-containing compound having 1 or 2 carbon atoms (hereinafter also referred to as "Cl compound") in the presence of a catalyst (hereinafter also referred to as "catalyst X") containing a metal compound having at least one metal element selected from Cr and Al (hereinafter also referred to as "metal A"). In other words, the production method of the present invention is a method for producing compound 2 by contacting compound 1 with a Cl compound 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] The compound 1 has 3 to 8 carbon atoms, preferably 3 to 6, and more preferably 3 to 5, in terms of enabling the compound 2 to be produced with higher selectivity.

[0011] Compound 1 is preferably a compound represented by formula (1). Formula (1) XLY X is -CHa F (3-a) Represents. a represents 0 or 1.

[0012] 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.

[0013] L represents an alkylene group having 1 to 6 carbon atoms in which at least a portion of hydrogen atoms may be substituted with fluorine atoms. Among them, from the viewpoint of availability of compound 1, an alkylene group having 1 to 3 carbon atoms in which a portion of hydrogen atoms may be substituted with fluorine atoms is preferred. L is more preferably a perfluoroalkylene group having 1 to 3 carbon atoms.

[0014] Compound 2 is preferably a compound represented by formula (2). Formula (2) XLZ The definitions of X and L are the same as those of X and L in formula (1). 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.

[0015] The relationships between a, b, and c in formula (1) and formula (2) are 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.

[0016] [Table 1]

[0017] In one preferred embodiment of 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. 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 atom substitutions, and replacement of fluorine atoms with chlorine atoms proceeds at the position of Y. Although the principle behind this is unclear, it is presumed that the fewer the number of fluorine atoms bonded to the carbon atom, the weaker the C-F bond. 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 number of carbon atoms in compound 2 is 3 to 8, preferably 3 to 6, and more preferably 3 to 5, in that compound 2 can be produced with higher selectivity. The number of chlorine atoms in compound 2 is preferably 1. That is, the production method of the present invention can be particularly suitably used in a reaction in which only one of the fluorine atoms in compound 1 is replaced with chlorine. 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.

[0018] Furthermore, for example, when 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorohexane is used as compound 1, 6-chloro-1,1,1,2,2,3,3,4,4,5,5,6-dodecafluorohexane and 6,6-dichloro-1,1,1,2,2,3,3,4,4,5,5-undecafluorohexane can be produced as compound 2.

[0019] As described above, in the production method of the present invention, the compound 1 is used as a raw material. The compound 1 may be one type or two or more types. The raw material may contain impurities in addition to compound 1. Examples of impurities include raw materials for producing compound 1 and by-products other than compound 1 produced during the production of compound 1. When the raw material contains the above-mentioned impurities, the 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.

[0020] The Cl compound has 1 or 2 carbon atoms, preferably 1 carbon atom. The Cl compound may be a saturated compound or an unsaturated compound having an unsaturated bond (eg, a double bond). The number of chlorine atoms in the Cl compound is not particularly limited, but a larger amount of chlorine per molecule is preferable from the viewpoint of producing compound 2 with higher selectivity. That is, when the carbon number is 1, the number of chlorine atoms is more preferably 2 to 4, and more preferably 3 to 4. When the carbon number is 2 and the compound is a saturated compound, the number of chlorine atoms is preferably 2 to 6, and more preferably 3 to 6, and even more preferably 4 to 6. When the carbon number is 2 and the compound is an unsaturated compound, the number of chlorine atoms is preferably 2 to 4, and even more preferably 3 to 4. Specific examples of Cl compounds include carbon tetrachloride, chloroform, dichloromethane, chlorotrifluoromethane, dichlorodifluoromethane, trichlorofluoromethane, chlorodifluoromethane, dichlorofluoromethane, chlorofluoromethane, 1,1-dichloroethylene, 1,2-dichloroethylene, trichloroethylene, and tetrachloroethylene. Among these, from the viewpoint of further improving the selectivity of compound 2, the Cl compound is preferably carbon tetrachloride, chloroform, dichloromethane, trichloroethylene, or tetrachloroethylene, more preferably carbon tetrachloride, chloroform, dichloromethane, or tetrachloroethylene, further preferably carbon tetrachloride, chloroform, or dichloromethane, and particularly preferably carbon tetrachloride or chloroform. As the Cl compound, two or more kinds may be used.

