Composite oxide catalyst and method for producing halogen compound

Abstract

This composite oxide catalyst contains constituent elements comprising an Al element and at least three elements selected from the group consisting of Cr, Mn, Fe, Co, Ni, Cu, Zn, Pr, La, Gd, Dy, Ce, Nd, Sm, Er, Mg, Zr, Hf, Bi, and In.

Description

Method for producing complex oxide catalysts and halogen compounds

[0001] This disclosure relates to a method for producing a complex oxide catalyst and a halogen compound.

[0002] Different types of catalysts are used in the production of compounds, depending on the purpose. For example, Patent Document 1 describes ZnO / Cr ２ O ３ / Al ２ O ３ It has been disclosed that 1,2-dichloro-1,3,3,3-tetrafluoro-1-propene (FC-1214) and 2-chloropentafluoropropene (FC-1215) were obtained by halogen exchange reaction using as a catalyst. Patent Document 2 discloses that trifluorotrichloroethane (R-113), dichlorotetrafluoroethane (R-114), and chloropentafluoroethane (R-115), etc., were obtained by disproportionation reaction using chromium oxide / magnesium oxide / aluminum oxide as a catalyst. Patent Document 3 discloses that 1-chloro-2,3,3-trifluoropropene (HCFO-1233yd) was obtained using Cr-Co-Zn as a catalyst.

[0003] Japanese Patent Publication No. 62-26239, Japanese Patent Publication No. 57-197233, Chinese Patent Application Publication No. 112125776 Specification

[0004] As described above, for example, ternary catalysts have been used in the production of compounds. However, from the viewpoint of productivity, there is a need for catalysts that can further improve production efficiency. This disclosure is made in view of the above, and relates to a composite oxide catalyst that is excellent in raw material conversion per unit catalyst mass, and a method for producing halogen compounds using the composite oxide catalyst.

[0005] This disclosure includes the following embodiments: <1> A composite oxide catalyst comprising constituent elements consisting of Al and at least three elements selected from the group consisting of Cr, Mn, Fe, Co, Ni, Cu, Zn, Pr, La, Gd, Dy, Ce, Nd, Sm, Er, Mg, Zr, Hf, Bi, and In. <2> The composite oxide catalyst according to <1>, wherein the constituent elements consist of Al and at least three elements selected from the group consisting of Cr, Mn, Fe, Co, Ni, Cu, Zn, Pr, La, Gd, and Dy. <3> The composite oxide catalyst according to <1>, wherein the constituent elements consist of Al and at least three elements selected from the group consisting of Cr, Mn, Fe, Co, Ni, Cu, and Zn. <4> The composite oxide catalyst according to <1>, wherein the constituent elements consist of an Al element, a Cr element, and at least two elements selected from the group consisting of Mn, Fe, Co, Ni, Cu, and Zn. <5> The composite oxide catalyst according to <1>, wherein the constituent elements consist of an Al element, a Cr element, a Ni element, and at least one element selected from the group consisting of Mn, Fe, Co, Cu, and Zn. <6> The composite oxide catalyst according to <1>, wherein the constituent elements consist of an Al element, a Cr element, a Ni element, and at least one element selected from the group consisting of Fe and Zn. <7> The composite oxide catalyst according to any one of <1> to <6>, wherein the content of the Al element is 60 mol% or more relative to the total amount of the constituent elements. <8> The composite oxide catalyst according to <6>, wherein the content of Al is 60 to 95 mol% of the total amount of the constituent elements, the content of Cr is 1 to 30 mol% of the total amount of the constituent elements, the content of Ni is 0.1 to 10 mol% of the total amount of the constituent elements, and the combined content of Fe and Zn is 0.1 to 10 mol% of the total amount of the constituent elements. <9> The composite oxide catalyst according to any one of <1> to <8>, wherein the content of Na is less than 150 ppm of the total amount of the composite oxide catalyst.<10> A method for producing a halogen compound, comprising contacting a first halogen compound with a composite oxide catalyst described in any one of <1> to <9> to obtain a second halogen compound different from the first halogen compound by a halogen exchange reaction. <11> The method for producing a halogen compound according to <10>, wherein the first halogen compound is chlorodifluoromethane, and the second halogen compound is at least one selected from the group consisting of trifluoromethane, dichlorofluoromethane, and trichloromethane. <12> The method for producing a halogen compound according to <10>, wherein the first halogen compound is 1,3-dichloro-1,1,2,2,3-pentafluoropropane, and the second halogen compound is at least one selected from the group consisting of 2,2,3-trichloro-1,1,1,3-tetrafluoropropane, 1,3,3-trichloro-1,1,2,2-tetrafluoropropane, 1-chloro-1,1,2,2,3,3-hexafluoropropane, 2,2-dichloro-1,1,1,3,3-pentafluoropropane, 2,3-dichloro-1,1,1,2,3-pentafluoropropane, 1,2-dichloro-1,1,2,3,3-pentafluoropropane, 3,3-dichloro-1,1,1,2,2-pentafluoropropane, and 1,1-dichloro-1,2,2,3,3-pentafluoropropane. <13> The method for producing a halogen compound according to <10>, wherein the first halogen compound is at least one selected from the group consisting of trifluoromethane and trichloromethane, and the second halogen compound is at least one selected from the group consisting of chlorodifluoromethane and dichlorofluoromethane. <14> The method for producing a halogen compound according to <10>, wherein the first halogen compound is (Z)-1-chloro-2,3,3-trifluoropropene, and the second halogen compound is at least one selected from the group consisting of 1,2-dichloro-3,3-difluoropropene, 2,3-dichloro-1,3-difluoropropene, 2,3,3,3-tetrafluoropropene, 1,2,3,3-tetrafluoropropene, (E)-1-chloro-2,3,3-trifluoropropene, and 2-chloro-1,3,3-trifluoropropene.<15> The method for producing a halogen compound according to <10>, wherein the first halogen compound is (Z)-1,2-dichloro-3,3-difluoropropene, and the second halogen compound is at least one selected from the group consisting of (E)-1-chloro-2,3,3-trifluoropropene, (Z)-1-chloro-2,3,3-trifluoropropene, 2-chloro-1,3,3-trifluoropropene, 1,2,3-trichloro-3-fluoropropene, and (E)-1,2-dichloro-3,3-difluoropropene.

