Method for producing trans-1-chloro-3,3,3-trifluoropropene

Abstract

The present invention relates to a method for producing trans-1-chloro-3,3,3-trifluoropropene. The present invention provides a method for efficiently producing 1-chloro-3,3,3-trifluoropropene from a low-reactive intermediate product. A method for producing trans-1-chloro-3,3,3-trifluoropropene is provided, characterized in that a halogenated hydrocarbon compound having 3 carbon atoms represented by the following general formula (1) is reacted with hydrogen fluoride in a gas phase in the presence of a solid catalyst and chlorine gas. C3H X Cl Y F Z (1) (wherein, X is 2 or 3, when X=2, Y is an integer of 1 to 4, and Z is an integer of 0 to 3, satisfying Y+Z=4. When X=3, Y is an integer of 1 to 5, and Z is an integer of 0 to 4, satisfying Y+Z=5. The general formula (1) represents a halogenated hydrocarbon compound having 3 carbon atoms other than trans-1-chloro-3,3,3-trifluoropropene.)

Description

[0001] The present application is a divisional application of an application filed on January 12, 2017, with application number 201780006302.1 and invention name “Method for producing trans-1-chloro-3,3,3-trifluoropropene”. Technical Field

[0002] The present invention relates to a method for producing trans-1-chloro-3,3,3-trifluoropropene from a halogenated hydrocarbon compound having 3 carbon atoms. Background Art

[0003] Trans-1-chloro-3,3,3-trifluoropropene (abbreviation: 1233zd(E)) is a useful compound as a next-generation polyurethane foaming agent, working fluid, refrigerant, etc., and has a low global warming potential (GWP).

[0004] Generally, 1-chloro-3,3,3-trifluoropropene (abbreviation: 1233zd) is produced by fluorinating 1,1,1,3,3-pentachloropropane (abbreviation: 240fa) with hydrogen fluoride or fluorinating 1,1,3,3-tetrachloro-2-propene (abbreviation: 1230za) with hydrogen fluoride using a fluorination catalyst. The fluorination is carried out by a gas phase or liquid phase reaction, and in the case of a liquid phase reaction, it is usually carried out under pressure.

[0005] For example, Patent Document 1 describes a method for obtaining 1-chloro-3,3,3-trifluoropropene (1233zd) by reacting 1,1,1,3,3-pentachloropropane (240fa) with hydrogen fluoride in the presence of a solid fluorination catalyst in a gas phase. Patent Document 2 describes a method for obtaining 1-chloro-3,3,3-trifluoropropene (1233zd) by reacting 1,1,1,3,3-pentachloropropane (240fa) with hydrogen fluoride in the absence of a catalyst. Patent Document 3 describes a method for producing 1-chloro-3,3,3-trifluoropropene (1233zd), comprising reacting 1,1,1,3,3-pentachloropropane (240fa) in a reaction vessel in the presence of a Lewis acid catalyst or a mixture of Lewis acid catalysts at a temperature lower than 150° C. in a liquid phase; continuously taking out hydrogen chloride and 1-chloro-3,3,3-trifluoropropene (1233zd) produced in the reaction vessel; and separating the 1-chloro-3,3,3-trifluoropropene (1233zd).

[0006] Prior art literature

[0007] Patent Literature

[0008] Patent Document 1: Japanese Patent Application Laid-Open No. 9-183740

[0009] Patent Document 2: Japanese Patent Application Laid-Open No. 11-180908

[0010] Patent Document 3: Japanese Patent Application No. 2007-501843 Summary of the invention

[0011] When 1,1,1,3,3-pentachloropropane (240fa) is reacted with hydrogen fluoride to obtain 1-chloro-3,3,3-trifluoropropene (1233zd) by the method of Patent Document 1, it becomes an equilibrium reaction affected by the partial pressure of hydrogen fluoride and hydrogen chloride, and the reaction products include, in addition to 1-chloro-3,3,3-trifluoropropene (1233zd), products such as further fluorinated 1,1,1,3,3-pentafluoropropane (abbreviation: 245fa), and products such as 1,1,3,3-tetrachloro-1-fluoropropane (abbreviation: 241fa) and 1,3,3-trichloro-1,1-difluoropropane (abbreviation: 242fa) having a low degree of fluorination. In particular, in the catalyst-free liquid phase fluorination reaction when producing 1233zd from 240fa, although 1,3,3-trichloro-1,1-difluoropropane (242fa) exists as an intermediate product, it accumulates in the reactor due to the significantly low reaction rate of the fluorination reaction, causing a decrease in productivity.

[0012] In Patent Document 2, when 1233zd and / or 1,3,3,3-tetrafluoropropene (abbreviation: 1234ze) is produced from 240fa by a gas phase fluorination reaction in the absence of a catalyst, heating at a high temperature for a long time is required.

[0013] The present invention solves the above problems and provides a method for efficiently producing trans-1-chloro-3,3,3-trifluoropropene from an intermediate product with low reactivity.

[0014] The present inventors have conducted intensive studies and found that halogenated hydrocarbon compounds such as 1,3,3-trichloro-1,1-difluoropropane, which are produced by the uncatalyzed fluorination reaction of 1,1,1,3,3-pentachloropropane in a liquid phase and have significantly low reactivity, can be effectively converted into trans-1-chloro-3,3,3-trifluoropropene by heating them in a gas phase together with chlorine and hydrogen fluoride in the presence of a solid catalyst. Thus, the method for producing trans-1-chloro-3,3,3-trifluoropropene of the present invention has been completed.

[0015] The applicant has found that trans-1-chloro-3,3,3-trifluoropropene can be produced by reacting a halogenated hydrocarbon compound having three carbon atoms represented by (1) with hydrogen fluoride in the presence of chlorine gas in a gas phase, and has filed an application (PCT / JP2015 / 069784).

[0016] C3H X Cl Y F Z (1)

[0017] (In the formula, X is 2 or 3. When X=2, Y is an integer of 1 to 4, and Z is an integer of 0 to 3, satisfying Y+Z=4. When X=3, Y is an integer of 1 to 5, and Z is an integer of 0 to 4, satisfying Y+Z=5. The general formula (1) above represents a halogenated hydrocarbon compound having 3 carbon atoms, except trans-1-chloro-3,3,3-trifluoropropene.)

[0018] In each of the examples in PCT / JP2015 / 069784, a “catalyst-free reaction” without using a solid catalyst is disclosed. Now, the present inventors have found that the reaction is preferably carried out in the presence of a solid catalyst, and have filed the present application.

[0019] That is, in the method of the present invention, the intermediate product accumulated in the reactor is extracted and efficiently converted into trans-1-chloro-3,3,3-trifluoropropene by a gas-phase solid catalytic fluorination reaction in the presence of chlorine, thereby improving productivity.

[0020] The present invention includes the following inventions 1 to 17.

[0021] "Invention 1"

[0022] A method for producing trans-1-chloro-3,3,3-trifluoropropene, characterized in that a halogenated hydrocarbon compound having three carbon atoms represented by the following general formula (1) is reacted with hydrogen fluoride in a gas phase in the presence of a solid catalyst and chlorine gas.

[0023] C3H X Cl Y F Z (1)

[0024] (In the formula, X is 2 or 3. When X=2, Y is an integer of 1 to 4, and Z is an integer of 0 to 3, satisfying Y+Z=4. When X=3, Y is an integer of 1 to 5, and Z is an integer of 0 to 4, satisfying Y+Z=5. The general formula (1) above represents a halogenated hydrocarbon compound having 3 carbon atoms, except trans-1-chloro-3,3,3-trifluoropropene.)

[0025] "Invention 2"

[0026] The production method according to Invention 1, wherein the solid catalyst is a metal fluoride containing at least one metal selected from the group consisting of aluminum, chromium, titanium, manganese, iron, nickel, cobalt, copper, magnesium, zirconium, molybdenum, zinc, tin, lanthanum, niobium, tantalum and antimony.

[0027] "Invention 3"

[0028] The production method according to any one of Inventions 1 to 2, characterized in that a hydrocarbon compound having 3 carbon atoms represented by the following general formula (2) is further added and reacted with hydrogen fluoride in a gas phase in the presence of chlorine gas.

[0029] C3H V F W (2)

[0030] (In the formula, when V+W=8, V is an integer of 0 to 8; when V+W=6, V is an integer of 0 to 6; when V+W=4, V is an integer of 0 to 4.)

