Catalyst, method for producing catalyst, and method for producing hydrocarbons

Abstract

To provide a novel COx hydrogenation catalyst that enables efficient hydrocarbon production from carbon monoxide or carbon dioxide.SOLUTION: A COx hydrogenation catalyst comprises a composite oxide carrier containing cerium and a trivalent metal element, and cobalt supported on the composite oxide carrier.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a catalyst and a method for producing the same.The present invention also relates to a method for producing hydrocarbons. [Background technology]

[0002] In recent years, various uses of carbon dioxide as a carbon resource have been investigated. For example, Patent Document 1 discloses a method for producing liquid hydrocarbons from carbon dioxide and hydrogen. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 7-80309 Summary of the Invention [Problem to be solved by the invention]

[0004] The present invention relates to a novel CO x An object of the present invention is to provide a hydrogenation catalyst. Another object of the present invention is to provide a method for producing the catalyst, and a method for producing hydrocarbons using the catalyst. [Means for solving the problem]

[0005] The present invention relates to, for example, the following [1] to [9]. [1] A composite oxide support containing cerium and a trivalent metal element; Cobalt supported on the composite oxide support; Including CO x Hydrogenation catalyst. [2] The catalyst according to [1], wherein the metal element is a rare earth element. [3] The catalyst according to [1] or [2], wherein the metal element is a metal element having an ionic radius larger than that of cerium. [4] The catalyst according to any one of [1] to [3], wherein the metal element is selected from the group consisting of La, Sm, Gd and Y. [5] The catalyst according to any one of [1] to [4], wherein in the composite oxide support, a ratio (M2 / (M1+M2)) of the content of the metal element M2 to the sum of the content of cerium M1 and the content of the metal element M2 is, in terms of molar ratio, 0.05 or more and 0.8 or less. [6] The catalyst according to any one of [1] to [5], which is a catalyst for producing hydrocarbons from CO2. [7] A method for producing a catalyst according to any one of [1] to [6], A method for producing a catalyst, comprising a step of supporting cobalt on a composite oxide support containing cerium and a trivalent metal element. [8] mixing an aqueous solution containing a first compound containing cerium and a second compound containing the metal element with a base to obtain a precipitate; calcining the precipitate to obtain the composite oxide support; The method for producing a semiconductor device according to [7], further comprising: [9] A reduction step of contacting the catalyst according to any one of [1] to [6] with a reducing agent; a hydrogenation step of contacting the catalyst that has been subjected to the reduction step with a feed gas containing hydrogen and at least one member selected from the group consisting of carbon monoxide and carbon dioxide to obtain a hydrocarbon; A method for producing hydrocarbons, comprising: Effect of the Invention

[0006] According to the present invention, a novel CO 2 oxidizer capable of efficiently producing hydrocarbons from carbon monoxide or carbon dioxide is provided. x The present invention also provides a hydrogenation catalyst, a method for producing the catalyst, and a method for producing hydrocarbons using the catalyst. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0007] Preferred embodiments of the present invention will now be described in detail.

[0008] The catalyst of this embodiment includes a composite oxide support containing cerium and a trivalent metal element, and cobalt supported on the composite oxide support. x (x is 1 or 2) to obtain a hydrocarbon. x It can be called a hydrogenation catalyst.

[0009] According to the catalyst of the present embodiment, at least one CO selected from the group consisting of carbon monoxide and carbon dioxide x From this, hydrocarbons (particularly, hydrocarbons having 5 or more carbon atoms (hereinafter, also referred to as liquid hydrocarbons)) can be efficiently produced.

[0010] In the catalyst of the present embodiment, for example, compared with a catalyst in which cobalt is supported on a cerium oxide support, x In the hydrogenation reaction of CO, the selectivity of methane is low and the selectivity of liquid hydrocarbons is high. x Liquid hydrocarbons can be efficiently obtained from the

[0011] In the catalyst of this embodiment, the composite oxide support contains cerium and a trivalent metal element, and has oxygen vacancy sites due to the trivalent metal element. x In other words, the catalyst of the present embodiment is thought to contribute to the activation of CO x The activation of increases the probability of chain growth, and CO x It is believed that the selectivity of liquid hydrocarbons in the hydrogenation reaction of

[0012] The composite oxide support contains cerium and a trivalent metal element (hereinafter also referred to as metal element A). In the composite oxide support, cerium may be present as a tetravalent oxide, and metal element A may be present as a trivalent oxide.