[0006] This disclosure provides a composite oxide catalyst that exhibits excellent raw material conversion rate per unit catalyst mass, and a method for producing halogen compounds using the composite oxide catalyst.

[0007] One embodiment of this disclosure is described in detail below. However, this disclosure is not limited to this embodiment. In the following disclosure, the components (including elemental steps, etc.) are not essential unless otherwise explicitly stated. The same applies to numerical values ​​and their ranges, and do not limit this disclosure.

[0008] In this disclosure, numerical ranges indicated using "~" include the numbers before and after "~" as the lower and upper limits, respectively. In numerical ranges described in stages in this disclosure, the upper or lower limit stated in one numerical range may be replaced with the upper or lower limit of another numerical range described in stages. Also, in numerical ranges described in this disclosure, the upper or lower limit of that numerical range may be replaced with the values ​​shown in the examples. In this disclosure, the content of each component in a composition means the total content of the multiple substances present in the composition, unless otherwise specified, if multiple substances corresponding to each component exist in the composition. In this disclosure, where multiple elements are listed using "or" or "or," the selection of multiple elements in combination is not excluded unless otherwise explicitly stated, as long as it does not result in a technical inconsistency. Even when an element is expressed in the singular form in this disclosure, the existence of multiple elements is not excluded unless otherwise explicitly stated, as long as it does not result in a technical inconsistency. In this disclosure, multiple exemplary embodiments described separately may be combined to form new embodiments, as long as they do not contradict each other.

[0009] ≪Combined Oxide Catalyst≫ The combined oxide catalyst of this disclosure contains constituent elements consisting of Al and at least three elements selected from the group consisting of Cr, Mn, Fe, Co, Ni, Cu, Zn, Pr, La, Gd, Dy, Ce, Nd, Sm, Er, Mg, Zr, Hf, Bi, and In. According to the combined oxide catalyst of this disclosure, it is estimated that the combination of elements contained in the combined oxide catalyst will result in excellent raw material conversion per unit catalyst mass.

[0010] <Constituent Elements> The composite oxide catalyst of this disclosure includes constituent elements. The constituent elements consist of Al and at least three elements selected from the group consisting of Cr, Mn, Fe, Co, Ni, Cu, Zn, Pr, La, Gd, Dy, Ce, Nd, Sm, Er, Mg, Zr, Hf, Bi, and In. In this disclosure, a constituent element means an element having a content of 0.1 mol% or more of the total amount of constituent elements. That is, even if an element is of a type that falls under the category of constituent elements, if its content is less than 0.1 mol% of the total amount of constituent elements, it is not considered a constituent element.

[0011] From the viewpoint of superior raw material conversion rate, the content of constituent elements is preferably 40 mol% or more, more preferably 50 mol% or more, and even more preferably 60 mol% or more, relative to the total amount of the composite oxide catalyst excluding hydrogen and oxygen atoms. The content of constituent elements may also be 90 mol% or less, 80 mol% or less, or 70 mol% or less, relative to the total amount of the composite oxide catalyst excluding hydrogen and oxygen atoms. The content of constituent elements is, for example, 30 to 100 mol% relative to the total amount of the composite oxide catalyst excluding hydrogen and oxygen atoms. In this disclosure, the content of constituent elements relative to the total amount of the composite oxide catalyst excluding hydrogen and oxygen atoms can be measured by elemental analysis using the X-ray fluorescence method. For example, the composite oxide catalyst is filled into a polyvinyl chloride ring with a diameter of φ10 mm and a height of 5 mm, and pressurized and molded at 30 kN for 1 minute. Next, the resulting molded body is placed in a Rigaku ZSX Primus II and its composition is analyzed using the EZ scan mode of X-ray fluorescence spectroscopy.

[0012] [Al element] From the viewpoint of superior raw material conversion rate, the Al element content is preferably 60 mol% or more, more preferably 65 mol% or more, and even more preferably 70 mol% or more, relative to the total amount of constituent elements. The Al element content may also be less than 99.7 mol%, 95 mol% or less, or 90 mol% or less, relative to the total amount of constituent elements. The Al element content is, for example, 60 to less than 99.7 mol%, and preferably 60 to 95 mol%, relative to the total amount of constituent elements. In this disclosure, the content of each element relative to the total amount of constituent elements can be measured by X-ray fluorescence.