[0031] "Invention 4"

[0032] The production method according to any one of Inventions 1 to 2, characterized in that the halogenated hydrocarbon compound having 3 carbon atoms is selected from 1,1,1,3,3-pentachloropropane (240fa), 1,1,3,3-tetrachloropropene (1230za), 1,3,3,3-tetrachloropropane (1230zd), 1,1,3,3-tetrachloro-1-fluoropropane (241fa), 1,1,1,3-tetrachloro-3-fluoropropane (241fb), 1,3,3-trichloro-3-fluoropropane (241fd), olefins (1231zd), 1,3,3-trichloro-1-fluoropropene (1231zb), 3,3,3-trichloro-1-fluoropropene (1231ze), 1,1,3-trichloro-3-fluoropropene (1231za), 1,3,3-trichloro-1,1-difluoropropane (242fa), 1,1,3-trichloro-1,3-difluoropropane (242fb), 1,1,1-trichloro-3,3-difluoropropane, 1,3-dichloro-3,3-difluoropropene (123 2zd), 3,3-dichloro-1,3-difluoropropene (1232ze), 3,3-dichloro-1,1-difluoropropene (1232zc), 1,3-dichloro-1,3-difluoropropene (1232zb), 1,1-dichloro-3,3-difluoropropane (1232za), cis-1-chloro-3,3,3-trifluoropropene (1233zd(Z)), 3-chloro-1,1,3-trifluoropropene (1233zc), 3-chloro-1,3,3-trifluoropropene At least one of the group consisting of olefin (1233ze), 1-chloro-1,3,3-trifluoropropene (1233zb), 3,3-dichloro-1,1,1-trifluoropropane (243fa), 1,3-dichloro-1,1,3-trifluoropropane (243fb), 1,1-dichloro-1,3,3-trifluoropropane (243fc), 1-chloro-1,1,3,3-tetrafluoropropane (244fb) and 3-chloro-1,1,1,3-tetrafluoropropane (244fa).

[0033] "Invention 5"

[0034] The production method according to any one of Inventions 1 to 2, wherein the reaction temperature is 100° C. or higher and 400° C. or lower.

[0035] "Invention 6"

[0036] A method for producing trans-1-chloro-3,3,3-trifluoropropene, characterized in that at least one halogenated hydrocarbon compound selected from the group consisting of 1,1,3,3-tetrachloro-1-fluoropropane (241fa), 1,1,1,3,3-pentachloropropane (240fa) and 1,3,3-trichloro-1,1-difluoropropane (242fa) is reacted with hydrogen fluoride in a gas phase at a temperature of 100° C. to 400° C. in the presence of a solid catalyst and chlorine gas.

[0037] "Invention 7"

[0038] The production method according to Invention 6 is characterized in that a hydrocarbon compound having 3 carbon atoms represented by the following general formula (2) is further added and reacted.

[0039] C3H V F W (2)

[0040] (In the formula, when V+W=8, V is an integer of 0 to 8; when V+W=6, V is an integer of 0 to 6; when V+W=4, V is an integer of 0 to 4.)

[0041] "Invention 8"

[0042] A method for producing trans-1-chloro-3,3,3-trifluoropropene, characterized in that it comprises:

[0043] Step (A), reacting 1,1,1,3,3-pentachloropropane (240fa) with hydrogen fluoride to obtain an intermediate product; and

[0044] In step (B), the intermediate product obtained in step (A) is reacted with hydrogen fluoride in a gas phase at 100° C. to 400° C. in the presence of a solid catalyst and chlorine gas to obtain trans-1-chloro-3,3,3-trifluoropropene.

[0045] "Invention 9"

[0046] The production method according to Invention 8 is characterized in that the reaction of the step (B) is carried out in the further presence of a hydrocarbon compound having 3 carbon atoms represented by the following general formula (2).

[0047] C3H V F W (2)

[0048] (In the formula, when V+W=8, V is an integer of 0 to 8; when V+W=6, V is an integer of 0 to 6; when V+W=4, V is an integer of 0 to 4.)

[0049] "Invention 10"

[0050] The production method according to Invention 8 is characterized in that the above step (A) is carried out in a liquid phase without a catalyst, and the reaction product gas containing trans-1-chloro-3,3,3-trifluoropropene is recovered.

[0051] The reaction liquid of the step (A) is recovered, and the intermediate product contained in the reaction liquid is used in the step (B).

[0052] "Invention 11"

[0053] The production method according to Invention 10 is characterized in that the 1,1,1,3,3-pentachloropropane and the hydrogen fluoride are introduced continuously or intermittently into the step (A),

[0054] The reaction product gas and the reaction liquid are recovered continuously or intermittently.

[0055] "Invention 12"

[0056] The production method according to Invention 8 is characterized in that the intermediate product is selected from the group consisting of 1,1,3,3-tetrachloro-1-fluoropropane (241fa), 1,1,1,3-tetrachloro-3-fluoropropane (241fb), 1,3,3-trichloro-3-fluoropropene (1231zd), 1,3,3-trichloro-1-fluoropropene (1231zb), 3,3,3-trichloro-1-fluoropropene (1231ze), 1,1,3-trichloro-3-fluoropropene (1231za), 1,3,3-trichloro-1,1-difluoropropane (242fa), 1,1,3-trichloro-1,3-difluoropropane (242fb), 1,3-dichloro-3,3-difluoropropene (123 At least one of the group consisting of 1-chloro-1,3-difluoropropane (244fb) and 3-chloro-1,1,1,3-trifluoropropane (244fa).

[0057] "Invention 13"

[0058] The production method according to Invention 8 is characterized in that the intermediate product contains at least 1,3,3-trichloro-1,1-difluoropropane (242fa).

[0059] "Invention 14"

[0060] The production method according to Invention 8 is characterized in that the reaction temperature in the step (B) is 150° C. or higher and 300° C. or lower.

[0061] "Invention 15"

[0062] The production method according to Invention 8 is characterized in that the unreacted intermediate product is recovered and used in the above-mentioned step (B).

[0063] "Invention 16"

[0064] The production method according to Invention 8 is characterized in that in the step (B), cis-1-chloro-3,3,3-trifluoropropene is obtained together with trans-1-chloro-3,3,3-trifluoropropene.

[0065] "Invention 17"

[0066] The production method according to Invention 16 is characterized in that the obtained cis-1-chloro-3,3,3-trifluoropropene is subjected to the above step (B).

[0067] "Invention 18"

[0068] The production method according to Invention 16 is characterized in that the obtained cis-1-chloro-3,3,3-trifluoropropene is heated at 100° C. to 400° C. to obtain trans-1-chloro-3,3,3-trifluoropropene.

[0069] Effects of the Invention

[0070] In the method for producing trans-1-chloro-3,3,3-trifluoropropene of the present invention, an intermediate product such as 1,3,3-trichloro-1,1-difluoropropane, which has significantly low reactivity in the non-catalyzed fluorination reaction of 1,1,1,3,3-pentachloropropane in a liquid phase, is heated in a gas phase together with chlorine gas and hydrogen fluoride in the presence of a solid catalyst, thereby preventing a decrease in catalytic activity and efficiently producing trans-1-chloro-3,3,3-trifluoropropene.

[0071] Generally, when a halogenated hydrocarbon with a high boiling point, especially a halogenated hydrocarbon with a high degree of chlorination, is subjected to a fluorination reaction in a gas phase in the presence of a solid catalyst, the catalytic activity is reduced due to tar formation, etc., which sometimes causes a reduction in the yield of trans-1-chloro-3,3,3-trifluoropropene (see Comparative Example 1 described later). However, it was found that by conducting a catalytic fluorination reaction in the presence of chlorine gas, the reduction in catalytic activity can be significantly suppressed, and trans-1-chloro-3,3,3-trifluoropropene can be stably produced. BRIEF DESCRIPTION OF THE DRAWINGS

[0072] Figure 1 It is a schematic diagram of a manufacturing apparatus 100 according to one embodiment of the present invention.

[0073] Figure 2 The results of the reaction time change measurement of the captured reaction product by gas chromatography in Example 5. It should be noted that, Figure 2 In the table, "1233E yield (%)" indicates the 1233E concentration (GC area %) in the reaction product.

[0074] Figure 3 This is the result of measuring the reaction time variation of the captured reaction product by gas chromatography in Example 6. It should be noted that, Figure 3 In the table, "1233E yield (%)" indicates the 1233E concentration (GC area %) in the reaction product. DETAILED DESCRIPTION

[0075] The present invention is a method for efficiently producing trans-1-chloro-3,3,3-trifluoropropene (1233zd(E)) from an intermediate product such as 1,3,3-trichloro-1,1-difluoropropane (242fa) having significantly low reactivity in the uncatalyzed fluorination reaction of 1,1,1,3,3-pentachloropropane (240fa) in a liquid phase, but is not limited thereto. That is, the present invention is a method for producing trans-1-chloro-3,3,3-trifluoropropene by using a halogenated hydrocarbon compound having 3 carbon atoms as a raw material and reacting it with hydrogen fluoride in the presence of a solid catalyst and chlorine gas.

