Catalyst composition for catalyzing fischer-tropsch reaction or direct fischer-tropsch reaction

Abstract

The present invention addresses the problem of providing a catalyst composition for catalyzing a Fischer-Tropsch reaction or a direct Fischer-Tropsch reaction, the catalyst composition being capable of suppressing the production of methane by the FT reaction or the direct FT reaction. The present invention provides a catalyst composition for catalyzing a Fischer-Tropsch reaction or a direct Fischer-Tropsch reaction, the catalyst composition containing: (a) an oxide that contains Ba and Co and may contain F; and (b) one or more substances selected from among oxides, carbonates, and nitrates of group 1 elements.

Description

Catalyst composition for catalyzing the Fischer-Tropsch reaction or the direct Fischer-Tropsch reaction

[0001] The present invention relates to a catalyst composition for catalyzing the Fischer-Tropsch reaction (hereinafter referred to as the "FT reaction") or the direct Fischer-Tropsch reaction (hereinafter referred to as the "direct FT reaction").

[0002] In recent years, due to increasingly stringent environmental regulations worldwide and growing environmental awareness, alternative energy sources to replace petroleum resources have attracted attention, particularly CO2 and H2. ２ The FT reaction, which is a reaction that synthesizes hydrocarbons from CO, and CO ２ and H ２ There is growing interest in direct FT reactions, which are reactions that synthesize hydrocarbons from materials. Patent Document 1 discloses an FT reaction catalyst in which a metal selected from iron, cobalt, nickel, and ruthenium is supported on a carrier having a specific average pore size. Patent Document 2 discloses an FT reaction process using a catalyst in which iron-containing particles are dispersed on an α-alumina carrier.

[0003] Japanese Patent Publication No. 2003-24786, Japanese Patent Publication No. 2013-509353

[0004] It is desirable to synthesize hydrocarbons with a large number of carbon atoms (e.g., hydrocarbons with 5 or more carbon atoms) by FT reactions or direct FT reactions. However, it is known that methane is produced by FT reactions or direct FT reactions. The production of methane by FT reactions or direct FT reactions hinders the production of hydrocarbons with a large number of carbon atoms by the same reaction.

[0005] Therefore, the object of the present invention is to provide a catalyst composition that catalyzes an FT reaction or a direct FT reaction and can suppress the production of methane by the FT reaction or the direct FT reaction.

[0006] To solve the above problems, the present invention provides the following catalyst compositions: [1] A catalyst composition for catalyzing a Fischer-Tropsch reaction or a direct Fischer-Tropsch reaction, comprising the following components: (a) an oxide comprising Ba and Co, which may also comprise F; and (b) one or more selected from oxides, carbonates, and nitrates of Group 1 elements. [2] The catalyst composition according to [1], wherein the ratio of the molar amount of Co to the molar amount of Ba is 0.20 or more and 1.20 or less. [3] The catalyst composition according to [1] or [2], wherein the ratio of the molar amount of F to the molar amount of Ba is 0.010 or more and 0.150 or less. [4] The catalyst composition according to any one of [1] to [3], wherein component (a) comprises one or more additional elements selected from Group 3 elements, Group 4 elements, and Group 5 elements. [5] The catalyst composition according to [4], wherein the one or more additional elements are selected from Group 3 elements and Group 4 elements. [6] The catalyst composition according to [4] or [5], wherein the ratio of the molar amount of the one or more additional elements to the molar amount of Ba is 0.40 or more and 0.85 or less. [7] The catalyst composition according to any one of [4] to [6], wherein the ratio of the total molar amount of Co and the one or more additional elements to the molar amount of Ba is 0.70 or more and 1.30 or less. [8] The catalyst composition according to any one of [4] to [7], wherein the ratio of the molar amount of Co to the total molar amount of Co and the one or more additional elements is 0.20 or more and 0.99 or less. [9] The catalyst composition according to any one of [4] to [8], wherein the one or more additional elements include one or more Group 4 elements, and the ratio of the molar amount of the one or more Group 4 elements to the total molar amount of Co and the one or more additional elements is 0.01 or more and 0.70 or less.

[10] The catalyst composition according to any one of [4] to [9], wherein component (a) comprises one or more selected from Y, Ce, and La.

[11] The catalyst composition according to any one of [4] to

[10] , wherein component (a) comprises Zr.

[12] The catalyst composition according to any one of [1] to

[11] , wherein at least a portion of component (b) is supported on component (a).

[13] The catalyst composition according to any one of [1] to

[12] , wherein component (b) comprises one or more selected from oxides, carbonates, and nitrates of Na.

[0007] According to the present invention, there is provided a catalyst composition that catalyzes the Fischer-Tropsch (FT) reaction or the direct FT reaction and can suppress the formation of methane by the FT reaction or the direct FT reaction.

[0008] When the catalyst composition of the present invention catalyzes the FT reaction or the direct FT reaction, it can exhibit an effect of suppressing the formation of methane by the FT reaction or the direct FT reaction (hereinafter referred to as the "methane formation suppression effect").