[0013] [Constituent elements other than Al] The constituent elements other than Al are at least three elements selected from the group consisting of Cr, Mn, Fe, Co, Ni, Cu, Zn, Pr, La, Gd, Dy, Ce, Nd, Sm, Er, Mg, Zr, Hf, Bi, and In.

[0014] From the viewpoint of superior raw material conversion rate, the constituent elements preferably consist of Al and at least three elements selected from the group consisting of Cr, Mn, Fe, Co, Ni, Cu, Zn, Pr, La, Gd, Dy, Mg, Zr, Hf, Bi, and In; more preferably consist of Al and at least three elements selected from the group consisting of Cr, Mn, Fe, Co, Ni, Cu, Zn, Pr, La, Gd, and Dy; even more preferably consist of Al and at least three elements selected from the group consisting of Cr, Mn, Fe, Co, Ni, Cu, and Zn; and even more preferably consist of Al and at least two elements selected from the group consisting of Cr and Mn, Fe, Co, Ni, Cu, and Zn. It is more preferable that the material consists of Al, Cr, Ni, and at least one element selected from the group consisting of Mn, Fe, Co, Cu, and Zn; it is particularly preferable that the material consists of Al, Cr, Ni, and at least one element selected from the group consisting of Fe and Zn; and it is most preferable that the material consists of Al, Cr, Ni, and Zn.

[0015] Furthermore, a composite oxide catalyst containing constituent elements consisting of Al and at least three elements selected from the group consisting of Cr, Mn, Fe, Co, Ni, Cu, Zn, Pr, La, Gd, and Dy has been conventionally used as an industrial catalyst. ２ O ３ Catalysts represented by and ZnO-Cr ２ O ３ This composite oxide catalyst exhibits superior raw material conversion rates per unit catalyst mass compared to catalysts represented by [formula].

[0016] From the viewpoint of improving the dispersibility of the constituent elements in the oxide catalyst, it is preferable that the constituent elements consist of four or five elements, and more preferably four elements.

[0017] From the viewpoint of superior raw material conversion, the content of Cr is preferably 1 to 30 mol%, more preferably 1 to 20 mol%, and even more preferably 5 to 15 mol% relative to the total amount of constituent elements. From the viewpoint of superior raw material conversion, the content of Ni is preferably 0.1 to 10 mol%, more preferably 0.2 to 9 mol%, and even more preferably 0.5 to 8 mol% relative to the total amount of constituent elements. From the viewpoint of superior raw material conversion, the combined content of Fe and Zn is preferably 0.1 to 10 mol%, more preferably 0.2 to 9 mol%, and even more preferably 0.5 to 8 mol% relative to the total amount of constituent elements.

[0018] From the viewpoint of superior raw material conversion rate, the Fe element content is preferably 0.1 to 10 mol%, more preferably 0.2 to 9 mol%, and even more preferably 0.5 to 8 mol% relative to the total amount of constituent elements. From the viewpoint of superior raw material conversion rate, the Zn element content is preferably 0.1 to 10 mol%, more preferably 0.2 to 9 mol%, and even more preferably 0.5 to 8 mol% relative to the total amount of constituent elements.

[0019] From the viewpoint of superior raw material conversion rate, the content of Mn, Co, Cu, Pr, La, Gd, Dy, Ce, Nd, Sm, Er, Mg, Zr, Hf, Bi, and In is preferably 0.1 to 10 mol%, more preferably 0.2 to 9 mol%, and even more preferably 0.5 to 8 mol% relative to the total amount of constituent elements.

[0020] <Other Elements> The composite oxide catalyst of this disclosure may also contain other elements other than the constituent elements, i.e., elements other than Al, Cr, Mn, Fe, Co, Ni, Cu, Zn, Pr, La, Gd, Dy, Ce, Nd, Sm, Er, Mg, Zr, Hf, Bi, and In. Examples of other elements include C, H, O, N, and Na. Since the composite oxide catalyst of this disclosure is a composite of metal oxides, it contains at least O.

[0021] The composite oxide catalysts of this disclosure preferably substantially contain at least one element selected from the group consisting of Ca, Sr, Y, Ag, Sb, and Pb, and more preferably substantially contain Ca, Sr, Y, Ag, Sb, and Pb. In this disclosure, "substantially contain an element" means that the element is not present, or that the content of the element is less than 0.1 mol% of the total amount of the constituent elements.

[0022] From the viewpoint of superior raw material conversion rate, in the composite oxide catalyst of this disclosure, the content of Na element is preferably 300 ppm or less, more preferably 200 ppm or less, and even more preferably less than 150 ppm, relative to the total amount of the composite oxide catalyst. The content of Na element may also be 0 ppm or more, 50 ppm or more, or 100 ppm or more, relative to the total amount of the composite oxide catalyst. The content of Na element is, for example, 0 to 300 ppm relative to the total amount of the composite oxide catalyst. A method for reducing the content of Na element to less than 150 ppm is to wash the composite oxide catalyst with a solvent (for example, water).