[0013] The metal element A may be, for example, a metal element having an ionic radius larger than that of cerium. With such a metal element, the above-mentioned effect of oxygen vacancy sites tends to be more pronounced. In this specification, the ionic radius of the metal element is the ionic radius of a trivalent ion with 8 coordinations.

[0014] The metal element A may be, for example, a rare earth element.

[0015] Examples of the metal element A include La, Sm, Gd, Y, Ho, and Er. Among these, La, Sm, Gd, and Y are preferred, La, Sm, and Gd are more preferred, and La is even more preferred, from the viewpoint of having a large ionic radius and being able to obtain the above-mentioned effects more significantly. Representative examples of the ionic radius are as follows. La:1.160Å, Sm:1.079Å, Gd:1.053Å, Y:1.019Å, Ce:0.9700Å

[0016] In the composite oxide support, the ratio (M2 / (M1+M2)) (molar ratio) of the content M2 of the metal element A to the total amount (M1+M2) of cerium and the metal element A may be, for example, 0.05 or more, and from the viewpoint of obtaining a more significant effect of the oxygen vacancy sites, may be 0.1 or more, 0.3 or more, or 0.5 or more. The above ratio (M2 / (M1+M2)) (molar ratio) may be, for example, 0.8 or less, 0.7 or less, 0.6 or less, or 0.5 or less.

[0017] The composite oxide support may further contain a metal element other than cerium and the metal element A, but is preferably composed mainly of cerium and the metal element A. The total amount of cerium and the metal element A (M1+M2) in the composite oxide support may be, for example, 80 mass% or more, 90 mass% or more, 95 mass% or more, 97 mass% or more, or 99 mass% or more, or may be 100 mass% based on the total amount of metal elements in the composite oxide support.

[0018] The method for producing the composite oxide support is not particularly limited, and it can be produced, for example, by the following method.

[0019] <Method of manufacturing composite oxide support> The method for producing the composite oxide support includes a first step of mixing an aqueous solution containing a first compound containing cerium and a second compound containing metal element A with a base to obtain a precipitate, and a second step of calcining the precipitate to obtain the composite oxide support.

[0020] The first compound may be any compound that contains cerium and is soluble in an aqueous solution. Examples of the first compound include cerium nitrate, cerium sulfate, cerium carbonate, and cerium chloride. From the viewpoint of preventing elements in the first compound from remaining as impurities, cerium nitrate and cerium carbonate are preferred.

[0021] The second compound may be any compound that contains the metal element A and is soluble in an aqueous solution. Examples of the second compound include nitrates, sulfates, carbonates, chlorides, etc., and from the viewpoint that elements in the second compound are unlikely to remain as impurities, nitrates and carbonates are preferred.

[0022] The solid content concentration in the aqueous solution (the total amount of the first compound and the second compound) is not particularly limited, and may be, for example, 1% by mass or more, 3% by mass or more, 10% by mass or more, or 20% by mass or more. The solid content concentration in the aqueous solution may be, for example, 50% by mass or less, 40% by mass or less, 35% by mass or less, or 30% by mass or less.

[0023] The base is not particularly limited as long as it can form a precipitate. Examples of the base include sodium hydroxide, aqueous ammonia, sodium carbonate, potassium hydroxide, etc., and aqueous ammonia is preferred from the viewpoint that elements in the compound are less likely to remain as impurities.

[0024] The amount of base may be any amount that allows sufficient formation of a precipitate, and is preferably, for example, an amount that allows the pH after mixing to be 7 or higher.

[0025] The mixing of the aqueous solution and the base may be mixing of the aqueous solution and the solution containing the base. For example, the mixing of the aqueous solution and the base may be performed by adding the aqueous solution to the solution containing the base (e.g., aqueous ammonia).