[0009] When the catalyst composition of the present invention catalyzes the FT reaction or the direct FT reaction, in addition to the methane formation suppression effect, it can exhibit an effect of promoting the formation of hydrocarbons having 5 or more carbon atoms by the FT reaction or the direct FT reaction (hereinafter referred to as the "C5+ formation promotion effect").

[0010] FIG. 1 is an XRD diffraction chart obtained by performing X-ray diffraction (XRD) on sample powders obtained by grinding each catalyst composition of Example 1 and Comparative Example 2 in an agate mortar, and on sample powders obtained by grinding each reference compound of BaZrO ３ , BaCO ３ , Co ３ O ４ and ZrO ２ in an agate mortar.

[0011] <<Catalyst Composition>> Hereinafter, the catalyst composition of the present invention (hereinafter referred to as "this composition") will be described.

[0012] This composition is a catalyst composition that catalyzes the FT reaction or the direct FT reaction.

[0013] The FT reaction is a reaction for synthesizing hydrocarbons from CO and H ２ and is represented by the following reaction formula. nCO + 2nH ２ → - (CH ２ ) ｎ - + nH ２ O

[0014] The direct FT reaction is a reaction for synthesizing hydrocarbons from CO ２ and H ２ and is represented by the following reaction formulas (1) and (2). CO ２+H ２ →CO+H ２ O...(1) nCO+2nH ２ →-(CH ２ ) ｎ - + nH ２ O ... (2)

[0015] The reaction represented by reaction equation (1) is a reverse water-gas shift reaction (hereinafter referred to as the "RWGS reaction"), and the reaction represented by reaction equation (2) is an FT reaction. The CO produced by the RWGS reaction is used as the raw material gas for the FT reaction.

[0016] When this catalyst composition catalyzes a direct FT reaction, it catalyzes a series of reactions including an RWGS reaction and an FT reaction carried out using CO produced by the RWGS reaction as the source gas.

[0017] The catalyst composition is, for example, in powder form. The catalyst composition may also be molded into any desired form, such as pellets or layers.

[0018] This catalyst composition comprises the following components: (a) an oxide containing Ba and Co, which may also contain F; and (b) one or more selected from oxides, carbonates, and nitrates of Group 1 elements.

[0019] This catalyst composition can exhibit a methane production suppression effect when catalyzing FT reactions or direct FT reactions. The methane production suppression effect can be evaluated based on the CH4 selectivity. Specifically, the lower the CH4 selectivity, the greater the methane production suppression effect. The significance of CH4 selectivity is as described in the examples.

[0020] This catalyst composition can exhibit both a methane production suppression effect and a C5+ production promotion effect when catalyzing FT reactions or direct FT reactions. The C5+ production promotion effect can be evaluated based on the C5+ selectivity. Specifically, the higher the C5+ selectivity, the greater the C5+ production promotion effect. The significance of C5+ selectivity is as described in the examples.

[0021] The component (a) is described below.

[0022] Component (a) is, for example, particulate.

[0023] Component (a) may or may not contain F. If component (a) does not contain F, component (a) is a complex oxide. If component (a) contains F, component (a) is a complex acid fluoride.

[0024] Each composite oxide and composite oxyfluoride contains two or more metallic elements. These two or more metallic elements consist of Ba, Co, and optionally one or more additional elements M. The additional elements M will be described later.

[0025] A composite oxide is a composite of two or more metal oxides. In the composite, the two or more metal oxides are chemically bonded. The composite also includes a solid solution of two or more metal oxides. In the present invention, the two or more metal oxides consist of an oxide of Ba, an oxide of Co, and optionally an oxide of one or more additional elements M. The oxide of Ba is BaO. The oxide of Co is CoO, Co ２ O ３ and Co ３ O ４ It is one or more selected from the following. The oxide of Co is preferably Co ３ O ４ The oxides of the additional element M will be discussed later.

[0026] Complex oxyfluorides are compounds in which some of the oxygen atoms in a complex oxide are replaced by fluorine atoms.

[0027] The Co contained in component (a) functions as a catalytically active component that catalyzes the FT reaction and the RWGS reaction. The catalytically active component is the raw material gas (CO ２ CO, H ２ It is involved in the adsorption and dissociation of ), activation of reaction intermediates on the surface of the catalyst composition, and stabilization of reaction intermediates retained on the surface of the catalyst composition.

[0028] The Co contained in component (a) is H in the raw material gas of the FT reaction or direct FT reaction. ２By means of this, or by a reduction treatment performed on the catalyst composition before using it in an FT reaction or a direct FT reaction, it can be reduced to metallic Co. When the Co contained in component (a) is reduced, methane production is promoted and the production of hydrocarbons with 5 or more carbon atoms is suppressed. Therefore, from the viewpoint of improving the methane production suppression effect and the C5+ production promotion effect, it is preferable that the reduction of the Co contained in component (a) is suppressed (i.e., the oxidation state of the Co contained in component (a) is maintained).

[0029] The Ba contained in component (a) contributes to improving the methane production suppression effect and the C5+ production promotion effect.