[0021] The catalyst X may contain a metal compound having the metal A, and preferably contains a metal oxide, a partial halide of a metal oxide, or a metal halide having the metal A, from the viewpoint of producing the compound 2 with a higher selectivity. In other words, the catalyst X preferably contains a metal oxide having the metal A, a partial halide of a metal oxide having the metal A, or a metal halide having the metal A. Among them, it is more preferable that the catalyst X contains a partial halide of a metal oxide having a metal A. As the catalyst X, one type may be used alone, or two or more types may be used in combination.

[0022] 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 consisting 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.

[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, which may contain a halogen other than fluorine.

[0024] The metal oxide, the partial halide of the metal oxide, and the metal halide may contain both Cr and Al. Among these, a metal oxide containing Cr, a partial halide of a metal oxide containing Cr, or a metal halide containing Cr is preferred, since the conversion rate of compound 1 is higher.

[0025] The above metal oxides, the above partial halides of metal oxides, and the above metal halides may contain metals 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 them, in terms of increasing the physical and chemical durability of the catalyst and enabling more efficient production of compound 2, it is preferable for the catalyst to contain Na, K, Mg, Zn, or Mn, and it is more preferable for the catalyst to contain Mg or Zn. 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.

[0026] When Cr is contained in the catalyst X, 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 the compound 1. The upper limit is 100% by mass. When the catalyst X 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 the metals contained in the catalyst, from the viewpoint of improving the conversion rate of the compound 1. The upper limit is 100% by mass. When catalyst X 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% based on the total mass of metals (100 mass%). On the other hand, the content of metals other than metal A is preferably 0.1 to 10 mass% and more preferably 1 to 5 mass% based on the total mass of metals (100 mass%).

[0027] 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.

[0028] 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.

[0029] In order to improve the reactivity, the catalyst X may be formed into pellets before use, or may be supported on a carrier before use. 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 X.

[0030] An example of a method for forming the catalyst X into pellets is a method in which the catalyst X is crushed into powder and formed into pellets using a tablet press or the like. As the pellet-shaped catalyst X, for example, a cylindrical shape 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 X. 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 X. In this case, the mixture of the catalyst X 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.

[0031] In order to improve the reactivity, the catalyst X 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 X may be dried in the same manner as above while being contained in the reactor. In addition, the catalyst X may be dried before being placed in the reactor.

[0032] The specific surface area of ​​catalyst X 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 faster the degradation tends to occur. 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 m2 / 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.

[0033] In addition, it is preferable that the catalyst X is previously subjected to an activation treatment in terms of improving reactivity (particularly in terms of improving the conversion rate of the compound 1). As a method of activation treatment, a method of contacting the catalyst X 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, the 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.

[0034] The catalyst X 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 X. 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.

[0035] In addition to the above-mentioned activation treatment before the reaction, the catalyst X can be subjected to a reactivation treatment. In particular, when the activity of the catalyst X is reduced and the conversion rate of the compound 1 is decreased, the catalyst X can be subjected to a reactivation treatment. This allows the activity of the catalyst X to be regenerated and the catalyst X to be reused.

[0036] The reactivation treatment method may be, as in the case of the activation treatment before use, a method in which the catalyst X is brought into contact with a treatment agent for reactivation treatment (reactivation treatment agent) under heating or without heating. 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.

[0037] When the activity of catalyst X has decreased to an extent that it cannot be reactivated, or when the production of compound 2 is stopped, the catalyst X may be extracted from the reactor and refilled with catalyst X. When extracting catalyst X, 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 catalyst X. 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.

[0038] In the above reactions (liquid phase reaction, gas phase reaction), the molar ratio of the Cl compound used to the compound 1 used (molar amount of the Cl compound / molar amount of the compound 1) varies depending on the Cl compound. When carbon tetrachloride or dichloromethane is used as the Cl compound, the molar ratio is preferably 0.05 to 5 in order to produce compound 2 with higher selectivity, and is more preferably 0.1 to 2.5, further preferably 0.15 to 2, and particularly preferably 0.15 to 0.8 in order to suppress the production of by-products and improve the volumetric efficiency of the reactor. When chloroform is used as the Cl compound, the ratio is preferably 0.03 to 3.3 in terms of producing compound 2 with higher selectivity, and more preferably 0.06 to 2, and even more preferably 0.1 to 1.5 in terms of suppressing the production of by-products and improving the volumetric efficiency of the reactor. When other Cl compounds are used, the ratio is preferably 0.02 to 10 in terms of producing compound 2 with higher selectivity, and more preferably 0.05 to 5, and even more preferably 0.1 to 3 in terms of suppressing the production of by-products and improving the volumetric efficiency of the reactor.