[0076] The C3 halogenated hydrocarbon compound used as a raw material in the present invention is a C3 halogenated hydrocarbon compound represented by the following general formula (1).

[0077] C3H X Cl Y F Z (1)

[0078] Here, in the formula, X is 2 or 3, when X=2, Y is an integer of 1 to 4, Z is an integer of 0 to 3, and Y+Z=4 is satisfied. When X=3, Y is an integer of 1 to 5, Z is an integer of 0 to 4, and Y+Z=5 is satisfied. Here, the general formula (1) represents a halogenated hydrocarbon compound having 3 carbon atoms, except trans-1-chloro-3,3,3-trifluoropropene.

[0079] For the halogenated hydrocarbon compound with 3 carbon atoms represented by the general formula (1), when X=2, it is C3H2Cl1F3, C3H2Cl2F2, C3H2Cl3F1, C3H2Cl4; when X=3, it is C3H3Cl1F4, C3H3Cl2F3, C3H3Cl3F2, C3H3Cl4F1, C3H3Cl5.

[0080] The halogenated hydrocarbon compound having 3 carbon atoms used as a raw material in the present invention is specifically selected from 1,1,3,3-tetrachloro-1-fluoropropane (abbreviation: 241fa), 1,1,1,3-tetrachloro-3-fluoropropane (abbreviation: 241fb), 1,3,3-trichloro-3-fluoropropene (abbreviation: 1231zd), 1,3,3-trichloro-1-fluoropropene (abbreviation: 1231zb), 3,3,3-trichloro-1-fluoropropene (abbreviation: 1231ze), 1,1,3-trichloro-3-fluoropropene (abbreviation: 1231za), 1,3,3-trichloro-1,1-difluoropropane (242fa), 1,1,3-trichloro-1,3-difluoropropane (abbreviation: 242fb), 1,3-dichloro-3,3-difluoropropene (abbreviation: 1232 At least one of the group consisting of 3,3-dichloro-1,3-difluoropropene (abbreviation: 1232ze), 3,3-dichloro-1,1-difluoropropene (abbreviation: 1232zc), 1,3-dichloro-1,3-difluoropropene (abbreviation: 1232zb), cis-1-chloro-3,3,3-trifluoropropene (1233zd(Z)), 3,3-dichloro-1,1,1-trifluoropropane (abbreviation: 243fa), 1,3-dichloro-1,1,3-trifluoropropane (abbreviation: 243fb), 1,1-dichloro-1,3,3-trifluoropropane (abbreviation: 243fc), 1-chloro-1,1,3,3-tetrafluoropropane (abbreviation: 244fb) and 3-chloro-1,1,1,3-tetrafluoropropane (abbreviation: 244fa).

[0081] When the uncatalyzed fluorination reaction of 1,1,1,3,3-pentachloropropane in the liquid phase is carried out, a trace amount of trans-1-chloro-3,3,3-trifluoropropene is present in the reaction liquid. However, the reaction of synthesizing trans-1-chloro-3,3,3-trifluoropropene from trans-1-chloro-3,3,3-trifluoropropene itself is not favorable as a production method, and therefore, it is excluded in this specification.

[0082] Along with the halogenated hydrocarbon compound having 3 carbon atoms as the reaction raw material used in the present invention, a hydrocarbon compound having 3 carbon atoms may also be used. The chlorine source such as hydrogen chloride and chlorine radicals generated in the production process of the present invention and derived from the halogenated hydrocarbon compound can also be converted into trans-1-chloro-3,3,3-trifluoropropene by the action of a chlorine source such as hydrogen chloride and chlorine radicals, thereby converting the hydrocarbon compound having 3 carbon atoms into trans-1-chloro-3,3,3-trifluoropropene. The hydrocarbon compound having 3 carbon atoms is represented by the following general formula (2).

[0083] C3H V F W (2)

[0084] (In the formula, when V+W=8, V is an integer of 0 to 8; when V+W=6, V is an integer of 0 to 6; when V+W=4, V is an integer of 0 to 4.)

[0085] For the hydrocarbon compound with 3 carbon atoms represented by general formula (2), when V+W=8, it is C3F8, C3H1F7, C3H2F6, C3H3F5, C3H4F4, C3H5F3, C3H6F2, C3H7F1, and C3H8; when V+W=6, it is C3F6, C3H1F5, C3H2F4, C3H3F3, C3H4F2, C3H5F1, and C3H6; when V+W=4, it is C3F4, C3H1F3, C3H2F2, C3H3F1, and C3H4.

[0086] Specific examples of the hydrocarbon compound having 3 carbon atoms include 1,1,1,3,3-pentafluoropropane (abbreviation: 245fa), trans-1,3,3,3-tetrafluoropropene (abbreviation: 1234ze(E)), cis-1,3,3,3-tetrafluoropropene (abbreviation: 1234ze(Z)), 1,1,3,3-tetrafluoropropene (abbreviation: 1234zc), and 3,3,3-trifluoropropyne.

[0087] The halogenated hydrocarbon compound having 3 carbon atoms as a raw material is not limited to the reaction product produced by the uncatalyzed fluorination reaction of 1,1,1,3,3-pentachloropropane (240fa) in the liquid phase, and may be a substance produced by any method. For example, the following methods may be mentioned: a method of fluorinating 1,1,1,3,3-pentachloropropane and hydrogen fluoride at 250° C. over a fluorinated chromium oxide catalyst (see Japanese Patent Application Laid-Open No. 9-183740); a method of mixing 1,1,1,3,3-pentachloropropane and hydrogen fluoride in a liquid phase at 100 kg / cm 2 (about 10 MPa), 200°C for 5 hours (see Japanese Patent Application Laid-Open No. 11-180908), etc.

[0088] [Solid Catalyst]

[0089] As disclosed in PCT / JP2015 / 069784, the present applicant believes that the reaction of the present invention (the reaction of converting the halogenated hydrocarbon compound having 3 carbon atoms represented by the general formula (1) into trans-1-chloro-3,3,3-trifluoropropene) can be carried out in the gas phase in the presence of chlorine gas, and can also be carried out without a catalyst. However, according to the current findings of the present inventors, by using a solid catalyst, it can be seen that the yield of 1233E at the same temperature tends to increase. As a result, even at a temperature lower than that without a catalyst, it is easy to obtain a 1233E yield equivalent to that of a higher temperature without a catalyst. The fluorination reaction of the present invention requires the coexistence of chlorine gas, and therefore sometimes causes a load on the reactor. That is, the reaction temperature can be lowered by using a solid catalyst, which has great technical significance. The "solid catalyst" used in the present invention is described in detail below.

[0090] The solid catalyst used in the present invention may be any one that can generate trans-1-chloro-3,3,3-trifluoropropene by contacting a halogenated hydrocarbon compound having three carbon atoms with the catalyst together with chlorine gas and hydrogen fluoride in a gas phase, and any one generally known as a solid catalyst (heterogeneous catalyst) may be used.

[0091] Specifically, metal compounds (metal oxides, metal fluorides, partially fluorinated metal oxides, metal complexes, etc.), activated carbon, etc. are solid catalysts that can be used in the present invention.

[0092] Among them, metal compounds are preferred, and metal oxides, metal fluorides, and "partially fluorinated metal oxides (sometimes also simply referred to as "fluorinated metal oxides")" are particularly preferred.

[0093] It should be noted that if the gas phase fluorination reaction of the present invention is carried out in the presence of a metal oxide as a solid catalyst, the metal oxide contacts HF, thereby gradually performing fluorine substitution. Specifically, when a reactor is filled with a metal oxide such as aluminum oxide or chromium oxide as a solid catalyst and HF is circulated, the oxygen atoms constituting these metal oxides are slowly replaced by fluorine atoms to form so-called "partially fluorinated metal oxides ("fluorinated aluminum oxide" and "fluorinated chromium oxide" are suitable examples thereof)". If fluorination is further carried out, it is close to a "metal fluoride" in which all oxygen is replaced by fluorine. The so-called "solid catalyst" in the present invention can be such a "metal oxide", "metal fluoride" or "partially fluorinated metal oxide (fluorinated metal oxide)".