[0030] The Ba contained in component (a) has the effect of suppressing the reduction of Co contained in component (a) and raising the reduction initiation temperature of Co contained in component (a). These effects are thought to contribute to the improvement of the methane production suppression effect and the C5+ production promotion effect. Furthermore, the higher the reduction initiation temperature of Co contained in component (a), the greater the tendency for the methane production suppression effect and the C5+ production promotion effect to improve.

[0031] The Ba contained in component (a) has the effect of assisting in the formation of complex oxides or complex acid fluorides. That is, complex oxides or complex acid fluorides containing Co and optionally one or more additional elements M but not Ba are difficult to form, but complex oxides or complex acid fluorides containing Co and optionally one or more additional elements M, as well as Ba, are easily formed.

[0032] The F contained in component (a) contributes to the improvement of the methane production suppression effect and the C5+ production promotion effect. The F contained in component (a) has the effect of stabilizing the oxidation state of the Co contained in component (a) and raising the reduction initiation temperature of the Co contained in component (a). These effects are thought to be involved in the improvement of the methane production suppression effect and the C5+ production promotion effect.

[0033] From the viewpoint of improving the methane production suppression effect and the C5+ production promotion effect, the ratio of the molar amount of Co to the molar amount of Ba (hereinafter referred to as "ratio R1") is preferably 0.20 or more and 1.20 or less, more preferably 0.40 or more and 1.00 or less, and even more preferably 0.40 or more and 0.60 or less. Each of the above lower limits may be combined with any of the above upper limits.

[0034] When component (a) contains F, from the viewpoint of improving the methane production suppression effect and the C5+ production promotion effect, the ratio of the molar amount of F to the molar amount of Ba (hereinafter referred to as "ratio R2") is preferably 0.010 or more and 0.150 or less, more preferably 0.060 or more and 0.100 or less, and even more preferably 0.065 or more and 0.090 or less. Each of the above lower limits may be combined with any of the above upper limits.

[0035] Component (a) may contain one or more additional elements M. The one or more additional elements M are selected from metallic elements other than Ba ​​and Co.

[0036] From the viewpoint of improving the methane production suppression effect and the C5+ production promotion effect, it is preferable that one or more additional elements M be selected from group 3 elements, group 4 elements, and group 5 elements, and more preferably from group 3 elements and group 4 elements.

[0037] The Group 3, Group 4, or Group 5 elements contained in component (a) contribute to the improvement of the methane production suppression effect and the C5+ production promotion effect. The Group 3, Group 4, or Group 5 elements contained in component (a) have the effect of suppressing the reduction of Co contained in component (a) and raising the reduction initiation temperature of Co contained in component (a). These effects are thought to be involved in the improvement of the methane production suppression effect and the C5+ production promotion effect.

[0038] Group 3 elements include Sc, Y, lanthanides, and actinides. Lanthanides are ５７ La~ ７１ Lu, actinoids ８９ Ac~ ９９ It is Es. Sc, Y, and lanthanides are collectively called rare earth elements. Oxides of rare earth elements other than Ce, Pr, and Tb are sesquioxides M２ O ３ (M represents rare earth elements other than Ce, Pr, and Tb), Ce oxides are CeO ２ , the oxide of Pr is Pr ６ O １１ The oxide of Tb is Tb ４ O ７ The oxides of actinides other than U are M ２ O ３ (M represents actinide elements excluding U), U oxide is UO ３ That is the case.

[0039] The improvement in the methane production suppression effect and C5+ production promotion effect due to the third group elements contained in component (a) is more pronounced when component (a) is a complex acid fluoride than when component (a) is a complex oxide. Therefore, when component (a) contains third group elements, it is preferable that component (a) is a complex acid fluoride.

[0040] From the viewpoint of improving the methane production suppression effect and the C5+ production promotion effect, the group 3 element is preferably selected from Y, Ce, and La, and more preferably selected from Y and Ce.

[0041] In one embodiment, component (a) comprises one or more elements selected from Y, Ce, and La. Component (a) may also contain other additional elements M.

[0042] Group 4 elements include Ti, Zr, and Hf. The oxide of Ti is TiO ２ Zr oxide is ZrO ２ Hf oxides are HfO ２ That is the case.

[0043] The improvement in the methane production suppression effect and C5+ production promotion effect due to the Group 4 elements contained in component (a) is significant whether component (a) is a composite oxide or a composite acid fluoride. Therefore, if component (a) contains Group 4 elements, component (a) may be either a composite oxide or a composite acid fluoride.

[0044] From the viewpoint of improving the methane production suppression effect and the C5+ production promotion effect, the Group 4 element is preferably Zr.

[0045] In one embodiment, component (a) contains Zr. Component (a) may also contain other additional elements M.

[0046] Group 5 elements include V, Nb, and Ta. The oxides of V are V ２ O ３ Nb oxides are Nb ２ O ５ Ta oxides are Ta ２ O ５ That is the case.

[0047] From the viewpoint of improving the methane production suppression effect and the C5+ production promotion effect, the Group 5 element is preferably Nb.