[0023] The sodium (Na) content in a composite oxide catalyst can be confirmed by elemental analysis using X-ray fluorescence. For example, a composite oxide catalyst is filled into a polyvinyl chloride ring with a diameter of 10 mm and a height of 5 mm, and molded under pressure at 30 kN for 1 minute. Next, the resulting molded body is set in a Rigaku ZSX Primus II and its composition is analyzed using the EZ scan mode of X-ray fluorescence. If the sodium content in the composite oxide catalyst falls below the detection limit of the instrument based on the mass percentage of the obtained chemical composition, the sodium content is less than 150 ppm.

[0024] Furthermore, even if the composition of the constituent elements of the composite oxide catalyst is the same, when the content of Na element in the composite oxide catalyst is less than 150 ppm, the amount of raw material converted per unit catalyst mass is particularly superior compared to when the content of Na element in the composite oxide catalyst is 150 ppm or more.

[0025] <Structure> The composite oxide catalyst of the present disclosure is a composite of metal oxides and preferably has a crystal structure. The fact that the composite oxide catalyst contains a crystal structure can be confirmed by detecting the diffraction pattern obtained by the X-ray diffraction method, that is, XRD (X-Ray Diffractometer). As XRD, a commercially available device can be used. For example, "SmartLab" manufactured by Rigaku Corporation is used. The composite oxide catalyst is analyzed by the X-ray diffraction method, and the presence or absence of a crystal structure is confirmed by the presence or absence of peaks attributable to the diffraction pattern of the oxide containing one or more corresponding compositions.

[0026] <Amount of raw material conversion per unit catalyst mass> As an index of the performance of the composite oxide catalyst of the present disclosure, from the viewpoint of considering the raw material load on the catalyst, the amount of raw material conversion per unit catalyst mass is used. The amount of raw material conversion per unit catalyst mass of the composite oxide catalyst can be measured by the method described in the <<Method for producing halogen compound>> described later.

[0027] <Method for producing composite oxide catalyst> The composite oxide catalyst of the present disclosure can be produced by a known method. More specifically, for example, a solution A in which a metal salt containing a desired element is dissolved in water is prepared. Examples of the metal salt include metal halides such as metal fluorides, metal chlorides, metal bromides, and metal iodides (including metal oxyhalides); metal nitrates; metal sulfates; metal carbonates; metal formates; metal phosphates; metal carboxylates; and metal alkoxides. To solution A, a 1 mol / L HNO ３ aqueous solution is added as necessary to dissolve the raw materials. Further, a solution B which is an alkaline aqueous solution is prepared. Examples of the alkali include ammonia; alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate. Next, the above solution A and solution B are mixed. By this mixing, a neutralization reaction occurs, and a solution containing a precipitate of hydroxide is obtained. Solution A and solution B may be mixed while being quantitatively supplied respectively. Next, the solution containing the precipitate of the obtained hydroxide is aged. The aging temperature is, for example, 40 to 90 °C. The aging time is, for example, 5 to 30 hours. Thereafter, the aged precipitate is filtered, washed, dried, and pulverized, and then an inert gas (for example, N ２The composite oxide catalyst powder is obtained by calcining under a specific atmosphere. The drying temperature is, for example, 80 to 150°C. The calcination temperature is, for example, 400 to 1000°C. The calcination time is, for example, 3 to 10 hours.

[0028] Examples of raw materials containing the desired metal element include metal nitrates, metal chlorides, and their hydrates.

[0029] <Applications> The composite oxide catalyst of this disclosure is preferably used in the production of halogen compounds. The composite oxide catalyst of this disclosure is preferably used in halogen exchange reactions, and more preferably used in at least one selected from the group consisting of isomerization reactions and disproportionation reactions.

[0030] ≪Method for Producing Halogen Compounds≫ The method for producing halogen compounds according to this disclosure (hereinafter also referred to as the "method for producing halogen compounds according to this disclosure") involves contacting a first halogen compound with the composite oxide catalyst according to this disclosure and obtaining a second halogen compound different from the first halogen compound by a halogen exchange reaction.

[0031] The halogen exchange reaction is preferably at least one selected from the group consisting of isomerization reactions and disproportionation reactions.

[0032] From the viewpoint of suppressing the accumulation of by-products on the catalyst, the manufacturing method of the present disclosure preferably involves contacting a mixed gas of a first halogen compound and an inert gas with the composite oxide catalyst of the present disclosure. The inert gas is, for example, nitrogen gas. The content of the first halogen compound is, for example, 1 to 80 mol% of the total amount of the mixed gas. The contact time is, for example, 0.01 to 60 seconds. The temperature of the composite oxide catalyst of the present disclosure when in contact is, for example, 100 to 500°C.

[0033] Contact between the first halogen compound and the composite oxide catalyst of this disclosure may be carried out, for example, by flowing the first halogen compound through a reaction tube made of stainless steel or the like, which is filled with the composite oxide catalyst of this disclosure.

[0034] The composite oxide catalyst of the present disclosure may be a pre-dehydrated composite oxide catalyst. The dehydration may be carried out, for example, by heating to 100 to 500 °C while flowing nitrogen through a reaction tube made of stainless steel or the like filled with the composite oxide catalyst of the present disclosure.

[0035] The composite oxide catalyst of the present disclosure may be a pre-activated composite oxide catalyst, or may be a pre-dehydrated and activated composite oxide catalyst. The activation may be carried out, for example, by flowing a 2.0 / 1 (mol / mol) mixed gas of nitrogen / HFC-22 through a reaction tube made of stainless steel or the like filled with the composite oxide catalyst of the present disclosure for 1 to 24 hours with a contact time of 0.01 to 60 seconds.