[0094] In particular, the catalytic activity of the method of carrying out the reaction of the present invention after temporarily circulating a predetermined amount of HF at a predetermined temperature is mostly stable compared to carrying out the reaction of the present invention immediately after filling the "metal oxide". Therefore, it is believed that the "partially fluorinated metal oxide (fluorinated metal oxide)" generated in the system (by contact with HF) is one of the particularly preferred substances as the solid catalyst of the present invention.

[0095] The type of metal contained in these metal compounds is not particularly limited, and at least one metal selected from the group consisting of aluminum, chromium, manganese, zirconium, titanium and magnesium is particularly preferred. The metal may be used alone or in combination of two or more metals.

[0096] As a catalyst using two or more metals in combination, it is particularly preferred to contain one metal selected from the group consisting of aluminum, chromium, manganese, zirconium, titanium and magnesium as a main component, and further contain at least one metal selected from the group consisting of aluminum, chromium, titanium, manganese, iron, nickel, copper, cobalt, magnesium, zirconium, molybdenum, niobium, tantalum and antimony as a subcomponent (wherein the metals of the main component and the subcomponent are different).

[0097] The catalysts using two or more metals in combination include the following, all of which can be applied:

[0098] Form (a), a metal material containing multiple metal substances is filled into a reactor and used as a "solid catalyst" as a whole;

[0099] Form (b), a solution (aqueous solution, etc.) containing a second (and further third and subsequent) metal is impregnated into a metal material containing a first metal, and the second (and further third and subsequent) metal is supported on the metal material containing the first metal, and the reactor is filled with the second (and further third and subsequent) metal;

[0100] In form (c), a "metal-free solid catalyst" such as activated carbon is used as a carrier, and an aqueous solution containing a plurality of metals is impregnated therein.

[0101] Among these, (a) and (b) are described below.

[0102] As the form of (a), the metal itself can be alloyed and then oxidized or fluorinated at the same time. However, such alloying treatment is not necessary, and for example, a mixture of aluminum oxide and chromium oxide, aluminum oxide and zirconium oxide, aluminum oxide and titanium oxide, or aluminum oxide and magnesium oxide (including a mixture further fluorinated) can also be used as the form of (a).

[0103] On the other hand, (b) is a simple method for adding a second (and, depending on the situation, a third or fourth) metal as a secondary component to an oxide or fluoride of a first metal as a primary component, and the "second (and, depending on the situation, a third or fourth) metal" is also referred to as a "supported catalyst" in the same sense as a catalyst supported on the "first metal". As the form of (b), as shown in the examples described later, the catalytic activity of "alumina catalyst supported with chromium" and "partially fluorinated alumina catalyst supported with chromium" is particularly stable, and the halogenated hydrocarbon compound having 3 carbon atoms represented by formula (1) can be smoothly converted into the target trans-1-chloro-3,3,3-trifluoropropene, so it is particularly preferred.

[0104] When using multiple metals as solid catalysts, the above (a) and (b) are preferably composed mainly of aluminum. Specifically, when the metal component contains more than 50 atomic % of aluminum, the fluorination reaction can be carried out at a good conversion rate, so it is particularly preferred. It is further preferred to contain more than 80 atomic % of aluminum. It should be noted that the metal component may be a single component (such as aluminum), but when 0.1 to 20 atomic % of metals are used in combination as secondary components, the catalytic activity is sometimes further improved (refer to the examples described later). The combined use of metals containing 90 to 99 atomic % of aluminum and 1 to 10 atomic % of chromium is a particularly preferred example.

[0105] The "metal oxide" used as the solid catalyst of the present invention or as the raw material of the "partially fluorinated metal oxide" or "metal fluoride" may take more than one crystal form. For example, alumina has γ-alumina and α-alumina, and titanium oxide has anatase and rutile crystal forms. The crystal form of the metal oxide is any, and among alumina, γ-alumina is preferred because of its large surface area.

[0106] As mentioned above, as the solid catalyst of the present invention, "partially fluorinated metal oxide (fluorinated metal oxide)" is particularly preferred. The preparation method of such "partially fluorinated metal oxide (fluorinated metal oxide)" and the "metal fluoride" generated by further fluorination thereof is not particularly limited. For example, it can be carried out by contacting a fluorinating agent such as hydrogen fluoride, fluorinated hydrocarbons, fluorinated chlorinated hydrocarbons with the aforementioned "metal oxide (including oxides of multiple metals)". The fluorination treatment is usually preferably carried out in stages. That is, when solid catalysts such as metal oxides are fluorinated with hydrogen fluoride, it is accompanied by a large release of heat. Therefore, it is preferably carried out at a relatively low temperature using an initially diluted hydrofluoric acid aqueous solution or hydrogen fluoride gas while slowly increasing the concentration and / or temperature. The final stage is preferably carried out at a temperature above the "fluorination reaction of a halogenated hydrocarbon compound having 3 carbon atoms represented by formula (1)"). On the basis of this condition, in order to carry out the reaction more stably, the fluorination treatment of the catalyst is carried out at a temperature above 100°C, preferably above 200°C, and more preferably above 300°C with hydrogen fluoride. The upper limit of the temperature is not particularly limited, but if it exceeds 900°C, it is difficult from the viewpoint of the heat resistance of the fluorination treatment apparatus, and it is practically preferably performed at 600°C or lower.

[0107] The catalysts such as metal oxides and metal fluorides used in the present invention are particularly preferably subjected to fluoridation treatment using a fluoriding agent such as HF just before use. The fluoridation treatment can be carried out according to the examples of the preparation methods of the above-mentioned metal fluorides and partially fluorinated metal oxides. Even in the case where the preparation of metal fluorides and partially fluorinated metal oxides is carried out in advance using the above-mentioned method, it is particularly preferred to carry out fluoridation treatment again at a prescribed temperature or above before use so that the fluoridation reaction of the target carbon number 3 halogenated hydrocarbon compound is carried out stably. When the fluoridation treatment is carried out in the same reactor after the solid catalyst is filled in the reactor of the fluoridation reaction of the present invention and during the period from the start of the target reaction, it is simple and effective, so it is particularly preferred.

[0108] [About supported catalyst]

[0109] As the solid catalyst of the present invention, a supported catalyst in which a metal compound is supported on a carrier (corresponding to the above (b) and (c)) is particularly preferred. Hereinafter, the "supported catalyst" will be described in detail even if there are overlaps with the above description.

[0110] As a carrier of a supported catalyst, in addition to carbon (activated carbon, etc.), the above-mentioned metal (including composite metal) compounds can be used. When a metal compound is used as a carrier, it is suitable to use the above-mentioned metal oxide, and then to fluorinate it to obtain a "metal fluoride" or "partially fluorinated metal oxide". Specifically, an oxide, fluoride, or partially fluorinated metal oxide of at least one metal selected from the group consisting of aluminum, chromium, manganese, zirconium, titanium and magnesium can be used as a carrier.

[0111] As the carrier, oxides of various metals may also be used. For example, oxides containing one metal selected from the group consisting of aluminum, chromium, manganese, zirconium, titanium and magnesium as a main component and at least one metal selected from the group consisting of aluminum, chromium, titanium, manganese, iron, nickel, copper, cobalt, magnesium, zirconium, molybdenum, niobium, tantalum and antimony as a secondary component are preferred.

[0112] In particular, a "supported catalyst" is a catalyst that can impregnate a "metal solution" into a carrier. That is, when a "supported catalyst" is a "metal compound" as a "carrier" and a metal compound different therefrom is used as a "supported metal compound (also referred to as a "support" in this specification)", it itself plays the role of "combination of multiple metals". In such a case, the necessity of intentionally using a combination of multiple metals in a "carrier" is not necessarily high. However, according to the expectations of those skilled in the art, it is not excluded to select such a form.

[0113] On the other hand, as the metal contained in the "metal compound (support) of the load", aluminum, chromium, titanium, manganese, iron, nickel, cobalt, copper, magnesium, zirconium, molybdenum, zinc, tin, lanthanum, niobium, tantalum, antimony, etc. can be cited. Among them, aluminum, chromium, titanium, iron, nickel, cobalt, copper, zirconium, zinc, tin, lanthanum, niobium, tantalum, antimony, etc. are preferred. These metals are loaded in the form of fluoride, chloride, fluoride chloride, oxyfluoride, oxychloride, oxyfluoride chloride, etc. The metal compound can be loaded alone or in combination with more than two loads. It should be noted that "loaded catalyst" is a catalyst that makes the solution of the loaded metal infiltrate the carrier to play the composite of the metal. Therefore, as a principle, as a "metal compound (support) of the load", a compound different from the "carrier" is used.