[0048] From the viewpoint of improving the methane production suppression effect and the C5+ production promotion effect, it is preferable that one or more additional elements M are selected from group 3 elements, group 4 elements, and group 5 elements, and that one or more group 4 elements are included.

[0049] The one or more additional elements M may consist of one or more Group 4 elements, or one or more Group 4 elements and one or more Group 3 elements and / or one or more Group 5 elements. In the latter case, from the viewpoint of improving the methane production suppression effect and the C5+ production promotion effect, it is preferable that the one or more additional elements M consist of one or more Group 4 elements and one or more Group 3 elements. It is preferable that the one or more Group 4 elements include Zr. It is preferable that the one or more Group 3 elements include Y and / or Ce, and more preferably Y.

[0050] In one embodiment, one or more additional elements M are composed of Zr. In another embodiment, one or more additional elements M are composed of Y and Zr. In yet another embodiment, one or more additional elements M are composed of Ce and Zr.

[0051] When one or more additional elements M are selected from Group 3, Group 4, and Group 5 elements (especially when one or more additional elements M are selected from Group 3, Group 4, and Group 5 elements, and one or more Group 4 elements are included), from the viewpoint of improving the methane production suppression effect and the C5+ production promotion effect, the ratio of the molar amount of one or more additional elements M to the molar amount of Ba (hereinafter referred to as "ratio R3") is preferably 0.40 or more and 0.85 or less, more preferably 0.70 or more and 0.80 or less, and even more preferably 0.73 or more and 0.77 or less. Each of the above lower limits may be combined with any of the above upper limits. When component (a) contains two or more additional elements M, "molar amount of one or more additional elements M" means the total molar amount of the two or more additional elements M (the same applies hereinafter).

[0052] When one or more additional elements M are selected from Group 3, Group 4, and Group 5 elements (especially when one or more additional elements M are selected from Group 3, Group 4, and Group 5 elements and include one or more Group 4 elements), from the viewpoint of improving the methane production suppression effect and the C5+ production promotion effect, the ratio of the total molar amount of Co and one or more additional elements M to the molar amount of Ba (hereinafter referred to as "ratio R4") is preferably 0.70 or more and 1.30 or less, more preferably 0.95 or more and 1.30 or less, and even more preferably 1.00 or more and 1.20 or less. Each of the above lower limits may be combined with any of the above upper limits.

[0053] When one or more additional elements M are selected from Group 3, Group 4, and Group 5 elements (especially when one or more additional elements M are selected from Group 3, Group 4, and Group 5 elements and include one or more Group 4 elements), from the viewpoint of improving the methane production suppression effect and the C5+ production promotion effect, the ratio of the molar amount of Co to the total molar amount of Co and one or more additional elements M (hereinafter referred to as "ratio R5") is preferably 0.20 or more and 0.99 or less, more preferably 0.25 or more and 0.60 or less, and even more preferably 0.30 or more and 0.40 or less. Each of the above lower limits may be combined with any of the above upper limits.

[0054] When one or more additional elements M are selected from Group 3, Group 4, and Group 5 elements, and one or more Group 4 elements are included, from the viewpoint of improving the methane production suppression effect and the C5+ production promotion effect, the ratio of the molar amount of one or more Group 4 elements to the total molar amount of Co and one or more additional elements M (hereinafter referred to as "ratio R6") is preferably 0.01 or more and 0.70 or less, more preferably 0.20 or more and 0.50 or less, and even more preferably 0.38 or more and 0.48 or less. Each of the above lower limits may be combined with any of the above upper limits. When component (a) contains two or more Group 4 elements, "molar amount of one or more Group 4 elements" means the total molar amount of two or more Group 4 elements (the same applies hereinafter).

[0055] From the viewpoint of improving the methane production suppression effect and the C5+ production promotion effect, the ratio of the molar amount of Ba to the total molar amount of all metal elements contained in component (a) (hereinafter referred to as "ratio R7") is preferably 0.40 or more and 0.55 or less, more preferably 0.43 or more and 0.48 or less, and even more preferably 0.44 or more and 0.46 or less. Each of the above lower limits may be combined with any of the above upper limits.

[0056] In one embodiment, all the metallic elements contained in component (a) are Ba and Co.

[0057] In another embodiment, all metal elements contained in component (a) are Ba, Co, and one or more additional elements M.

[0058] R1 to R7 can be determined by the following methods. Compositional analysis and quantitative analysis of the catalyst composition are performed by X-ray fluorescence analysis (XRF) to identify all metal elements contained in component (a) and measure the molar amount of each identified metal element. XRF can be performed according to the conditions described in the examples. The molar amount of F is measured by performing quantitative analysis of F using the fluoride ion electrode method on the catalyst composition. The fluoride ion electrode method can be performed according to the conditions described in the examples. R1 and R3 to R7 can be determined from the XRF results. R2 can be determined from the XRF results and the fluoride ion electrode method results.