[0039] 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 catalyst X 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.

[0040] In the production method of the present invention, the reaction between compound 1 and the Cl compound may be either a liquid phase reaction or a gas phase reaction. The liquid phase reaction refers to reacting compound 1 with a Cl compound in a liquid state. The gas phase reaction refers to reacting compound 1 with a Cl compound in a gaseous state. The above reaction may be carried out in a batch manner, a semi-continuous manner, or a continuous flow manner.

[0041] 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 a Cl compound is continuously or discontinuously supplied to a reactor in which a mixture of compound 1 in a liquid state and catalyst X 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).

[0042] 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, compound 1 and a Cl compound, heated to a gaseous state into a reactor, and bring the catalyst X filled in the reactor into contact with the gaseous compound 1 and the Cl compound 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.

[0043] 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 160° C. or higher), the conversion rate of compound 1 increases. When the reaction temperature is 450° 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.

[0044] The reaction time in the gas phase reaction is preferably from 0.1 to 1000 seconds, more preferably from 0.2 to 800 seconds, and even more preferably from 0.5 to 600 seconds. The reaction time corresponds to the residence time of the raw materials in the reactor, and can be controlled by adjusting the amount (flow rate) of the raw materials fed to the reactor.

[0045] 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.

[0046] The content of the by-product in the product is preferably 40% by mass or less, more preferably 30% by mass or less, and even more preferably 10% 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 having 3 or more carbon atoms produced by the reaction of compound 1 with a Cl compound. 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.

[0047] 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 the Cl compound, 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 Cl compound 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 Cl compound, and the supply line 4 for nitrogen are connected. As a result, a mixture of the compound 1, the Cl compound, and nitrogen is supplied to the reactor 1 via the mixture supply line 5.

[0048] In the reaction apparatus 20 shown in FIG. 1, the supply line 2 for the compound 1, the supply line 3 for the Cl compound, 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, the Cl compound, and the 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, the Cl compound, and the 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.

[0049] 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).

[0050] 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, and Cl compounds. The compounds other than compound 2 contained in the outlet gas also differ depending on the type of Cl compound used. For example, when carbon tetrachloride is used as the Cl compound, compounds contained in the outlet gas other than compound 2 also include carbon tetrachloride, trichlorofluoromethane (CFC-11), dichlorodifluoromethane (CFC-12), and chlorotrifluoromethane (CFC-13). Furthermore, when chloroform is used as the Cl compound, examples of compounds contained in the outlet gas other than compound 2 include chloroform, dichlorofluoromethane (HCFC-21), chlorodifluoromethane (HCFC-22), and trifluoromethane (HFC-23). In addition, when tetrachloroethylene is used as the Cl compound, the compounds contained in the outlet gas other than compound 2 are tetrachloroethylene, trichlorofluoroethylene (CFO-1111), 1,1-dichlorodifluoroethylene (CFO-1112a), 1,2-dichlorodifluoroethylene (CFO-1112), pentachlorofluoroethane (CFC-111), 1,2-tetrachlorodifluoroethane (CFC-112), 1,1-tetrachlorodifluoroethane (CFC-112a) ), 1,1,2-trichlorotrifluoroethane (CFC-113), 1,1,1-trichlorotrifluoroethane (CFC-113a), 1,2-dichlorotetrafluoroethane (CFC-114), 1,1-dichlorotetrafluoroethane (CFC-114a), tetrachlorofluoroethane (HCFC-121), trichlorodifluoroethane (HCFC-122), dichlorotrifluoroethane (HCFC-123), and chlorotetrafluoroethane (HCFC-124). Furthermore, when dichloromethane is used as the Cl compound, compounds other than compound 2 contained in the outlet gas also include chlorofluoromethane (HCFC-31) and difluoromethane (HFC-32).

[0051] 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.

[0052] In the production method of the present invention, when compound 1 is 1,1,2,2,3-pentafluoropropane (HFC-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.

[0053] 245ca can be produced by known methods, for example, by the method described in WO 1994 / 27939.

[0054] 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, 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), chlorotrifluoropropene, dichlorotrifluoropropene, and the compounds listed above depending on the Cl compound used. 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.

[0055] From the standpoint of efficiency in separating 244ca from components other than 244ca after production, it is preferable to use dichloromethane as the Cl compound when producing 244ca by a gas-phase reaction using 245ca as a raw material.