[0036] <First halogen compound and second halogen compound> From the viewpoint of excellent raw material conversion amount, the carbon number of the first halogen compound is preferably 1 to 3, more preferably 1 or 2, and still more preferably 1. The carbon number of the second halogen compound is also preferably 1 to 3, more preferably 1 or 2, and still more preferably 1. From the viewpoints of the raw material conversion amount and the usefulness of the obtained second halogen compound, the first halogen compound is preferably a first fluorine compound, and the second halogen compound is preferably a second fluorine compound. When the carbon number of the first halogen compound and the second halogen compound is 2 or more, each may independently have one or more carbon-carbon double bonds.

[0037] In the production method of the present disclosure, the first halogen compound may be contained alone or in combination of two or more. Similarly, the second halogen compound may be contained alone or in combination of two or more.

[0038] The abbreviations of each halogen compound used in the present disclosure are as follows. HCC-20: trichloromethane HCFC-21: dichlorofluoromethane HCFC-22: chlorodifluoromethane HFC-23: trifluoromethane

[0039] HCFC-224aa: 2,2,3-trichloro-1,1,1,3-tetrafluoropropane HCFC-224ca: 1,3,3-trichloro-1,1,2,2-tetrafluoropropane HCFC-225aa: 2,2-dichloro-1,1,1,3,3-pentafluoropropane HCFC-225ba: 2,3-dichloro-1,1,1,2,3-pentafluoropropane HCFC-225bb: 1,2-dichloro-1,1,2,3,3-pentafluoropropane HCFC-225ca: 3,3-dichloro-1,1,1,2,2-pentafluoropropane HCFC-225cb: 1,3-dichloro-1,1,2,2,3-pentafluoropropane HCFC-225cc: 1,1-dichloro-1,2,2,3,3-pentafluoropropane HCFC-226cb: 1-chloro-1,1,2,2,3,3-hexafluoropropane

[0040] HCFO-1231xd: 1,2,3-trichloro-3-fluoropropene HCFO-1232xd: 1,2-dichloro-3,3-difluoropropene HCFO-1232xd(E): (E)-1,2-dichloro-3,3-difluoropropene HCFO-1232xd(Z): (Z)-1,2-dichloro-3,3-difluoropropene HCFO-1232xe: 2,3-dichloro-1,3-difluoropropene HCFO-1233xe: 2-chloro-1,3,3-trifluoropropene HCFO-1233yd(E): (E)-1-chloro-2,3,3-trifluoropropene HCFO-1233yd(Z): (Z)-1-chloro-2,3,3-trifluoropropene HFO-1234ye: 1,2,3,3-tetrafluoropropene HFO-1234yf: 2,3,3,3-tetrafluoropropene

[0041] In the manufacturing method of this disclosure, the first halogen compound is preferably HCFC-22, and the second halogen compound is preferably at least one selected from the group consisting of HFC-23, HCFC-21, and HCC-20. In this case, the halogen exchange reaction is a disproportionation reaction.

[0042] Alternatively, in the production method of the present disclosure, the first halogen compound is HCFC-225cb, and the second halogen compound is preferably at least one selected from the group consisting of HCFC-224aa, HCFC-224ca, HCFC-226cb, HCFC-225aa, HCFC-225ba, HCFC-225bb, HCFC-225ca, and HCFC-225cc. In this case, the halogen exchange reaction is an isomerization reaction and a disproportionation reaction.

[0043] Alternatively, in the production method of the present disclosure, the first halogen compound is at least one selected from the group consisting of HFC-23 and HCC-20, and the second halogen compound is preferably at least one selected from the group consisting of HCFC-22 and HCFC-21. In this case, the halogen exchange reaction is a disproportionation reaction.

[0044] Alternatively, in the production method of the present disclosure, the first halogen compound is HCFO-1233yd(Z), and the second halogen compound is preferably at least one selected from the group consisting of HCFO-1232xd, HCFO-1232xe, HFO-1234yf, HFO-1234ye, HCFO-1233yd(E), and HCFO-1233xe. In this case, the halogen exchange reaction is an isomerization reaction and a disproportionation reaction, and further an E-Z isomerization reaction occurs.

[0045] Alternatively, in the production method of the present disclosure, the first halogen compound is HCFO-1232xd(Z), and the second halogen compound is preferably at least one selected from the group consisting of HCFO-1233yd(E), HCFO-1233yd(Z), HCFO-1233xe, HCFO-1231xd, and HCFO-1232xd(E). In this case, the halogen exchange reaction is an isomerization reaction and a disproportionation reaction, and further an E-Z isomerization reaction occurs.