[0026] In the first step, the temperature at which the aqueous solution and the base are mixed is not particularly limited, and may be, for example, 10°C to 60°C, or 15°C to 30°C.

[0027] In the first step, a precipitate is obtained that contains cerium and the metal element A. In the first step, the precipitate formed in the aqueous solution may be collected by a known method such as filtration.

[0028] In the second step, the precipitate is calcined to obtain a composite oxide support.

[0029] In the second step, it is preferable to wash the precipitate before calcining it in order to remove impurities. The precipitate is preferably washed with water, more preferably with ion-exchanged water. After washing, it is preferable to dry it. The drying temperature may be, for example, 80° C. or higher, preferably 100° C. or higher. The drying time may be, for example, about several hours.

[0030] The calcination temperature in the second step may be, for example, 300° C. or higher, 350° C. or higher, or 400° C. or higher. The calcination temperature in the second step may be, for example, 800° C. or lower, and from the viewpoint of suppressing a decrease in surface area due to aggregation of the support, may be 600° C. or lower, 500° C. or lower, or 450° C. or lower.

[0031] The amount of cobalt supported on the composite oxide support may be, for example, 1 mass % or more based on the total amount of the catalyst. x From the viewpoint of further improving the reaction activity of the hydrogenation reaction, the amount of cobalt supported on the composite oxide support may be, for example, 30 mass % or less based on the total amount of the catalyst, and from the viewpoint of dispersibility of cobalt, it may be 27 mass % or less, 25 mass % or less, or 23 mass % or less.

[0032] The method for supporting cobalt on the composite oxide support is not particularly limited and may be appropriately selected from known methods (e.g., the incipient wetness method, the evaporation to dryness method, the chemical adsorption method, etc.) From the viewpoint of production costs, the method for supporting cobalt on the composite oxide support is preferably the incipient wetness method.

[0033] The catalyst of the present embodiment can be suitably used, for example, in the following hydrocarbon production method.

[0034] The method for producing hydrocarbons of the present embodiment includes a reduction step of contacting the above-mentioned catalyst with a reducing agent, and a hydrogenation step of contacting the catalyst that has been subjected to the reduction step with a feed gas containing hydrogen and at least one member selected from the group consisting of carbon monoxide and carbon dioxide, to obtain hydrocarbons.

[0035] In the reduction step, the reducing agent may be used as a gas containing the reducing agent (reducing gas) or as a solution containing the reducing agent. When the reducing agent is a reducing gas, the reduction is carried out in the gas phase (gas phase reduction method). When the reducing agent is a solution containing the reducing agent, the reduction is carried out in the liquid phase (liquid phase reduction method).

[0036] The reducing agent may be, for example, hydrogen, NaBH4, hydrazine, etc., preferably hydrogen.

[0037] The reducing gas may contain only the reducing agent or may be diluted with an inert gas, i.e., the reducing gas may further contain an inert gas (e.g., nitrogen, helium, argon, etc.).

[0038] The reducing gas may further contain components other than the reducing agent and the inert gas, such as methane and ethane.

[0039] When a reducing agent is used as the reducing gas, the reduction temperature in the reduction step (the temperature of the catalyst contacted with the reducing gas) may be, for example, 200° C. or higher, 250° C. or higher, 300° C. or higher, or 350° C. or higher. The reduction temperature in the reduction step (the temperature of the catalyst contacted with the reducing gas) may be, for example, 500° C. or lower, and from the viewpoint of suppressing aggregation of cobalt, may be 450° C. or lower, 430° C. or lower, or 420° C. or lower.

[0040] When a reducing agent is used as the reducing gas, the reduction time in the reduction step (the time during which the reducing gas is brought into contact with the catalyst) may be, for example, 1 hour or more, or 2 hours or more. Also, the reduction time in the reduction step (the time during which the reducing gas is brought into contact with the catalyst) may be, for example, 20 hours or less, or 10 hours or less.

[0041] The reduction step may be carried out, for example, by passing a reducing gas through a flow reactor filled with a catalyst, or may be carried out, for example, by a liquid phase reduction method.