[0059] Component (a) preferably contains a composite oxide or composite acid fluoride having a perovskite-type structure. The presence of a composite oxide or composite acid fluoride having a perovskite-type structure in component (a) can be confirmed by assigning peaks in the XRD diffraction pattern of the composition. Component (a) may contain a composite oxide or composite acid fluoride having a structure other than a perovskite-type structure, but it is preferable that it is composed of a composite oxide or composite acid fluoride having a perovskite-type structure.

[0060] In one embodiment, the composite oxide having a perovskite-type structure has a stoichiometric composition represented by the following compositional formula (1) or (2): BaCoO ３ ...(1) BaCo ｘ M １－ｘ O ３ ... (2)

[0061] In another embodiment, the complex acid fluoride having a perovskite-type structure has a stoichiometric composition represented by the following compositional formula (3): Ba(Co ｘ M １－ｘ ) ｗ O ｙ F ｚ ... (3)

[0062] In compositional formulas (2) and (3), M represents one or more additional elements M.

[0063] From the viewpoint of improving the methane production suppression effect and the C5+ production promotion effect, w is preferably 0.50 to 1.50, more preferably 0.75 to 1.25, and even more preferably 0.78 to 1.02. Each of the above lower limits may be combined with any of the above upper limits. In one embodiment, w is 1.00. In another embodiment, w is 0.80.

[0064] From the viewpoint of improving the methane production suppression effect and the C5+ production promotion effect, x is preferably 0.05 to 0.95, more preferably 0.20 to 0.60, and even more preferably 0.35 to 0.45. Each of the above lower limits may be combined with any of the above upper limits.

[0065] From the perspective of improving the methane generation inhibition effect and the C5+ generation promotion effect, y is preferably 1.50 or more and 6.00 or less, more preferably 2.00 or more and 5.00 or less, still more preferably 2.00 or more and 4.00 or less, and still more preferably 2.50 or more and 3.50 or less. Each of the above lower limit values may be combined with any of the above upper limit values.

[0066] From the perspective of improving the methane generation inhibition effect and the C5+ generation promotion effect, z is preferably 0.01 or more and 0.30 or less, more preferably 0.04 or more and 0.15 or less, and still more preferably 0.60 or more and 0.90 or less. Each of the above lower limit values may be combined with any of the above upper limit values.

[0067] When one or more additional elements M are composed of Zr, the composition formula (2) is BaCo ｘ Zr １－ｘ O ３ , and the composition formula (3) is Ba(Co ｘ Zr １－ｘ ) ｗ O ｙ F ｚ .

[0068] When one or more additional elements M are composed of Zr and Y, the composition formula (2) is BaCo ｘ Zr ａ Y １－ｘ－ａ O ３ , and the composition formula (3) is Ba(Co ｘ Zr ａ Y １－ｘ－ａ ) ｗ O ｙ F ｚ .

[0069] When one or more additional elements M are composed of Zr and Ce, the composition formula (2) is BaCo ｘ Zr ａ Ce １－ｘ－ａ O ３ , and the composition formula (3) is Ba(Co ｘ Zr ａ Ce １－ｘ－ａ ) ｗ O ｙ F ｚ .

[0070] From the viewpoint of improving the methane production suppression effect and the C5+ production promotion effect, a is preferably 0.10 to 0.90, more preferably 0.15 to 0.80, and even more preferably 0.55 to 0.65. Each of the above lower limits may be combined with any of the above upper limits.

[0071] From the viewpoint of improving the methane production suppression effect and the C5+ production promotion effect, the percentage of the mass of component (a) relative to the mass of the catalyst composition (hereinafter referred to as "percentage P1") is preferably 90.0% by mass or more and 99.9% by mass or less, more preferably 95.0% by mass or more and 99.5% by mass or less, and even more preferably 97.0% by mass or more and 99.0% by mass or less. Each of the above lower limits may be combined with any of the above upper limits.

[0072] The percentage P1 can be determined from the composition of the raw materials used in the production of the catalyst composition, but it is preferable to measure it by method A described below.

[0073] The component (b) is described below.

[0074] At least some of the Group 1 elements are preferably present in one or more states selected from oxides and carbonates, and more preferably in the oxide state.

[0075] Component (b) is, for example, particulate.

[0076] Component (b) is a co-catalyst component, and the raw material gas (CO ２ CO, H ２ It is involved in the enhancement of adsorption of ) and the promotion of reaction intermediate formation by donating electrons to the catalytically active component, and the stabilization of the bond between the catalytically active component and the reaction intermediate by donating electrons to the catalytically active component (stabilization of the reaction intermediate retained on the surface of the catalyst composition through the bond between the catalytically active component and the reaction intermediate).

[0077] If component (b) is composed of two or more components (for example, oxides of two or more Group 1 elements), component (b) may be a mixture of the two or more components or a complex of the two or more components. In the complex, the two or more components are chemically bonded together. The complex also includes solid solutions of the two or more components.

[0078] The Group 1 elements include Li, Na, K, Rb, Cs, and Fr. The oxide of the Group 1 element is A ２ O (where A represents the Group 1 element). The carbonate of the Group 1 element is A ２ CO ３ (where A represents the Group 1 element). The nitrate of the Group 1 element is ANO ３ (where A represents the Group 1 element).