[0056] 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.

[0057] 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.

[0058] 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.

[0059] Furthermore, in the production method of the present invention, when compound 1 is 1,1,2,2,3,3,4,4,5-nonafluoropentane (HFC-449pccc), 5-chloro-1,1,2,2,3,3,4,4-octafluoropentane (HCFC-448occc) is obtained as compound 2. Below, we will explain in detail the case where 449pccc is used as the raw material.

[0060] 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.

[0061] 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.) 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.

[0062] 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.

[0063] 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.

[0064] In the production method of the present invention, when compound 1 is 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorohexane, 6-chloro-1,1,1,2,2,3,3,4,4,5,5,6-dodecafluorohexane and 6,6-dichloro-1,1,1,2,2,3,3,4,4,5,5-undecafluorohexane can be produced as compound 2. As compound 1, a commercially available product (AC-2000, manufactured by AGC Inc.) can be used. The resulting 6-chloro-1,1,1,2,2,3,3,4,4,5,5,6-dodecafluorohexane and 6,6-dichloro-1,1,1,2,2,3,3,4,4,5,5-undecafluorohexane can be separated by known methods. 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 14 and 16 to 18 described below correspond to working examples. Example 15 corresponds to a comparative example.

[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 21.4 mm and a length of 24 cm.

[0068] (Catalyst Preparation Example 1) 109.2 g of chromium zinc composite oxide (PRICAT62-3M, Johnson Matthey) was filled into a 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 volume ppm or less. Thereafter, the reactor was heated to 350°C, and trifluoromethane (HFC-23) was supplied at a flow rate of 75 Nml / min and N2 at a flow rate of 150 NmL / min for 15 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 96.3 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 73.2 g of alumina (N612N, JGC Catalysts and Chemicals) was used instead of the chromium-zinc composite oxide (PRICAT62-3M, Johnson Matthey), to obtain partially fluorinated alumina. The obtained catalyst corresponds to a partial fluoride of a metal oxide.

[0071] (Catalyst Preparation Example 4) 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 104.9 g of the chromium oxide obtained above.

[0072] (Catalyst Preparation Example 5) A reactor was filled with 109.2 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.

[0073] <Example 1> The reactor temperature was set to 175°C while N2 was circulated at a flow rate of 26.2 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 0.313 g / min and carbon tetrachloride was fed to the reactor at a flow rate of 0.180 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 carbon tetrachloride are shown in Table 2. The reaction results shown in Table 2 are for compounds with 3 or more carbon atoms. Carbon tetrachloride, CFC-11, CFC-12, and CFC-13 were observed as compounds with 2 or less carbon atoms contained in the crude gas.

[0074] <Example 2> As shown in Table 2, the products were obtained according to the same procedure as in Example 1, except that the feeding amounts of 245ca and Cl compound were changed.

[0075] <Example 3> As shown in Table 2, products were obtained according to the same procedure as in Example 1, except that the type of Cl compound, the reaction temperature, and the supply amounts of various raw materials were changed. In addition, chloroform, HCFC-21, HCFC-22, and HFC-23 were observed as compounds with carbon numbers of 2 or less contained in the obtained crude gas.

[0076] <Example 4> As shown in Table 2, products were obtained in the same manner as in Example 1, except that the type of Cl compound and the supply amounts of various raw materials were changed. In addition, the following compounds with carbon numbers of 2 or less were observed in the obtained crude gas: tetrachloroethylene, CFO-1111, CFO-1112, CFC-111, CFC-112, CFC-113, CFC-114, HCFC-121, HCFC-122, HCFC-123, and HCFC-124.

[0077] <Example 5> 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.

[0078] <Example 10> As shown in Table 2, the products were obtained according to the same procedure as in Example 1, except that the reaction temperature and the amounts of the various raw materials were changed.

[0079] <Example 11> As shown in Table 2, the products were obtained according to the same procedure as in Example 1, except that the reaction temperature and the amounts of the various raw materials were changed.

[0080] <Example 12> As shown in Table 2, the products were obtained according to the same procedure as in Example 1, except that the type of Cl compound, the reaction temperature, and the amounts of the various raw materials were changed. In addition, dichloromethane, chlorofluoromethane (HCFC-31), and difluoromethane (HFC-32) were observed as compounds with carbon numbers of 2 or less contained in the obtained crude gas.

[0081] <Example 13> 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.