[0042] In the hydrogenation process, the raw gas is brought into contact with the catalyst that has been through the reduction process to produce CO x The hydrogenation reaction of carbon monoxide and / or carbon dioxide is carried out. The raw gas is CO x and hydrogen.

[0043] Since the above catalyst has a high selectivity for liquid hydrocarbons in the hydrogenation reaction of carbon dioxide, the raw material gas preferably contains carbon dioxide.

[0044] Conventionally, methods for obtaining hydrocarbons have been known, including a reverse shift reaction for producing carbon monoxide and water from carbon dioxide and hydrogen, and FT synthesis of carbon monoxide. In conventional methods, it was necessary to remove water and carbon dioxide from the reaction gas of the reverse shift reaction, and to supply a mixed gas of carbon monoxide and hydrogen to the FT synthesis. However, in the production method of this embodiment, as described above, liquid hydrocarbons can also be efficiently produced from the hydrogenation reaction of carbon dioxide. Therefore, in the production method of this embodiment, a mixed gas obtained by removing only water from the reaction gas of the reverse shift reaction can be used as a raw material gas.

[0045] In the raw gas, CO x The proportion of carbon dioxide in the total may be, for example, 1 mol % or more, 10 mol % or more, 30 mol % or more, or 50 mol % or more, or may be 100 mol %.

[0046] CO in the feed gas x The content of CO in the raw material gas may be, for example, 1% by volume or more, 2% by volume or more, 5% by volume or more, or 8% by volume or more. x The content may be, for example, 25 vol. % or less, 20 vol. % or less, 15 vol. % or less, or 10 vol. % or less.

[0047] The hydrogen content in the source gas may be, for example, 5 vol% or more, 10 vol% or more, 20 vol% or more, or 30 vol% or more, and the hydrogen content in the source gas may be, for example, 75 vol% or less, 70 vol% or less, 65 vol% or less, or 60 vol% or less.

[0048] The volume ratio of hydrogen to carbon dioxide (H2 / CO2) in the raw material gas may be 1.5 or more, preferably 2 or more, more preferably 2.5 or more, and even more preferably 3 or more. The volume ratio of hydrogen to carbon monoxide (H2 / CO) in the raw material gas may be 0.7 or more, preferably 1 or more, more preferably 1.5 or more, and even more preferably 2 or more.

[0049] The source gas may further contain an inert gas (eg, nitrogen, argon, helium, etc.).

[0050] The content of the inert gas in the raw material gas may be, for example, 5% by volume or more, or 10% by volume or more, and the content of the inert gas in the raw material gas may be, for example, 80% by volume or less, or 50% by volume or less.

[0051] In addition, the raw gas is CO x The raw material gas may further contain other components other than hydrogen and inert gas. Examples of other components include methane. The content of other components in the raw material gas may be, for example, 20% by volume or less, 10% by volume or less, 5% by volume or less, 3% by volume or less, or 1% by volume or less, or may be 0% by volume. That is, the raw material gas may contain CO x The total amount of hydrogen and the inert gas may be, for example, 80 vol.% or more, 90 vol.% or more, 95 vol.% or more, 97 vol.% or more, or 99 vol.% or more, or may be 100 vol.%, based on the total amount of the raw material gas.

[0052] The reaction temperature in the hydrogenation reaction (the temperature of the catalyst contacted with the raw material gas) may be, for example, 180° C. or higher, 200° C. or higher, 220° C. or higher, or 240° C. or higher. The reaction temperature in the hydrogenation reaction (the temperature of the catalyst contacted with the raw material gas) may be, for example, 280° C. or lower, or 260° C. or lower.

[0053] In the hydrogenation reaction, the supply amount of the raw material gas may be appropriately adjusted depending on the amount of catalyst in the reactor, the composition of the raw material gas, etc. -1It may be more than 200h -1 Over 500h -1 or more than 1000h -1 The GHSV of the source gas may be, for example, 10,000 h -1 may be less than 6000h -1 Below, 3000h -1 Less than or equal to 2000h -1 It may be the following.