[0114] As a supported material, specifically, chromium nitrate, chromium trichloride, potassium dichromate, titanium tetrachloride, manganese nitrate, manganese chloride, ferric chloride, nickel nitrate, nickel chloride, cobalt nitrate, cobalt chloride, antimony pentachloride, magnesium chloride, magnesium nitrate, zirconium chloride, zirconium oxychloride, zirconium nitrate, copper chloride (II), zinc chloride (II), lanthanum nitrate, tin tetrachloride, etc. can be used, but are not limited to these. Preferably, they are in the form of a solution (usually an aqueous solution) in contact with the above-mentioned carrier, the metal compound is impregnated in the carrier, and then heated to evaporate water and fixed on the carrier (with reference to Preparation Example 3 described later). It should be noted that the metal chlorides that are liquid at room temperature such as titanium tetrachloride, antimony pentachloride, tin tetrachloride are not loaded in the form of a solution, but are directly loaded in the form of a stock solution.

[0115] The catalyst prepared by supporting the above-mentioned metal compound on a carrier may be subjected to fluorination treatment before use in order to stably carry out the reaction, and it is preferred to do so. That is, like other solid catalysts, it is preferred to treat it with a fluorinating agent such as hydrogen fluoride, fluorinated hydrocarbon, fluorinated chlorinated hydrocarbon, etc. at a temperature above the prescribed reaction temperature before use.

[0116] As the catalyst for the fluorination reaction of the present invention, chromium fluoride-supported alumina, fluorinated alumina, and chromium-supported activated carbon can be cited as preferred specific examples, and chromium fluoride-supported alumina and fluorinated alumina are particularly preferred. These catalysts are preferably fluorinated in advance with a fluorinating agent such as HF before the reaction.

[0117] The mass of the metal is 0.1 to 80 mass %, preferably 1 to 50 mass % relative to the total mass of the catalyst including the carrier and the supported material. If it is 0.1 mass % or more, a good catalytic effect can be obtained, and if it is 80 mass % or less, it can be stably supported. It should be noted that when the supported material is a solid metal salt, the mass of the metal is 0.1 to 40 mass %, preferably 1 to 30 mass % relative to the total mass of the catalyst.

[0118] [Production process of trans-1-chloro-3,3,3-trifluoropropene]

[0119] The molar ratio of the halogenated hydrocarbon compound with a carbon number of 3 to the hydrogen fluoride supplied to the reaction zone in this reaction step may be changed according to the reaction temperature, and is 1 / 1 to 1 / 20, preferably 1 / 1 to 1 / 10. When the hydrogen fluoride exceeds 20 mole times of the halogenated hydrocarbon compound with a carbon number of 3, it may cause a decrease in the amount of organic matter treated in the same reactor and an obstacle in separating the mixture of unreacted hydrogen fluoride and the product discharged from the reaction system. On the other hand, when the hydrogen fluoride is less than 1 mole time, the reaction rate decreases and the selectivity decreases, so it is not preferred.

[0120] The molar ratio of the halogenated hydrocarbon compound with 3 carbon atoms / chlorine gas supplied to the reaction zone may vary depending on the reaction temperature, and is 1 / 0.001 to 1 / 0.5, preferably 1 / 0.01 to 1 / 0.1, and most preferably 1 / 0.01 to 1 / 0.05. When the chlorine gas exceeds 0.5 mole times of the halogenated hydrocarbon compound with 3 carbon atoms, the generation of high chlorides increases, so it is not preferred. On the other hand, when the chlorine gas is less than 0.001 mole times, the reaction rate decreases and the conversion rate decreases, so it is not preferred.

[0121] Unreacted hydrogen fluoride can be separated from the unreacted organic matter and the reaction product and reused in the reaction system. The separation of hydrogen fluoride and the organic matter can be carried out by a known means.

[0122] The temperature for carrying out the reaction of the present invention is not particularly limited, and is 100°C to 500°C, preferably 150°C to 400°C, and more preferably 150°C to 300°C. When the reaction temperature is lower than 100°C, the reaction is slow and impractical. On the other hand, when the reaction temperature exceeds 500°C, the generation of tar and decomposition products increases, so it is not preferred. It should be noted that, as mentioned above, in the present invention, due to the use of a solid catalyst, compared with the case without a catalyst, even at a lower temperature (specifically, a temperature below 300°C), the yield of 1233E is high compared to "the case of a temperature higher than 300°C", and it is not inferior. As a result, the load on the reactor is correspondingly less, and in most cases the energy consumption is also less, which can be a major advantage of the present invention.

[0123] In the reaction of the present invention, the halogenated hydrocarbon compound having three carbon atoms supplied to the reaction zone may be supplied together with a diluent gas such as nitrogen, helium, argon, etc. which does not participate in the reaction.

[0124] Such gas is preferably 10 mol or less, based on a ratio of 100 mol or less per 1 mol of the halogenated hydrocarbon compound having 3 carbon atoms. However, the reaction of the present invention is carried out in the gas phase, and therefore, when the gas not participating in the reaction is supplied, the raw material is diluted and the productivity is reduced accordingly.

[0125] Furthermore, it has been determined that even if the reaction of the present invention is carried out in the absence of such a diluent gas, the selectivity is unlikely to be adversely affected. Therefore, it is usually preferred not to use a diluent gas.

[0126] The reaction of the present invention is not particularly limited to pressure. It can be carried out at normal pressure, that is, without pressure adjustment such as pressurization or decompression. From the perspective of the apparatus, it is preferably carried out at 0.01 to 1 MPa (expressed in the form of absolute pressure in this specification, and the same applies hereinafter).

[0127] When pressurizing, the balance sometimes tends to the direction in which the addition reaction proceeds undesirably, therefore, it is necessary to be careful. On the other hand, the reaction of the present invention can also be carried out under reduced pressure. When determining the pressure, it is desirable to select a condition in which organic substances such as raw materials present in the system do not liquefy in the reaction system.

[0128] The contact time (reaction time) of the reaction of the present invention is usually 1 to 500 seconds, preferably 10 to 300 seconds under standard conditions (0°C, 1 atm). If the contact time is short, the reaction rate decreases, and if the contact time is too long, side reactions may occur, which is not preferred.

[0129] The reaction of the present invention is carried out by adjusting the temperature and introducing a halogenated hydrocarbon compound having a carbon number of 3, hydrogen fluoride and chlorine gas into a reactor substantially at the same time. The reactor used is generally a tubular reactor made of stainless steel, Hastelloy (TM), Monel (TM), platinum, carbon, fluororesin or a material lined with these substances.

[0130] It should be noted that in the present invention, as the halogenated hydrocarbon compound having 3 carbon atoms, at least one selected from the group consisting of 1,1,3,3-tetrachloro-1-fluoropropane (241fa), 1,1,1,3,3-pentachloropropane (240fa), and 1,3,3-trichloro-1,1-difluoropropane (242fa) is preferred. When these halogenated hydrocarbon compounds having 3 carbon atoms are used as raw material organic substances, they are reacted with hydrogen fluoride in a gas phase in the presence of a solid catalyst and in the presence of chlorine at a predetermined reaction temperature to produce trans-1-chloro-3,3,3-trifluoropropene.

[0131] [Method for producing trans-1-chloro-3,3,3-trifluoropropene using 1,1,1,3,3-pentachloropropane as a starting material]

[0132] A method for producing trans-1-chloro-3,3,3-trifluoropropene using 1,1,1,3,3-pentachloropropane (240fa) as a raw material organic substance is described. The production method of one embodiment of the present invention includes the following steps: step (A), reacting 1,1,1,3,3-pentachloropropane (240fa) with hydrogen fluoride; step (B), reacting the intermediate product obtained in step (A) with hydrogen fluoride in a gas phase in the presence of a solid catalyst and chlorine gas to obtain trans-1-chloro-3,3,3-trifluoropropene.

[0133] Figure 1Schematic diagram of a manufacturing apparatus 100 according to an embodiment. The manufacturing apparatus 100 includes, for example, a liquid phase reaction tank 10, a condenser 30, a tank 50, a tank 70, and a gas phase reaction tower 90, but is not limited thereto. The liquid phase reaction tank 10 is, for example, a stainless steel autoclave, and the raw material organic matter is supplied from a pipe 11 via a valve 1. In addition, hydrogen fluoride is supplied to the liquid phase reaction tank 10 from a pipe 13 via a valve 2. Figure 1 In the embodiment, the raw material organic matter and hydrogen fluoride are supplied from different pipes, but they may be supplied to the liquid phase reaction tank 10 from one pipe or supplied to the liquid phase reaction tank 10 as a mixture.