[0046] Compounds contained in the composition obtained by the manufacturing method of this disclosure can be analyzed by gas chromatography. Specifically, for example, the analysis is performed by attaching a column (product name "DB-1701", manufactured by Agilent, length 60 m, inner diameter 0.25 mm, film thickness 0.25 μm) to a gas chromatograph (product name "GC6850", manufactured by Agilent). From the Area% of the obtained chart, the conversion rate of the raw material (i.e., the first halogen compound) is calculated, and further, the amount of raw material converted per unit catalyst mass is calculated from the raw material supply amount per unit time and the mass of composite oxide catalyst used. • Conversion rate (%) = 100 - [Raw material content in the obtained composition (%)] • Amount of raw material converted per unit catalyst mass (g-raw material / g-cat / h) = [Raw material supply amount per unit time (g / h) × Conversion rate (%) / 100] / [Mass of composite oxide catalyst used (g)]

[0047] The present disclosure will be further described below with reference to examples, but the present disclosure is not limited to the following examples unless it exceeds the spirit of the disclosure. Unless otherwise specified, "%" is by mass. Examples 1-4 to 1-12, 2-4 to 2-12, 3-4 to 3-5, 4-1 to 4-2, 5-1 to 5-2, and 6-1 to 6-2 are examples, and examples 1-1 to 1-3, 2-1 to 2-3, and 3-1 to 3-3 are comparative examples.

[0048] <Combined Oxide Catalysts (Examples 1-1 to 1-12)> [Preparation] Solution A was prepared by dissolving the first to fourth raw materials of the type and mass shown in Table 1 in the mass shown in Table 1 of water. Solution A was also prepared by adding 1 mol / L of HNO in the mass shown in Table 1 as needed. ３ An aqueous solution was added. Furthermore, solution B was prepared by dissolving the mass of sodium carbonate (or 28% by mass aqueous ammonia solution) shown in Table 1 in water as an alkaline raw material. Next, solutions A and B were added to a glass beaker at a quantitative rate of 10 mL / min each, and mixed while stirring to neutralize and obtain a solution containing a hydroxide precipitate. The entire volume of the obtained solution was transferred to an Erlenmeyer flask and aged for 20 hours while immersed in an oil bath at 50°C and stirred. After that, it was removed from the oil bath, allowed to return to room temperature, filtered, washed with pure water, dried at 120°C, ground in an alumina mortar, and then N ２Under atmospheric conditions, the composite oxide catalyst powder was obtained by calcining at the calcination temperature shown in Table 1 for 3 hours. Table 1 shows the composition of the constituent elements in the obtained composite oxide catalyst. Each value in the composition indicates the percentage of each element when the total amount of constituent elements is set to 100 mol%. In other words, elements such as oxygen (O) in the composite oxide catalyst are omitted from the composition.

[0049] [Analysis] (Na content) The Na content in the obtained composite oxide catalyst was confirmed by elemental analysis using X-ray fluorescence. The composite oxide catalyst was filled into a φ10 mm, 5 mm high polyvinyl chloride ring and molded under pressure at 30 kN for 1 minute. Next, the resulting molded body was set in a Rigaku ZSX Primus II and compositional analysis was performed using the EZ scan mode of X-ray fluorescence. If the Na content in the composite oxide catalyst was below the detection limit of the instrument based on the mass percent of the obtained chemical composition, the Na content was considered to be less than 150 ppm. The results are shown in Table 1.

[0050] (Crystal Structure) The presence of a crystal structure in the obtained composite oxide catalyst was confirmed by X-ray diffraction, i.e., detection of the diffraction pattern obtained by XRD (X-Ray Diffractometer). A "SmartLab" manufactured by Rigaku Corporation was used as the XRD. The composite oxide catalyst was analyzed by X-ray diffraction, and the presence or absence of a crystal structure was confirmed by the presence or absence of peaks that could be attributed to the diffraction pattern of an oxide containing one or more of the relevant components. The results are shown in Table 1.

[0051] The above analysis of the Na element content and crystal structure was performed on the composite oxide catalyst immediately before contact with the first halogen compound, or on a composite oxide catalyst that replicated the same state as the composite oxide catalyst immediately before contact with the first halogen compound.

[0052]

[0053] <Preparation of the second halogen compound from the first halogen compound> [First halogen compound: HCFC-22 (Examples 2-1 to 2-12)] A reaction tube made of stainless steel (SUS304) with an inner diameter of 1.02 cm and a length of 30 cm was filled with the type and mass of composite oxide catalysts shown in Table 2 and placed in a tubular electric furnace. The catalyst-filled section was heated at the contact temperature shown in Table 2 while circulating nitrogen to dehydrate the composite oxide catalyst. Subsequently, a 2.0 / 1 (mol / mol) mixed gas of nitrogen / HCFC-22 was circulated for 5 hours at the pressure, linear velocity, and contact time shown in Table 2, and the circulated gas was obtained as the composition.

[0054] [First halogen compound: HCFC-225cb (Examples 3-1 to 3-5)] A reaction tube made of stainless steel (SUS304) with an inner diameter of 1.02 cm and a length of 30 cm was filled with the type and mass of composite oxide catalysts shown in Table 3 and placed in a tubular electric furnace. The catalyst-filled section was heated at the contact temperature shown in Table 3 while nitrogen was flowed through it to dehydrate the composite oxide catalyst. Then, a 2.0 / 1 (mol / mol) mixed gas of nitrogen / HCFC-22 was flowed through it for 5 hours at the pressure, linear velocity, and contact time shown in Table 3 to activate the composite oxide catalyst. Next, a 5.0 / 1 (mol / mol) mixed gas of nitrogen / HCFC-225cb was flowed through it for 5 hours at the pressure, linear velocity, and contact time shown in Table 3 to obtain the resulting gas as a composition.