[0054] In the hydrogenation reaction, the reaction pressure is not particularly limited, and may be, for example, 0.6 MPa (absolute pressure) or more, 0.8 MPa (absolute pressure) or more, or 1.0 MPa (absolute pressure) or more.

[0055] The hydrogenation reaction may be carried out, for example, by flowing the feed gas through a flow reactor packed with a catalyst. The hydrogenation reaction may also be carried out, for example, in a slurry bed reactor.

[0056] In the hydrogenation process, CO x Hydrocarbons are produced by the hydrogenation reaction of the above. In the method for producing hydrocarbons of this embodiment, the selectivity of liquid hydrocarbons in the hydrogenation reaction is excellent due to the use of the above catalyst. Therefore, the production method of this embodiment may be a method for producing liquid hydrocarbons.

[0057] The hydrocarbons may include, for example, methane, hydrocarbons having 2 to 4 carbon atoms, and hydrocarbons having 5 or more carbon atoms (liquid hydrocarbons). The hydrocarbons may be, for example, saturated hydrocarbons (alkanes) or unsaturated hydrocarbons (alkenes).

[0058] Although the preferred embodiments of the present invention have been described above, the present invention is not limited to the above-described embodiments. EXAMPLES

[0059] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0060] (Example A-1) (1) Preparation of Catalyst A-1 Catalyst A-1 was prepared in the following manner. (Manufacture of Carriers) A metal nitrate aqueous solution, in which 0.01 mol of lanthanum nitrate hexahydrate and 0.01 mol of cerium nitrate hexahydrate were dissolved in 20 mL of distilled water, was added dropwise to a 10% aqueous ammonia solution at room temperature while stirring. After stirring at room temperature for 24 hours, the precipitate was filtered and washed. The precipitate was dried overnight at 100°C and then calcined in a calcination furnace at 400°C for 5 hours in air. This produced La 0.5 Ce 0.5 O x As a result, a composite oxide support was obtained. (Production of Catalyst A-1) The carrier obtained above was impregnated with an aqueous solution of cobalt nitrate hexahydrate so that the amount of cobalt supported in the catalyst was 20 mass%. After drying at 80°C for 3 hours and then at 110°C for 21 hours, the carrier was calcined at 400°C for 6 hours in a calcination furnace. Thus, catalyst A-1 was obtained.

[0061] (2) Evaluation of oxygen vacancies The amount of oxygen vacancy sites was evaluated by the following method. The O1s orbital of the support was measured by XPS, and the percentages of oxygen in the CeO2 lattice (OL), hydroxyl groups adsorbed to oxygen vacancies (Ov), and oxygen adsorbed to the carbon tape (Oc) were calculated by peak separation of the obtained spectrum, and the amount of oxygen vacancies (Ov / (OL+Ov)) was calculated.

[0062] (3) Hydrogenation reaction test The hydrogenation reaction of carbon dioxide was carried out and evaluated by the following method. (Reduction of catalyst) A fixed-bed flow reactor was packed with 0.3 g of catalyst, and reduction was carried out at 400°C for 2 hours using 20% ​​H2 / N2 as the reducing gas at 50 mL / min. (Hydrogenation reaction) After the reduction, while flowing the reducing gas, the reaction pressure was set to 1.0 MPa (absolute pressure) and the catalyst layer temperature to 260° C. Then, H2 / CO2 / N2=3 / 1 / 1 was flowed as the reaction gas at 120 mL / min. (Analysis of reaction products) The reaction gas was collected using a gas bag and analyzed using GC-TCD and GC-FID. The liquid product was collected using a gas-liquid separator cooled at 10°C, and after oil / water separation, the produced oil and water were analyzed using GC-FID.