[0134] The pipe 15 is connected to the upper part of the liquid phase reaction tank 10 and is connected to the condenser 30. The pipe 31 is connected to the condenser 30 and is connected to the tank 50 via the valve 3. The tank 50 stores trans-1-chloro-3,3,3-trifluoropropene liquefied in the condenser 30. In addition, the pipe 17 is connected to the bottom of the liquid phase reaction tank 10 and is connected to the tank 70 via the valve 4. The tank 70 stores the reaction liquid containing the intermediate product generated in the liquid phase reaction tank 10.

[0135] The pipe 71 connected to the tank 70 is connected to the gas phase reaction tower 90 via the valve 5. The pipe 91 is connected to the gas phase reaction tower 90 via the valve 6 to supply chlorine gas to the gas phase reaction tower 90. In addition, the pipe 93 is connected to the gas phase reaction tower 90 via the valve 7 to supply hydrogen fluoride to the gas phase reaction tower 90. The gas phase reaction tower 90 is filled with a "solid catalyst". It should be noted that Figure 1 In the example in which chlorine gas and hydrogen fluoride are supplied from different pipes, they may be supplied from one pipe to the gas phase reaction tower 90 separately or supplied as a mixture to the gas phase reaction tower 90 .

[0136] The pipe 95 connected to the upper part of the gas phase reaction tower 90 is connected to the condenser 35 via the valve 8. The condenser 35 is connected to the tank 50 via the pipe 36. The tank 50 stores the trans-1-chloro-3,3,3-trifluoropropene liquefied in the condenser 35. It should be noted that Figure 1 In FIG. 1 , trans-1-chloro-3,3,3-trifluoropropene produced in two systems is stored in a common tank 50 , but the trans-1-chloro-3,3,3-trifluoropropene may be stored in different tanks.

[0137] The production method of one embodiment of the present invention may include: step (A) of reacting 1,1,1,3,3-pentachloropropane (240fa) with hydrogen fluoride in a liquid phase reaction tank 10; and step (B) of introducing the intermediate product obtained in step (A) into a gas phase reaction tower 90, reacting it with hydrogen fluoride in a gas phase in the presence of a solid catalyst and chlorine to obtain trans-1-chloro-3,3,3-trifluoropropene. The reaction product gas containing trans-1-chloro-3,3,3-trifluoropropene generated in the liquid phase reaction tank 10 is extracted from the liquid phase reaction tank 10 via a pipe 15, liquefied in a condenser 30, and recovered to a tank 50. It should be noted that the introduction of 1,1,1,3,3-pentachloropropane (240fa) and hydrogen fluoride can be carried out continuously or intermittently by opening and closing a valve 3. The recovery of trans-1-chloro-3,3,3-trifluoropropene may be performed continuously or intermittently by opening and closing the valve 3 .

[0138] On the other hand, the reaction liquid containing the intermediate product generated in the liquid phase reaction tank 10 is recovered to the tank 70 via the pipe 17. The reaction liquid stored in the tank 70 is supplied to the gas phase reaction tower 90 via the pipe 71. In the gas phase reaction tower 90, in the presence of a solid catalyst and chlorine, the intermediate product (the aforementioned halogenated hydrocarbon compound with a carbon number of 3) contained in the reaction liquid reacts with hydrogen fluoride in the gas phase to generate trans-1-chloro-3,3,3-trifluoropropene. At this time, the aforementioned hydrocarbon compound with a carbon number of 3 can be further added to the reaction liquid stored in the tank 70 as a reaction raw material, and reacted with hydrogen fluoride in the gas phase reaction tower 90. The reaction product gas containing trans-1-chloro-3,3,3-trifluoropropene generated in the gas phase reaction tower 90 is extracted from the gas phase reaction tower 90 via the pipe 95, liquefied in the condenser 35, and recovered to the tank 50 via the pipe 36.

[0139] The method for reacting 1,1,1,3,3-pentachloropropane with hydrogen fluoride is not limited to the above-mentioned one embodiment, and a conventionally known method may be adopted. For example, a method for reacting them in a gas phase (for example, see Japanese Patent Application Laid-Open No. 9-183740); a method for reacting them in a liquid phase (for example, see Japanese Patent Application Laid-Open No. 11-180908), etc. may be mentioned, but the method is not limited to these.

[0140] Trans-1-chloro-3,3,3-trifluoropropane can be produced by reacting the intermediate product obtained by reacting 1,1,1,3,3-pentachloropropane with hydrogen fluoride in the presence of chlorine gas in the gas phase. Here, the method of reacting the intermediate product with hydrogen fluoride in the presence of a solid catalyst and chlorine gas in the gas phase can be described based on the method of reacting the aforementioned halogenated hydrocarbon compound having 3 carbon atoms with hydrogen fluoride in the presence of a solid catalyst and chlorine gas in the gas phase. That is, the description can be made by replacing "halogenated hydrocarbon compound having 3 carbon atoms" with "intermediate product".

[0141] In the reaction mixture obtained by the reaction of step (B), in addition to the trans-1-chloro-3,3,3-trifluoropropene of the target, unreacted aforementioned intermediate products and reaction byproducts are sometimes included. They can be taken out and supplied to the reaction system of step (B), and then reacted. Thus, the trans-1-chloro-3,3,3-trifluoropropene of the target can be efficiently manufactured.

[0142] The method for separating trans-1-chloro-3,3,3-trifluoropropene from the reaction mixture is not particularly limited. The separation can be carried out, for example, by distillation. In addition, in order to facilitate separation, the acid component that may be contained in the reaction mixture can be removed by methods such as water washing as needed.

[0143] By the reaction of step (B), the target trans-1-chloro-3,3,3-trifluoropropene is obtained, but cis-1-chloro-3,3,3-trifluoropropene is also produced at the same time. At this time, cis-1-chloro-3,3,3-trifluoropropene can be taken out from the reaction mixture and supplied to the reaction system of step (B) as described above to further react, or it can be heated at 150° C. to 600° C. to isomerize to produce trans-1-chloro-3,3,3-trifluoropropene.

[0144] In the method of the present invention, when a fluorination reaction is carried out in a gas phase in the presence of a solid catalyst, the catalytic activity is reduced due to tar formation, etc., for a halogenated hydrocarbon with a high boiling point, especially a halogenated hydrocarbon with a high degree of chlorination, and sometimes the yield of trans-1-chloro-3,3,3-trifluoropropene is reduced (see Comparative Example 1 described later). However, by carrying out the reaction in the presence of chlorine gas, the reduction in catalytic activity can be significantly suppressed, and it has been established as an industrial production method.

[0145] According to the present invention, low-reactive intermediates are also consumed efficiently, and trans-1-chloro-3,3,3-trifluoropropene can be efficiently synthesized using 1,1,1,3,3-pentachloropropane (240fa) as a starting material.

[0146] Example

[0147] The method for producing trans-1-chloro-3,3,3-trifluoropropene of the present invention will be described based on the following examples, but the present invention is not limited to the following examples.

[0148] [Preparation Example 1]

[0149] In a 2000 ml stainless steel autoclave equipped with a condenser through which a 100° C. coolant circulates, 4.1 g / min of 1,1,1,3,3-pentachloropropane (240fa) and 3.8 g / min of hydrogen fluoride (molar ratio: 240fa / hydrogen fluoride = 1 / 10) were introduced, and the autoclave was heated to 150° C. When the pressure exceeded 4 MPa, the reaction product gas containing 1233E as the main component was extracted from the needle valve at the outlet of the condenser in such a manner as to maintain 4 MPa. The extracted gas was passed through a fluororesin gas purge bottle containing ice water cooled in an ice water bath to absorb the acid, and then recovered as reaction product organic matter in a glass trap in a dry ice acetone bath.

[0150] When the liquid volume in the autoclave reaches 1000 ml, a needle valve is passed through the immersion tube to maintain 1000 ml, and the reaction liquid is extracted. The extracted reaction liquid is recovered in a fluororesin gas purge bottle containing ice water cooled in an ice water bath. After the reaction is continued for 24 hours, all the reaction liquid in the autoclave is recovered in a fluororesin gas purge bottle containing ice water. The total amount of reaction-generated organic matter recovered from the condenser outlet is 2952 g, and the total amount of reaction liquid extracted from the immersion tube is 1879 g. The same reaction is then carried out 9 times, and a total of 19.1 kg of reaction liquid is recovered. The reaction liquid is distilled in a glass distillation tower, and 10.9 kg of the fraction at 100°C to 145°C is recovered. The results of gas chromatography analysis are shown in Table 1.