[0082] <Example 14> As shown in Table 2, the products were obtained according to the same procedure as in Example 1, except that the type of catalyst, the reaction temperature, and the amounts of the various raw materials were changed.

[0083] <Example 16> As shown in Table 2, the reaction temperature and the amounts of the various raw materials fed were changed, but the same procedures as in Example 12 were followed to obtain the product.

[0084] <Example 17> As shown in Table 2, the reaction temperature and the amounts of the various raw materials fed were changed, but the same procedures as in Example 12 were followed to obtain the product.

[0085] 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 other selectivity represents the ratio (unit: %) of the molar amount of compounds having 3 or more carbon atoms other than the above components in the product to the molar amount of 245ca consumed in the reaction. In Examples 1 to 5, 12 to 14, and 16 to 17, the reaction pressure (pressure in the reactor) was 0 MPaG, and the residence time was 30 seconds. In Example 10, the reaction pressure (pressure in the reactor) was 0 MPaG, and the residence time was 40 seconds. In Example 11, the reaction pressure (pressure in the reactor) was 0 MPaG, and the residence time was 4 seconds. In Example 6 described later, the reaction pressure (pressure in the reactor) was 0 MPaG, and the residence time was 30 seconds.

[0086] [Table 2]

[0087] As shown in Table 2, according to the production process of the present invention, the conversion rate and selectivity were high, and HCFCs could be produced efficiently. 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 6). However, the conversion rate was lower than that of Example 5, and the selectivity was also somewhat inferior, at about 75%. Comparing Examples 1 to 6, it was confirmed that the catalyst containing Cr was more effective.

[0088] Comparing Example 1 and Example 10, it was confirmed that the conversion rate was better when the reaction temperature was 160° C. or higher. A comparison between Example 1 and Example 14 confirmed that the conversion rate was better when an activation treatment was performed (in other words, when a partial halide of a metal oxide was used).

[0089] <Example 7> The reactor temperature was set to 175°C while N2 was circulated at a flow rate of 26.2 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 0.561 g / min and carbon tetrachloride was fed to the reactor at a flow rate of 0.180 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. Analysis of the crude gas 2 hours after the start of the feed of 449pccc and carbon tetrachloride showed that the conversion of 449pccc was 56.2%, the selectivity of 448occc was 94.1%, 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.

[0090] <Example 8> 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%.

[0091] <Example 9> 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 7 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 layer 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.

[0092] (Catalyst Comparative Preparation Example 1) An activated carbon catalyst (Granular Shirasagi C2x, Osaka Gas Chemicals) was filled into a 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 filled catalyst 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 75 Nml / min and N2 at a flow rate of 150 NmL / min for 15 hours.

[0093] <Example 15> The reactor temperature was set to 175°C while N2 was circulated at a flow rate of 26.2 NmL / min through the reactor containing the catalyst prepared in Catalyst Comparative Preparation Example 1. After the reactor temperature stabilized, 245ca was fed to the reactor at a flow rate of 0.313 g / min and carbon tetrachloride was fed to the reactor at a flow rate of 0.180 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. The conversion rate of 245ca was 1% or less, the selectivity of 244ca was 50% or less, and almost no 244ca was obtained.

[0094] <Example 18> The reactor temperature was set to 350°C while N2 was circulated at a flow rate of 56.0 NmL / min through the reactor containing the catalyst prepared in Catalyst Preparation Example 1. After the reactor temperature stabilized, 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorohexane (HFC-52-13p) was fed to the reactor at a flow rate of 0.401 g / min and carbon tetrachloride was fed to the reactor at a flow rate of 0.193 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 2 hours after the start of the supply of HFC-52-13p and carbon tetrachloride showed that the conversion of HFC-52-13p was 29.3%, the selectivity of 6-chloro-1,1,1,2,2,3,3,4,4,5,5,6-dodecafluorohexane was 69.2%, and the selectivity of 6,6-dichloro-1,1,1,2,2,3,3,4,4,5,5-undecafluorohexane was 17.5%. The conversion rate mentioned above indicates the ratio (unit: %) of the molar amount of HFC-52-13p consumed in the reaction to the molar amount of HFC-52-13p used in the reaction. The 6-chloro-1,1,1,2,2,3,3,4,4,5,5,6-dodecafluorohexane selectivity represents the ratio (unit: %) of the molar amount of 6-chloro-1,1,1,2,2,3,3,4,4,5,5,6-dodecafluorohexane in the product to the molar amount of HFC-52-13p consumed in the reaction. The 6,6-dichloro-1,1,1,2,2,3,3,4,4,5,5-undecafluorohexane selectivity represents the ratio (unit: %) of the molar amount of 6,6-dichloro-1,1,1,2,2,3,3,4,4,5,5-undecafluorohexane in the product to the molar amount of HFC-52-13p consumed in the reaction. As the HFC-52-13p, Asahiklin AC-2000 manufactured by AGC was used. The entire contents of the specification, claims, abstract and drawings of Japanese Patent Application No. 2019-084194, filed on April 25, 2019, are hereby incorporated by reference as the disclosure of the specification of the present invention. [Explanation of symbols]