[0063] (Example A-2) (1) Preparation of Catalyst A-2 The carrier (La) was prepared in the same manner as in Example A-1, except that the amount of lanthanum nitrate hexahydrate was changed to 0.006 mol and the amount of cerium nitrate hexahydrate was changed to 0.014 mol. 0.3 Ce 0.7 O x ) and catalyst production was carried out to obtain catalyst A-2. (2) Evaluation of oxygen vacancies The amount of oxygen vacancy sites of catalyst A-2 was evaluated in the same manner as in Example A-1, and the results are shown in Table 1. (3) Hydrogenation reaction test A carbon dioxide hydrogenation reaction was carried out and evaluated in the same manner as in Example A-1, except that Catalyst A-2 was used instead of Catalyst A-1. The results are shown in Table 1.

[0064] (Example A-3) (1) Preparation of Catalyst A-3 The carrier (La) was prepared in the same manner as in Example A-1, except that the amount of lanthanum nitrate hexahydrate was changed to 0.002 mol and the amount of cerium nitrate hexahydrate was changed to 0.018 mol. 0.1 Ce 0.9 O x ) and catalyst production was carried out to obtain catalyst A-3. (2) Hydrogenation reaction test A carbon dioxide hydrogenation reaction was carried out and evaluated in the same manner as in Example A-1, except that Catalyst A-3 was used instead of Catalyst A-1. The results are shown in Table 1.

[0065] (Comparative example a-1) (1) Preparation of catalyst a-1 The same procedure as in Example A-1 was repeated except that lanthanum nitrate hexahydrate was not added and the amount of cerium nitrate hexahydrate was changed to 0.02 mol. x) and catalyst production were carried out to obtain catalyst a-1. (2) Evaluation of oxygen vacancies The amount of oxygen vacancy sites of catalyst a-1 was evaluated in the same manner as in Example A-1. The results are shown in Table 1. (3) Hydrogenation reaction test A carbon dioxide hydrogenation reaction was carried out and evaluated in the same manner as in Example A-1, except that catalyst a-1 was used instead of catalyst A-1. The results are shown in Table 1.

[0066] [Table 1]

[0067] In the table, "M2 / (M1+M2) (molar ratio)" indicates the molar ratio (M2 / (M1+M2)) of the content of metal element A M2 to the sum of the content of cerium M1 and the content of metal element A M2, "C2-C4 selectivity (%)" indicates the selectivity (%) for hydrocarbons having 2 to 4 carbon atoms, and "C5 or more selectivity % (%)" indicates the selectivity (%) for hydrocarbons having 5 or more carbon atoms.

[0068] (Example B-1) (1) Preparation of Catalyst B-1 A catalyst was produced in the same manner as in Example A-1, except that the amount of supported cobalt was changed to 2 mass % (based on the total amount of the catalyst), to obtain Catalyst B-1. (2) Hydrogenation reaction test The hydrogenation reaction of carbon dioxide was carried out and evaluated in the same manner as in Example A-1, except that Catalyst B-1 was used instead of Catalyst A-1. The results are shown in Table 2.

[0069] (Example B-2) (1) Preparation of Catalyst B-2 A catalyst was produced in the same manner as in Example A-1, except that the amount of supported cobalt was changed to 5 mass % (based on the total amount of the catalyst), to obtain catalyst B-2. (2) Hydrogenation reaction test The hydrogenation reaction of carbon dioxide was carried out and evaluated in the same manner as in Example A-1, except that the catalyst B-2 was used instead of the catalyst A-1. The results are shown in Table 2.

[0070] (Example B-3) (1) Preparation of Catalyst B-3 A catalyst was produced in the same manner as in Example A-1, except that the amount of supported cobalt was changed to 10 mass % (based on the total amount of the catalyst), to obtain Catalyst B-3. (2) Hydrogenation reaction test The hydrogenation reaction of carbon dioxide was carried out and evaluated in the same manner as in Example A-1, except that the catalyst B-3 was used instead of the catalyst A-1. The results are shown in Table 2.

[0071] (Example B-4) (1) Preparation of Catalyst B-4 A catalyst was produced in the same manner as in Example A-1 (the amount of supported cobalt was 20 mass % (based on the total amount of the catalyst)), to obtain Example B-4. (2) Hydrogenation reaction test The hydrogenation reaction of carbon dioxide was carried out and evaluated in the same manner as in Example A-1, except that Catalyst B-4 was used instead of Catalyst A-1. The results are shown in Table 2.