[0151] In Table 1, 1233E represents trans-1-chloro-3,3,3-trifluoropropene (1233zd(E)), and 1233Z represents cis-1-chloro-3,3,3-trifluoropropene (1233zd(Z)).

[0152] The "fraction" obtained in Preparation Example 1 was used as a raw material (a liquid composition containing a halogenated hydrocarbon compound having 3 carbon atoms) in Examples 1 to 6 and Comparative Example 1 described below.

[0153] [Table 1]

[0154]

[0155] Note: In addition to the compounds listed in the table, the reaction solution and fractions contain a number of trace intermediates.

[0156] nd: indicates GC area % less than 0.01%.

[0157] [Preparation Example 2] Preparation of fluorinated alumina catalyst

[0158] A cylindrical stainless steel (SUS316L) reaction tube with a diameter of 2.7 cm and a length of 40 cm equipped with an electric furnace was filled with 130 ml of granular γ-alumina (KHS-46 manufactured by Sumika Alchem ​​Co., Ltd.), and the temperature was raised to 200° C. while nitrogen gas was flowing. When no water was seen to flow out, hydrogen fluoride (HF) was added to the nitrogen gas to slowly increase its concentration. When the hot spot generated by the fluorination of the filled alumina reached the outlet end of the reaction tube, the reactor temperature was raised stepwise by 100° C., and each step temperature was maintained for 1 hour, and finally raised to 400° C., and this state was maintained for 1 hour to perform a fluorination treatment of the catalyst, thereby preparing a fluorinated alumina catalyst.

[0159] [Preparation Example 3] Preparation of chromium-supported fluorinated alumina catalyst

[0160] A 20 mass % chromium chloride aqueous solution was prepared in a conical flask, and 130 ml of the fluorinated alumina prepared in Preparation Example 2 was impregnated for 3 hours. The fluorinated alumina was filtered and dried at 70° C. under reduced pressure using a rotary evaporator to obtain a chromium-supported fluorinated alumina catalyst.

[0161] 130 ml of the above-mentioned chromium-supported fluorinated alumina catalyst was filled in a cylindrical stainless steel (SUS316L) reaction tube with a diameter of 2.7 cm and a length of 40 cm equipped with an electric furnace, and the temperature was raised to 200° C. while nitrogen gas was flowing. When no water was seen to flow out, hydrogen fluoride (HF) was added to the nitrogen gas to slowly increase its concentration. When the hot spot generated by the fluorination of the filling reached the outlet end of the reaction tube, the reactor temperature was raised stepwise by 100° C. for 1 hour, and finally maintained at 400° C. for 1 hour to perform a fluorination treatment of the supported catalyst, thereby performing a treatment to improve the activity of the chromium-supported fluorinated alumina catalyst).

[0162] [Example 1]

[0163] A cylindrical stainless steel (SUS316L) reaction tube with an inner diameter of 2.7 cm and a length of 40 cm equipped with an electric furnace was filled with 130 ml of the chromium-supported fluorinated alumina catalyst prepared in Preparation Example 3, and the temperature was raised while nitrogen gas was flowing at a rate of 10 ml / min. When the temperature of the reaction tube reached 150° C., the vaporized fraction of Preparation Example 1 (liquid composition containing a halogenated hydrocarbon compound having 3 carbon atoms) as a reaction raw material was supplied at a flow rate of 0.30 g / min, hydrogen fluoride: 0.10 g / min, and chlorine gas: 1.0 ml / min (molar ratio: halogenated hydrocarbon compound having 3 carbon atoms / hydrogen fluoride / chlorine gas=1 / 3.28 / 0.028, contact time: 51 seconds), and the supply of nitrogen gas was stopped when the flow rate was stable.

[0164] The number of moles of the "halogenated hydrocarbon compound having 3 carbon atoms" is a value obtained by calculating the molar amount from the GC% of the gas chromatography analysis result and adding them together.

[0165] The generated gas flowing out of the reactor was passed through a fluororesin gas cleaning bottle containing ice water cooled in an ice water bath, unreacted hydrogen fluoride and hydrogen chloride were absorbed, and the reaction product was collected. The results of gas chromatography analysis of the collected reaction product are shown in Table 3. In Table 3, 1234E represents trans-1,3,3,3-tetrafluoropropene (1234ze (E)), 1234Z represents cis-1,3,3,3-tetrafluoropropene (1234ze (Z)), 1233E represents trans-1-chloro-3,3,3-trifluoropropene (1233zd (E)), and 1233Z represents cis-1-chloro-3,3,3-trifluoropropene (1233zd (Z)).

[0166] [Example 2]

[0167] When the temperature of the reaction tube reached 200° C., the reaction was carried out in the same manner as in Example 1 except that the vaporized fraction of Preparation Example 1 (liquid composition containing a halogenated hydrocarbon compound having 3 carbon atoms) as a reaction raw material was supplied at flow rates of 0.39 g / min, hydrogen fluoride: 0.09 g / min, and chlorine gas: 1.0 ml / min (molar ratio: halogenated hydrocarbon compound having 3 carbon atoms / hydrogen fluoride / chlorine gas=1 / 2.23 / 0.022, contact time: 52 seconds). The results are shown in Table 3.

[0168] [Example 3]

[0169] When the temperature of the reaction tube reached 250°C, the reaction was carried out in the same manner as in Example 1 except that the vaporized fraction of Preparation Example 1 (halogenated hydrocarbon compound having 3 carbon atoms) as the reaction raw materials was supplied at flow rates of 0.25 g / min, hydrogen fluoride: 0.06 g / min, and chlorine: 1.0 ml / min (molar ratio: halogenated hydrocarbon compound having 3 carbon atoms / hydrogen fluoride / chlorine gas = 1 / 2.26 / 0.033, contact time: 80 seconds).

[0170] The results are shown in Table 3.

[0171] [Example 4]

[0172] When the temperature of the reaction tube reached 300° C., the reaction was carried out in the same manner as in Example 1 except that the vaporized fraction of Preparation Example 1 (halogenated hydrocarbon compound having 3 carbon atoms) as the reaction raw material was supplied at flow rates of 0.26 g / min, hydrogen fluoride: 0.07 g / min, and chlorine gas: 1.0 ml / min (molar ratio: halogenated hydrocarbon compound having 3 carbon atoms / hydrogen fluoride / chlorine gas=1 / 2.37 / 0.032, contact time: 74 seconds). The results are shown in Table 3.

[0173] Table 2 also shows the reaction temperature, contact time, and supply amount of the reaction raw materials in Examples 1 to 4.

[0174] [Table 2]

[0175]

[0176] In Table 2, "organic matter" refers to 243fa, 242fa, and 241fa, which are "halogenated hydrocarbon compounds having 3 carbon atoms", and the number of moles refers to the sum of the numbers of moles calculated from their GC area %.

[0177] [Table 3]

[0178]

[0179] nd: indicates GC area % less than 0.01%.

[0180] As can be seen from the above, in all Examples 1 to 4, the formation of the target product 1233E was confirmed, and in particular, in Examples 2 to 4 where the reaction temperature was 200° C. or higher, the GC% of 1233E became high.

[0181] [Comparative Example 1]

[0182] The reaction was carried out for 1 hour in the same manner as in Example 1 except that the feed amount of the reaction raw materials was set to be the fraction of Preparation Example 1 (liquid composition containing a halogenated hydrocarbon compound having 3 carbon atoms) which had been vaporized: 0.41 g / min, hydrogen fluoride: 0.11 g / min, and chlorine: about 1.0 ml / min (molar ratio: halogenated hydrocarbon compound having 3 carbon atoms / hydrogen fluoride / chlorine = 1 / 2.36 / 0.020, contact time: 47 seconds). After that, the reaction was carried out for 1 hour in the same manner as in Example 1. After that, only the introduction of chlorine was stopped, and the reaction was continued, and analysis was carried out after 8 hours and 13 hours. The results are shown in Table 4.

[0183] [Table 4]

[0184]

[0185] nd: indicates GC area % less than 0.01%.

[0186] According to Comparative Example 1, when chlorine gas is not supplied as a reaction raw material, the conversion rate of the organic raw material and the yield of 1233E gradually decrease with the passage of time.