[0079] From the viewpoint of enhancing the action of component (b), component (b) preferably contains one or more selected from oxides, carbonates, and nitrates of Na, more preferably contains one or more selected from oxides and carbonates of Na, and even more preferably contains an oxide of Na.

[0080] From the viewpoint of enhancing the action of component (b), at least a part of component (b) is preferably supported on component (a).

[0081] From the viewpoint of enhancing the action of component (b), the percentage of the mass of component (b) with respect to the mass of the present catalyst composition (hereinafter referred to as "percentage P2") is preferably 0.1% by mass or more and 10.0% by mass or less, more preferably 0.5% by mass or more and 5.0% by mass or less, and even more preferably 1.0% by mass or more and 3.0% by mass or less. Any of the above lower limit values may be combined with any of the above upper limit values.

[0082] Percentage P2 can be determined from the composition of the raw materials used in the production of the catalyst composition, but it is preferably measured by Method A described below.

[0083] From the viewpoint of improving the methane generation inhibitory effect and the C5+ generation promoting effect and enhancing the action of component (b), the percentage of the total mass of components (a) and (b) with respect to the mass of the present catalyst composition is preferably 5.0% by mass or more, more preferably 50.0% by mass or more, even more preferably 80.0% by mass or more, even more preferably 90.1% by mass or more, more preferably 95.5% by mass or more, and even more preferably 98.0% by mass or more. The upper limit is 100% by mass. In one embodiment, the sum of percentage P1 and P2 is 100% by mass.

[0084] [Method A] Method A for measuring percentages P1 and P2 will be described below. Compositional analysis and quantitative analysis will be performed on the catalyst composition by XRF to identify all metal elements contained in the catalyst composition, all metal elements contained in component (a), and all metal elements contained in component (b), and the molar amount of each identified metal element will be measured. XRF can be performed according to the conditions described in the examples. From the XRF results, the oxide equivalent mass of each metal element will be calculated. "Oxide equivalent mass of metal element" means the mass of the oxide of the metal element obtained by assuming that the metal element exists as an oxide of the metal element. For Co, Co ３ O ４ The converted mass is the mass of Co in terms of oxides. A quantitative analysis of F is performed on the catalyst composition using the fluoride ion electrode method to measure the molar amount of F. The fluoride ion electrode method can be performed according to the conditions described in the examples. The mass of F is calculated from the results of the fluoride ion electrode method. The sum of the total mass of all metal elements in component (a) in terms of oxides and the mass of F is determined and taken as the mass of component (a). The total mass of all metal elements in component (b) in terms of oxides is determined and taken as the mass of component (b). The sum of the total mass of all metal elements in the catalyst composition in terms of oxides and the mass of F is determined and taken as the mass of the catalyst composition. Percentage P1 is determined from the mass of component (a) and the mass of the catalyst composition, and percentage P2 is determined from the mass of component (b) and the mass of the catalyst composition.

[0085] ≪Method for Manufacturing the Catalyst Composition≫ The method for manufacturing this catalyst composition will be described below.

[0086] If component (a) is a composite oxide, component (a) can be produced by mixing, for example, an oxide of barium carbonate, cobalt(II) oxide, and optionally one or more additional elements M, and firing the mixture. If component (a) is a composite acid fluoride, component (a) can be produced by mixing, for example, an oxide of barium carbonate, cobalt(II) oxide, barium fluoride, and optionally one or more additional elements M, and firing the mixture. In the production of component (a), the firing temperature can be, for example, 900°C to 2000°C, preferably 1200°C to 1400°C, and the firing time can be, for example, 4 hours to 20 hours, preferably 8 hours to 12 hours, and the firing can be carried out in an oxidizing atmosphere such as an air atmosphere.

[0087] This catalyst composition can be produced, for example, by impregnating component (a) with a solution containing the raw materials for component (b) and then calcining it. Specifically, the process is as follows: Component (a) is added to a solution containing the raw materials for component (b) and stirred. The resulting dispersion is dried and heated to obtain a powder. The obtained powder is dried, and the dried powder is calcined. In the catalyst composition thus obtained, at least a portion of component (b) is supported on component (a). Drying and calcination can be carried out according to conventional methods. The drying temperature is, for example, 30°C to 100°C, preferably 55°C to 65°C, and the drying time is, for example, 1 hour to 12 hours, preferably 5 hours to 7 hours. The calcination temperature is, for example, 300°C to 500°C, preferably 380°C to 420°C, and the calcination time is, for example, 1 hour to 8 hours, preferably 2 hours to 4 hours. Calcination can be carried out under an oxidizing atmosphere such as an air atmosphere.

[0088] A solution containing the raw materials for component (b) can be prepared by dissolving the raw materials for component (b) in water. As the raw materials for component (b), for example, a water-soluble salt of a group 1 element can be used. The water-soluble salt can be selected from, for example, nitrates, chlorides, acetates, etc. If the group 1 element is Na, as the raw materials for component (b), for example, a water-soluble Na salt such as sodium nitrate, sodium chloride, or sodium acetate can be used.