[0072] [Table 2]

[0073] (Example C-1) (1) Preparation of Catalyst C-1 Catalyst C-1 was prepared in the following manner. (Manufacture of Carriers) A metal nitrate aqueous solution in which 0.01 mol of yttrium nitrate hexahydrate and 0.01 mol of cerium nitrate hexahydrate were dissolved in 20 mL of distilled water was added dropwise to a 10% aqueous ammonia solution at room temperature while stirring. After stirring at room temperature for 24 hours, the precipitate was filtered and washed. The precipitate was dried overnight at 100°C and then calcined in a calcination furnace at 400°C for 5 hours in air. This produced Y 0.5 Ce 0.5 O x As a result, a composite oxide support was obtained. (Production of Catalyst C-1) The carrier obtained above was impregnated with an aqueous solution of cobalt nitrate hexahydrate so that the amount of cobalt supported in the catalyst was 20 mass%. The catalyst was dried at 80°C for 3 hours and then at 110°C for 21 hours, and then calcined in a calcination furnace at 400°C for 6 hours. Thus, catalyst C-1 was obtained.

[0074] (2) Hydrogenation reaction test The hydrogenation reaction of carbon dioxide was carried out and evaluated by the following method. (Reduction of catalyst) A fixed-bed flow reactor was packed with 0.3 g of catalyst, and reduction was carried out at 400°C for 2 hours using 20% ​​H2 / N2 as the reducing gas at 50 mL / min. (Hydrogenation reaction) After the reduction, while flowing the reducing gas, the reaction pressure was set to 1.0 MPa (absolute pressure) and the catalyst layer temperature to 260° C. Then, H2 / CO2 / N2=3 / 1 / 1 was flowed as the reaction gas at 30 mL / min. (Analysis of reaction products) The reaction gas was collected using a gas bag and analyzed using GC-TCD and GC-FID. The liquid product was collected using a gas-liquid separator cooled at 10°C, and after oil / water separation, the produced oil and water were analyzed using GC-FID.

[0075] (Example C-2) (1) Preparation of Catalyst C-2 Catalyst C-2 was prepared in the following manner. (Manufacture of Carriers) A metal nitrate aqueous solution, in which 0.01 mol of gadolinium nitrate hexahydrate and 0.01 mol of cerium nitrate hexahydrate were dissolved in 20 mL of distilled water, was added dropwise to a 10% aqueous ammonia solution at room temperature while stirring. After stirring for 24 hours at room temperature, the precipitate was filtered and washed. The precipitate was dried overnight at 100°C and then calcined in a calcination furnace at 400°C for 5 hours in air. This produced Gd 0.5 Ce 0.5 O x As a result, a composite oxide support was obtained. (Production of Catalyst C-2) The carrier obtained above was impregnated with an aqueous solution of cobalt nitrate hexahydrate so that the amount of cobalt supported in the catalyst was 20 mass%. After drying at 80°C for 3 hours and then at 110°C for 21 hours, the catalyst was calcined at 400°C for 6 hours in a calcination furnace. Thus, catalyst C-2 was obtained. (2) Hydrogenation reaction test The hydrogenation reaction of carbon dioxide was carried out and evaluated in the same manner as in Example C-1, except that the catalyst C-2 was used instead of the catalyst C-1. The results are shown in Table 3.

[0076] (Example C-3) (1) Preparation of Catalyst C-3 Catalyst C-3 was prepared in the following manner. (Manufacture of Carriers) A metal nitrate aqueous solution, prepared by dissolving 0.01 mol of samarium nitrate hexahydrate and 0.01 mol of cerium nitrate hexahydrate in 20 mL of distilled water, was added dropwise to a 10% aqueous ammonia solution at room temperature while stirring. After stirring for 24 hours at room temperature, the precipitate was filtered and washed. The precipitate was dried overnight at 100°C and then calcined in a calcination furnace at 400°C for 5 hours in air. This produced Sm 0.5 Ce 0.5 O x As a result, a composite oxide support was obtained. (Production of Catalyst C-3) The carrier obtained above was impregnated with an aqueous solution of cobalt nitrate hexahydrate so that the amount of cobalt supported in the catalyst was 20 mass%. After drying at 80°C for 3 hours and then at 110°C for 21 hours, the catalyst was calcined at 400°C for 6 hours in a calcination furnace. Thus, catalyst C-3 was obtained. (2) Hydrogenation reaction test The hydrogenation reaction of carbon dioxide was carried out and evaluated in the same manner as in Example C-1, except that the catalyst C-3 was used instead of the catalyst C-1. The results are shown in Table 3.