[0095] 1: Reactor 2: Compound 1 supply line 2a: Preheater 3:Cl compound 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 saturated hydrofluorocarbon having 3 to 8 carbon atoms with a chlorine-containing compound having 1 or 2 carbon atoms in the presence of a catalyst containing a metal compound having at least one metal element selected from Cr and Al, to produce a saturated hydrochlorofluorocarbon having 3 to 8 carbon atoms, The hydrofluorocarbon is a compound represented by formula (1), The hydrochlorofluorocarbon is a compound represented by formula (2), The production method, wherein the chlorine-containing compound is carbon tetrachloride, chloroform, dichloromethane, chlorotrifluoromethane, dichlorodifluoromethane, trichlorofluoromethane, chlorodifluoromethane, dichlorofluoromethane, chlorofluoromethane, 1,1-dichloroethylene, 1,2-dichloroethylene, trichloroethylene, or tetrachloroethylene. Formula (1) Formula (2) X-L-Z X represents -CH a F (3-a). Y represents -CHbF(3-b). Z represents -CHbClcF(3-bc). L represents an alkylene group having 1 to 6 carbon atoms in which at least a portion of hydrogen atoms may be substituted with fluorine atoms. 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 represents 1 or 2; when b is 2, c represents 1.

2. The method according to claim 1 , wherein the metal compound is a metal oxide, a partial halide of a metal oxide, or a metal halide.

3. 3. The method according to claim 1, wherein L is an alkylene group having 1 to 3 carbon atoms in which some hydrogen atoms may be substituted with fluorine atoms.

4. The method according to any one of claims 1 to 3, wherein a is 1, b is 2, and c is 1.

5. The method according to any one of claims 1 to 4, wherein the chlorine-containing compound is carbon tetrachloride, chloroform, dichloromethane, trichloroethylene, or tetrachloroethylene.

6. The method according to any one of claims 1 to 5, wherein the hydrofluorocarbon and the chlorine-containing compound are reacted in a gas phase.

7. The process according to any one of claims 1 to 6, wherein the reaction temperature is from 100 to 450°C.

8. the hydrofluorocarbon is 1,1,2,2,3-pentafluoropropane; The method according to any one of claims 1 to 7, wherein the hydrochlorofluorocarbon is 3-chloro-1,1,2,2-tetrafluoropropane.

9. A method for producing 1-chloro-2,3,3-trifluoropropene, comprising reacting 1,1,2,2,3-pentafluoropropane with a chlorine-containing compound having 1 or 2 carbon atoms in the presence of a catalyst containing a metal compound having at least one metal element selected from Cr and Al 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, The production method, wherein the chlorine-containing compound is carbon tetrachloride, chloroform, dichloromethane, chlorotrifluoromethane, dichlorodifluoromethane, trichlorofluoromethane, chlorodifluoromethane, dichlorofluoromethane, chlorofluoromethane, 1,1-dichloroethylene, 1,2-dichloroethylene, trichloroethylene, or tetrachloroethylene.

10. the hydrofluorocarbon is 1,1,2,2,3,3,4,4,5-nonafluoropentane; The method according to any one of claims 1 to 7, wherein the hydrochlorofluorocarbon is 5-chloro-1,1,2,2,3,3,4,4-octafluoropentane.

11. 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 a chlorine-containing compound having 1 or 2 carbon atoms in the presence of a catalyst containing a metal compound having at least one metal element selected from Cr and Al 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, The production method, wherein the chlorine-containing compound is carbon tetrachloride, chloroform, dichloromethane, chlorotrifluoromethane, dichlorodifluoromethane, trichlorofluoromethane, chlorodifluoromethane, dichlorofluoromethane, chlorofluoromethane, 1,1-dichloroethylene, 1,2-dichloroethylene, trichloroethylene, or tetrachloroethylene.

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