[0089] When a nitrate of a Group 1 element is used as a raw material for component (b), at least a portion of the nitrate of the Group 1 element will become an oxide of the Group 1 element upon calcination. Some of the nitrate of the Group 1 element may remain in the form of nitrate (nitrate oxide) of the Group 1 element even after calcination. The oxide of the Group 1 element may react with carbon dioxide in the air to become a carbonate of the Group 1 element.

[0090] <<Method for Producing Hydrocarbons>> The following describes a method for producing hydrocarbons using this catalyst composition.

[0091] The method for producing hydrocarbons using this catalyst composition includes the production method according to the first embodiment and the production method according to the second embodiment.

[0092] <First Embodiment> The manufacturing method according to the first embodiment involves the presence of the catalyst composition, CO gas and H ２ This process includes contacting a gas to produce hydrocarbons.

[0093] It is preferable that this catalyst composition be used in the above process after undergoing a reduction treatment. When this catalyst composition is subjected to a reduction treatment, component (b) is reduced. For example, a nitrate of a group 1 element is converted to an oxide of a group 1 element. The reduction of component (b) is CO ２ This is thought to contribute to an increase in adsorption sites and improved electron donating from component (b) to the active component. The reduction treatment can be carried out, for example, by heat-treating the catalyst composition in a hydrogen atmosphere at a temperature of 300°C to 400°C for 0.5 hours to 3 hours.

[0094] In the above process, CO gas and H in the presence of the catalyst composition ２ By contacting the gas, the FT reaction proceeds, producing hydrocarbons. The reaction conditions are not particularly limited, as long as the FT reaction can proceed. ２ The gas / CO gas molar ratio is, for example, 1 / 1 to 4 / 1, preferably 1.5 / 1 to 2.5 / 1. The space velocity is, for example, 1000 h. －１ Over 50,000 hours －１ Preferably 9500h －１ Over 40,500 hours －１The following conditions apply: The temperature is, for example, 200°C to 450°C, preferably 300°C to 400°C. The pressure is, for example, 0.5 MPa to 20 MPa, preferably 2.5 MPa to 5.0 MPa. The reaction time is, for example, 1 hour to 1000 hours, preferably 1.5 hours to 100 hours.

[0095] <Second Embodiment> The manufacturing method according to the second embodiment is: (i) in the presence of the catalyst composition, CO ２ Gas and H ２ (ii) A step of bringing the CO gas produced in step (i) into contact with H ２ This process includes contacting a gas to produce hydrocarbons.

[0096] The catalyst composition is preferably used in step (i) after undergoing a reduction treatment. The description of the reduction treatment is the same as in the first embodiment.

[0097] In step (i), CO is used in the presence of the catalyst composition. ２ Gas and H ２ By contacting it with gas, the RWGS reaction proceeds, CO ２ CO gas is produced from gas. ２ Gas and H ２ The conditions for contacting the gas are not particularly limited, as long as the RWGS reaction can proceed. ２ Gas / CO ２ The molar ratio of the gas is, for example, 1 / 1 to 5 / 1, preferably 2 / 1 to 4 / 1. The space velocity is, for example, 1000 h. －１ Over 50,000 hours －１ Preferably 9500h －１ Over 40,500 hours －１ The following conditions apply: The temperature is, for example, 200°C to 450°C, preferably 300°C to 400°C. The pressure is, for example, 0.5 MPa to 20 MPa, preferably 2.5 MPa to 5.0 MPa. The reaction time is, for example, 1 hour to 1000 hours, preferably 1.5 hours to 100 hours.

[0098] In step (ii), the CO gas produced in step (i) and H are used in the presence of the catalyst composition.２ By contacting the gas, the FT reaction proceeds, producing hydrocarbons. CO gas and H ２ The conditions for contacting the gas are not particularly limited as long as the FT reaction can proceed. The specific conditions are the same as those for the manufacturing method according to the first embodiment. The FT reaction and the RWGS reaction may be carried out in the same reactor or in separate reactors.

[0099] According to the manufacturing method of the first or second embodiment, the production of methane by the FT reaction or direct FT reaction can be suppressed. Furthermore, the production of hydrocarbons having 5 or more carbon atoms by the FT reaction or direct FT reaction can be promoted.

[0100] Hydrocarbons include chain-type saturated hydrocarbons (alkanes), chain-type unsaturated hydrocarbons (alkenes and alkynes), cyclic saturated hydrocarbons (cycloalkanes), and cyclic unsaturated hydrocarbons (cycloalkenes and cycloalkynes). Hydrocarbons are preferably alkanes, alkenes, and alkynes.

[0101] Examples of hydrocarbons having five or more carbon atoms include pentane, 2-methylbutane, 2-pentene, 1-pentine, hexane, heptane, 1-heptene, 2-methyloctane, and 1-decene.