[0077] (Example C-4) (1) Preparation of Catalyst C-4 A carrier and a catalyst were prepared in the same manner as in Example A-1 to obtain Catalyst C-4. (2) Hydrogenation reaction test The hydrogenation reaction of carbon dioxide was carried out and evaluated in the same manner as in Example C-1, except that the catalyst C-4 was used instead of the catalyst C-1. The results are shown in Table 3.

[0078] [Table 3]

[0079] (Example D-1) (1) Hydrogenation reaction test Using catalyst A-1, CO was produced by the following method. x The hydrogenation reaction was carried out and evaluated. (Reduction of catalyst) A fixed-bed flow reactor was packed with 0.3 g of catalyst, and reduction was carried out at 400°C for 2 hours using 20% ​​H2 / N2 as the reducing gas flowing at 50 mL / min. (Hydrogenation reaction) After reduction, the hydrogenation reaction was carried out at a reaction pressure of 1.0 MPa (absolute pressure), a reaction gas of H2 / CO / CO2 / N2=55.2 / 17.2 / 7.3 / 20.3 was circulated at 30 mL / min, and the catalyst layer temperature was 200°C, 220°C, or 240°C. (Analysis of reaction products) The reaction gas was collected using a gas bag and analyzed using GC-TCD and GC-FID. The liquid product was collected using a gas-liquid separator cooled at 10°C, and after oil-water separation, the produced oil and water were analyzed using GC-FID. The results are shown in Table 4.

[0080] (Comparative example d-1) A hydrogenation reaction was carried out and evaluated in the same manner as in Example D-1, except that catalyst a-1 was used instead of catalyst A-1. The results are shown in Table 4.

[0081] [Table 4]

[0082] As shown in Table 4, in Example D-1, a higher conversion rate than in Comparative Example d-1 was achieved while maintaining the same level of C5 or higher selectivity as in Comparative Example d-1.

Claims

1. a composite oxide support containing cerium and a trivalent metal element; Cobalt supported on the composite oxide support; Including CO ｘ Hydrogenation catalyst.

2. The catalyst according to claim 1 , wherein the metal element is a rare earth element.

3. The catalyst according to claim 1 , wherein the metal element has an ionic radius larger than that of cerium.

4. 2. The catalyst according to claim 1, wherein the metal element is selected from the group consisting of La, Sm, Gd and Y.

5. In the composite oxide support, the cerium content M １ and the content M of the metal element ２ The content M of the metal element relative to the total ２ The ratio (M ２ / (M １ +M ２ 2. The catalyst according to claim 1, wherein the molar ratio of the catalyst to the catalyst is 0.05 or more and 0.8 or less.

6. CO ２ 10. The catalyst of claim 1, which is a catalyst for producing hydrocarbons from

7. A method for producing the catalyst according to any one of claims 1 to 6, comprising the steps of: A method for producing a catalyst, comprising a step of supporting cobalt on a composite oxide support containing cerium and a trivalent metal element.

8. mixing an aqueous solution containing a first compound containing cerium and a second compound containing the metal element with a base to obtain a precipitate; calcining the precipitate to obtain the composite oxide support; The method of claim 7 further comprising:

9. A reduction step of contacting the catalyst according to any one of claims 1 to 6 with a reducing agent; a hydrogenation step of contacting the catalyst that has been subjected to the reduction step with a feed gas containing hydrogen and at least one member selected from the group consisting of carbon monoxide and carbon dioxide to obtain a hydrocarbon; A method for producing hydrocarbons, comprising:

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