[0055] [First halogen compound: HFC-23 + HCC-20 mixed gas (Examples 4-1 to 4-2)] A reaction tube made of stainless steel (SUS304) with an inner diameter of 1.02 cm and a length of 30 cm was filled with the type and mass of composite oxide catalysts shown in Table 4 and placed in a tubular electric furnace. The catalyst-filled section was heated at the contact temperature shown in Table 4 while circulating nitrogen to dehydrate the composite oxide catalyst. Subsequently, a 2.0 / 1 (mol / mol) mixed gas of nitrogen / HCFC-22 was circulated for 5 hours at the pressure and linear velocity shown in Table 4 with a contact time of 1.3 seconds to activate the composite oxide catalyst. Next, the temperature of the catalyst-filled section was changed to 350°C, and a mixed gas of HFC-23 / HCC-20 = 2 / 1 (mol / mol) and nitrogen / (HFC-23 + HCC-20) 2.0 / 1 (mol / mol) was flowed for 5 hours at the pressure and linear velocity shown in Table 4 with a contact time of 0.7 seconds, and the flowed gas was obtained as the composition.

[0056] [First halogen compound: HCFO-1233yd(Z) (Examples 5-1 to 5-2)] A reaction tube made of stainless steel (SUS304) with an inner diameter of 1.02 cm and a length of 30 cm was filled with the type and mass of composite oxide catalysts shown in Table 5 and placed in a tubular electric furnace. The catalyst-filled section was heated at the contact temperature shown in Table 5 while nitrogen was flowed through it to dehydrate the composite oxide catalyst. Subsequently, a 2.0 / 1 (mol / mol) mixed gas of nitrogen / HCFC-22 was flowed through it for 5 hours at the pressure and linear velocity shown in Table 5 with a contact time of 1.3 seconds to activate the composite oxide catalyst. Next, a 5.0 / 1 (mol / mol) mixed gas of nitrogen / HCFO-1233yd(Z) was flowed through it for 5 hours at the pressure and linear velocity shown in Table 5 with a contact time of 1.3 seconds to obtain the resulting gas as a composition.

[0057] [First halogen compound: HCFO-1232xd (Examples 6-1 to 6-2)] A reaction tube made of stainless steel (SUS304) with an inner diameter of 1.02 cm and a length of 30 cm was filled with the type and mass of composite oxide catalysts shown in Table 6 and placed in a tubular electric furnace. The catalyst-filled section was heated at the contact temperature shown in Table 6 while nitrogen was flowed through it to dehydrate the composite oxide catalyst. Then, a 2.0 / 1 (mol / mol) mixed gas of nitrogen / HCFC-22 was flowed through it for 2 hours with a contact time of 1.3 seconds at the pressure and linear velocity shown in Table 6 to activate the composite oxide catalyst. Next, a 10.0 / 1 (mol / mol) mixed gas of nitrogen / HCFO-1232xd was flowed through it for 5 hours with a contact time of 1.0 second at the pressure and linear velocity shown in Table 6 to obtain the resulting gas as the composition.

[0058] [Analysis of the Obtained Compositions] The obtained compositions were analyzed using a gas chromatograph (product name "GC6850", manufactured by Agilent) with a column (product name "DB-1701", manufactured by Agilent, length 60 m, inner diameter 0.25 mm, film thickness 0.25 μm). The conversion rate of the raw material (i.e., the first halogen compound) was calculated from the Area% of the obtained chart. Furthermore, the amount of raw material converted per unit catalyst mass was calculated from the raw material supply amount per unit time and the mass of composite oxide catalyst used. The analysis results of the obtained compositions are shown in Tables 2 to 6. • Conversion rate (%) = 100 - [Raw material content in the obtained composition (%)] • Amount of raw material converted per unit catalyst mass (g-raw material / g-cat / h) = [Raw material supply amount per unit time (g / h) × Conversion rate (%) / 100] / [Mass of composite oxide catalyst used (g)]

[0059]

[0060]

[0061]

[0062]

[0063]

[0064] In Examples 2-4 to 2-12, HFC-23, HCFC-21, and HCC-20 were obtained as second halogen compounds from the first halogen compound, HCFC-22, through a disproportionation reaction.

[0065] In Examples 3-4 to 3-5, the second halogen compounds obtained from the first halogen compound, HCFC-225cb, were subjected to isomerization and disproportionation reactions to obtain HCFC-224aa, HCFC-224ca, HCFC-226cb, HCFC-225aa, HCFC-225ba, HCFC-225bb, HCFC-225ca, and HCFC-225cc.

[0066] In Examples 4-1 to 4-2, HCFC-22 and HCFC-21 were obtained as second halogen compounds from the first halogen compounds HFC-23 and HCC-20 by a disproportionation reaction.

[0067] In Examples 5-1 to 5-2, the second halogen compounds obtained from the first halogen compound HCFO-1233yd(Z) through isomerization and disproportionation reactions were HCFO-1232xd, HCFO-1232xe, HFO-1234yf, HFO-1234ye, HCFO-1233yd(E), and HCFO-1233xe.

[0068] In Examples 6-1 to 6-2, the second halogen compounds HCFO-1233yd(E), HCFO-1233yd(Z), HCFO-1233xe, HCFO-1231xd, and HCFO-1232xd(E) were obtained from the first halogen compound HCFO-1232xd(Z) through isomerization and disproportionation reactions.