[0187] [Example 5]

[0188] A cylindrical stainless steel (SUS316L) reaction tube with an inner diameter of 2.7 cm and a length of 40 cm equipped with an electric furnace was filled with 130 ml of the chromium-supported fluorinated alumina prepared in Preparation Example 3, and the temperature was raised while nitrogen gas was flowing at a rate of 10 ml / min. When the temperature of the reaction tube reached 250°C, the vaporized fraction of Preparation Example 1 (liquid composition containing a halogenated hydrocarbon compound with a carbon number of 3) was supplied as a reaction raw material at a flow rate of 0.51 g / min, hydrogen fluoride: 0.08 g / min, and chlorine gas: 1.0 ml / min (molar ratio: halogenated hydrocarbon compound with a carbon number of 3 / hydrogen fluoride / chlorine gas = 1 / 1.54 / 0.017, contact time: 50 seconds). When the flow rate was stable, the supply of nitrogen gas was stopped. The generated gas flowing out of the reactor was passed through a fluororesin gas purge bottle containing ice water cooled in an ice water bath, and the unreacted hydrogen fluoride and hydrogen chloride were absorbed to capture the reaction product. The captured reaction product was analyzed by gas chromatography. The results of the reaction time change are shown in FIG. Figure 2 It should be noted that Figure 2 In the figures, the 1233E yield indicates the 1233E concentration (GC%) in the reaction product.

[0189] Depend on Figure 2 It can be seen that in the present invention, the activity of the chromium-supported fluorinated alumina catalyst is maintained well over 60 hours.

[0190] [Example 6]

[0191] A cylindrical stainless steel (SUS316L) reaction tube with an inner diameter of 2.7 cm and a length of 40 cm equipped with an electric furnace was filled with 130 ml of the fluorinated alumina prepared in Preparation Example 2, and the temperature was raised while nitrogen gas was flowing at a rate of 10 ml / min. When the temperature of the reaction tube reached 280°C, the vaporized fraction of Preparation Example 1 (halogenated hydrocarbon compound with a carbon number of 3): 0.64 g / min, hydrogen fluoride: 0.12 g / min, and chlorine gas: 1.0 ml / min were supplied as reaction raw materials (molar ratio: halogenated hydrocarbon compound with a carbon number of 3 / hydrogen fluoride / chlorine gas = 1 / 1.75 / 0.013, contact time: 37 seconds). When the flow rate was stable, the supply of nitrogen gas was stopped. The generated gas flowing out of the reactor was passed through a fluororesin gas purge bottle containing ice water cooled in an ice water bath, and the unreacted hydrogen fluoride and hydrogen chloride were absorbed to collect the reaction product. The collected reaction product was analyzed by gas chromatography and the results of the reaction time change are shown in Figure 3 .

[0192] Depend on Figure 3 It is understood that in the present invention, the activity of the fluorinated alumina catalyst is maintained well over a long period of time such as 45 hours.

[0193] Description of Reference Numerals

[0194] 1: valve, 2: valve, 3: valve, 4: valve, 5: valve, 6: valve, 7: valve, 8: valve, 10: liquid phase reaction tank, 11: pipe, 13: pipe, 15: pipe, 17: pipe, 30: condenser, 31: pipe, 35: condenser, 36: pipe, 50: tank, 70: tank, 71: pipe, 90: gas phase reaction tower, 91: pipe, 93: pipe, 95: pipe, 100: manufacturing device

Claims

1. A method for producing trans-1-chloro-3,3,3-trifluoropropene, comprising: Step (A), reacting 1,1,1,3,3-pentachloropropane with hydrogen fluoride to obtain a halogenated hydrocarbon compound having 3 carbon atoms represented by the following general formula (1); and Step (B), reacting the halogenated hydrocarbon compound having 3 carbon atoms obtained in step (A) with hydrogen fluoride in a gas phase in the presence of a solid catalyst and chlorine to obtain trans-1-chloro-3,3,3-trifluoropropene, C3H X Cl Y F Z (1) In the formula, X is 2 or 3. When X=2, Y is an integer of 1 to 4, and Z is an integer of 0 to 3, satisfying Y+Z=4; when X=3, Y is an integer of 1 to 5, and Z is an integer of 0 to 4, satisfying Y+Z=5; wherein the general formula (1) represents a halogenated hydrocarbon compound having 3 carbon atoms except trans-1-chloro-3,3,3-trifluoropropene.

2. The manufacturing method according to claim 1, wherein: The step (A) is carried out in a liquid phase in the absence of a catalyst.

3. The manufacturing method according to claim 1, wherein: The solid catalyst used in the step (B) is a metal fluoride containing at least one metal selected from the group consisting of aluminum, chromium, titanium, manganese, iron, nickel, cobalt, copper, magnesium, zirconium, molybdenum, zinc, tin, lanthanum, niobium, tantalum and antimony.

4. The manufacturing method according to claim 1, characterized in that: In the step (B), a hydrocarbon compound having 3 carbon atoms represented by the following general formula (2) is further added and reacted with hydrogen fluoride in a gas phase in the presence of chlorine gas. C3H V F W (2) In the formula, when V+W=8 is satisfied, V is an integer of 0 to 8, when V+W=6 is satisfied, V is an integer of 0 to 6, and when V+W=4 is satisfied, V is an integer of 0 to 4.

5. The manufacturing method according to claim 1, characterized in that: The halogenated hydrocarbon compound having 3 carbon atoms is at least one selected from the group consisting of 1,1,3,3-tetrachloro-1-fluoropropane, 1,3,3-trichloro-1,1-difluoropropane, cis-1-chloro-3,3,3-trifluoropropene, 3,3-dichloro-1,1,1-trifluoropropane and 3-chloro-1,1,1,3-tetrafluoropropane.

6. The manufacturing method according to claim 1, wherein: The halogenated hydrocarbon compound having 3 carbon atoms includes at least one selected from the group consisting of 1,1,3,3-tetrachloro-1-fluoropropane, 1,3,3-trichloro-1,1-difluoropropane, and 3,3-dichloro-1,1,1-trifluoropropane.

7. The manufacturing method according to claim 1, wherein: The halogenated hydrocarbon compound having 3 carbon atoms contains at least 1,3,3-trichloro-1,1-difluoropropane.

8. The manufacturing method according to claim 1, characterized in that: The halogenated hydrocarbon compound having 3 carbon atoms is a plurality of compounds selected from the group consisting of 1,1,3,3-tetrachloro-1-fluoropropane, 1,3,3-trichloro-1,1-difluoropropane, cis-1-chloro-3,3,3-trifluoropropene, 3,3-dichloro-1,1,1-trifluoropropane and 3-chloro-1,1,1,3-tetrafluoropropane.

9. The manufacturing method according to claim 8, characterized in that: The halogenated hydrocarbon compound having 3 carbon atoms is at least three selected from the group consisting of 1,1,3,3-tetrachloro-1-fluoropropane, 1,3,3-trichloro-1,1-difluoropropane, cis-1-chloro-3,3,3-trifluoropropene, 3,3-dichloro-1,1,1-trifluoropropane and 3-chloro-1,1,1,3-tetrafluoropropane.

10. The manufacturing method according to claim 1, characterized in that: The reaction temperature of the step (B) is 100° C. or higher and 400° C. or lower.

11. The manufacturing method according to claim 10, characterized in that: The reaction temperature of the step (B) is 150° C. or higher and 300° C. or lower.

12. The manufacturing method according to claim 1, characterized in that: The step (A) is carried out in a liquid phase without a catalyst, and the reaction gas containing trans-1-chloro-3,3,3-trifluoropropene is recovered. The reaction liquid in the step (A) is recovered, and the C3 halogenated hydrocarbon compound contained in the reaction liquid is used in the step (B).

13. The manufacturing method according to claim 12, characterized in that: The 1,1,1,3,3-pentachloropropane and the hydrogen fluoride are continuously or intermittently introduced into the step (A), The reaction product gas and the reaction liquid are recovered continuously or intermittently.

14. The manufacturing method according to claim 1, characterized in that: The unreacted intermediate product is recovered and used in the step (B).

15. The manufacturing method according to claim 1, characterized in that: In the step (B), cis-1-chloro-3,3,3-trifluoropropene is obtained together with trans-1-chloro-3,3,3-trifluoropropene.

16. The manufacturing method according to claim 15, characterized in that: The obtained cis-1-chloro-3,3,3-trifluoropropene is supplied to the above step (B).

17. The manufacturing method according to claim 15, characterized in that: The obtained cis-1-chloro-3,3,3-trifluoropropene is heated at 100° C. to 400° C. to obtain trans-1-chloro-3,3,3-trifluoropropene.

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