[0069] Furthermore, as shown in Tables 1 to 6, in Examples 1-4 to 1-12, 2-4 to 2-12, 3-4 to 3-5, 4-1 to 4-2, 5-1 to 5-2, and 6-1 to 6-2, composite oxide catalysts with excellent raw material conversion rates per unit catalyst mass were obtained, and halogen compounds could be produced using these composite oxide catalysts.

[0070] Furthermore, the disclosure of Japanese Patent Application No. 2025-007021, filed on 17 January 2025, is incorporated herein by reference in its entirety. In addition, all documents, patent applications, and technical standards described herein are incorporated herein by reference to the same extent as if each individual document, patent application, and technical standard were specifically and individually noted to be incorporated by reference.

Claims

1. A composite oxide catalyst comprising constituent elements consisting of Al and at least three elements selected from the group consisting of Cr, Mn, Fe, Co, Ni, Cu, Zn, Pr, La, Gd, Dy, Ce, Nd, Sm, Er, Mg, Zr, Hf, Bi, and In.

2. The composite oxide catalyst according to claim 1, wherein the constituent elements consist of Al and at least three elements selected from the group consisting of Cr, Mn, Fe, Co, Ni, Cu, Zn, Pr, La, Gd, and Dy.

3. The composite oxide catalyst according to claim 1, wherein the constituent elements consist of Al and at least three elements selected from the group consisting of Cr, Mn, Fe, Co, Ni, Cu, and Zn.

4. The composite oxide catalyst according to claim 1, wherein the constituent elements consist of Al, Cr, and at least two elements selected from the group consisting of Mn, Fe, Co, Ni, Cu, and Zn.

5. The composite oxide catalyst according to claim 1, wherein the constituent elements consist of Al, Cr, Ni, and at least one element selected from the group consisting of Mn, Fe, Co, Cu, and Zn.

6. The composite oxide catalyst according to claim 1, wherein the constituent elements consist of Al, Cr, Ni, and at least one element selected from the group consisting of Fe and Zn.

7. The composite oxide catalyst according to claim 1 or 2, wherein the content of the Al element is 60 mol% or more relative to the total amount of the constituent elements.

8. The composite oxide catalyst according to claim 6, wherein the content of Al is 60 to 95 mol% of the total amount of the constituent elements, the content of Cr is 1 to 30 mol% of the total amount of the constituent elements, the content of Ni is 0.1 to 10 mol% of the total amount of the constituent elements, and the combined content of Fe and Zn is 0.1 to 10 mol% of the total amount of the constituent elements.

9. The composite oxide catalyst according to claim 1 or 2, wherein the content of Na element is less than 150 ppm relative to the total amount of the composite oxide catalyst.

10. A method for producing a halogen compound, comprising contacting a first halogen compound with a composite oxide catalyst according to claim 1 or 2, and obtaining a second halogen compound different from the first halogen compound by a halogen exchange reaction.

11. The method for producing a halogen compound according to claim 10, wherein the first halogen compound is chlorodifluoromethane, and the second halogen compound is at least one selected from the group consisting of trifluoromethane, dichlorofluoromethane, and trichloromethane.

12. The method for producing a halogen compound according to claim 10, wherein the first halogen compound is 1,3-dichloro-1,1,2,2,3-pentafluoropropane, and the second halogen compound is at least one selected from the group consisting of 2,2,3-trichloro-1,1,1,3-tetrafluoropropane, 1,3,3-trichloro-1,1,2,2-tetrafluoropropane, 1-chloro-1,1,2,2,3,3-hexafluoropropane, 2,2-dichloro-1,1,1,3,3-pentafluoropropane, 2,3-dichloro-1,1,1,2,3-pentafluoropropane, 1,2-dichloro-1,1,2,3,3-pentafluoropropane, 3,3-dichloro-1,1,1,2,2-pentafluoropropane, and 1,1-dichloro-1,2,2,3,3-pentafluoropropane.

13. The method for producing a halogen compound according to claim 10, wherein the first halogen compound is at least one selected from the group consisting of trifluoromethane and trichloromethane, and the second halogen compound is at least one selected from the group consisting of chlorodifluoromethane and dichlorofluoromethane.

14. The method for producing a halogen compound according to claim 10, wherein the first halogen compound is (Z)-1-chloro-2,3,3-trifluoropropene, and the second halogen compound is at least one selected from the group consisting of 1,2-dichloro-3,3-difluoropropene, 2,3-dichloro-1,3-difluoropropene, 2,3,3,3-tetrafluoropropene, 1,2,3,3-tetrafluoropropene, (E)-1-chloro-2,3,3-trifluoropropene, and 2-chloro-1,3,3-trifluoropropene.

15. The method for producing a halogen compound according to claim 10, wherein the first halogen compound is (Z)-1,2-dichloro-3,3-difluoropropene, and the second halogen compound is at least one selected from the group consisting of (E)-1-chloro-2,3,3-trifluoropropene, (Z)-1-chloro-2,3,3-trifluoropropene, 2-chloro-1,3,3-trifluoropropene, 1,2,3-trichloro-3-fluoropropene, and (E)-1,2-dichloro-3,3-difluoropropene.

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