[0102] <Example 1> Barium carbonate, zirconium oxide, yttrium oxide, cobalt(II) oxide, and barium fluoride were weighed so that the molar ratio of Ba, Co, Zr, Y, and F was Ba:Co:Zr:Y:F = 1:0.4:0.4:0.2:0.1, and these were mixed in a ball mill for more than 10 hours. The resulting mixed powder was calcined at 1300°C for 10 hours in the Tammann tube of a Tammann-type electric furnace in air generated by an air compressor, and BaCo ０．４ Zr ０．４ Y ０．２ O ｙ F ０．１ A complex acid fluoride having a starting composition of (2 ≤ y ≤ 4) was obtained.

[0103] Using the impregnation-supporting method, Na was supported on the obtained composite acid fluoride, and the catalyst composition of Example 1 (Na / BaCo ０．４ Zr ０．４Y ０．２ O ｙ F ０．１ ) was obtained. Specifically, the following was done: 0.376 g of sodium nitrate was dissolved in 50 g of pure water to prepare an aqueous sodium nitrate solution. 5 g of complex acid fluoride was added to the aqueous sodium nitrate solution and stirred to obtain a dispersion. The obtained dispersion was reduced to 70 Pa using an evaporator and heated to 60°C using a water bath to obtain a powder. The obtained powder was dried overnight in a drying oven (atmospheric atmosphere) at 100°C. The dried powder was calcined at 400°C for 3 hours to obtain the catalyst composition of Example 1. At least a portion of the Na nitrate becomes Na oxide upon calcination. A portion of the Na nitrate may remain in the form of Na nitrate (nitrate oxide) even after calcination. The Na oxide can react with carbon dioxide in the air to become Na carbonate.

[0104] <Example 2> The same procedure as in Example 1 was carried out, except that barium carbonate, zirconium oxide, cerium oxide, cobalt(II) oxide, and barium fluoride were weighed so that the molar ratio of Ba, Co, Zr, Ce, and F was Ba:Co:Zr:Ce:F = 1:0.4:0.4:0.2:0.1. ０．４ Zr ０．４ Ce ０．２ O ｙ F ０．１ A composite acid fluoride having a starting composition of (2 ≤ y ≤ 4) is obtained, Na is supported on the obtained composite acid fluoride, and the catalyst composition of Example 2 (Na / BaCo ０．４ Zr ０．４ Ce ０．２ O ｙ F ０．１ ) was obtained.

[0105] <Example 3> The same procedure as in Example 1 was carried out, except that barium carbonate and cobalt(II) oxide were weighed so that the molar ratio of Ba to Co was Ba:Co = 1:1, resulting in BaCoO ３ A composite oxide having the following composition is obtained, Na is supported on the obtained composite oxide, and the catalyst composition of Example 3 (Na / BaCoO ３ ) was obtained.

[0106] <Example 4> The same procedure as in Example 1 was carried out, except that barium carbonate, zirconium oxide, cobalt(II) oxide, and barium fluoride were weighed so that the molar ratio of Ba, Co, Zr, and F was Ba:Co:Zr:F = 1:0.4:0.6:0.1. ０．４ Zr ０．６ O ｙ F ０．１ A composite acid fluoride having a starting composition of (2 ≤ y ≤ 4) is obtained, Na is supported on the obtained composite acid fluoride, and the catalyst composition of Example 4 (Na / BaCo ０．４ Zr ０．６ O ｙ F ０．１ ) was obtained.

[0107] <Example 5> The same procedure as in Example 1 was carried out, except that barium carbonate, zirconium oxide, and cobalt(II) oxide were weighed so that the molar ratio of Ba, Co, and Zr was Ba:Co:Zr = 1:0.4:0.6. ０．４ Zr ０．６ O ３ A composite oxide having the following composition is obtained, Na is supported on the obtained composite oxide, and the catalyst composition of Example 5 (Na / BaCo ０．４ Zr ０．６ O ３ ) was obtained.

[0108] <Example 6> The same procedure as in Example 1 was carried out, except that barium carbonate, zirconium oxide, yttrium oxide, cobalt(II) oxide, and barium fluoride were weighed so that the molar ratio of Ba, Co, Zr, Y, and F was Ba:Co:Zr:Y:F = 1:0.4:0.4:0.2:0.2. ０．４ Zr ０．４ Y ０．２ O ｙ F ０．２ A composite acid fluoride having a starting composition of (2 ≤ y ≤ 4) is obtained, Na is supported on the obtained composite acid fluoride, and the catalyst composition of Example 6 (Na / BaCo ０．４ Zr ０．４ Y ０．２ O ｙ F ０．２ ) was obtained.

[0109] <Example 7> The same procedure as in Example 1 was carried out, except that barium carbonate, zirconium oxide, cobalt(II) oxide, and barium fluoride were weighed so that the molar ratio of Ba, Co, Zr, and F was Ba:Co:Zr:F = 1:0.4:0.4:0.1. ０．４ Zr ０．４ O ｙ F ０．１ A composite acid fluoride having a starting composition of (2 ≤ y ≤ 4) is obtained, Na is supported on the obtained composite acid fluoride, and the catalyst composition of Example 7 (Na / BaCo ０．４ Zr ０．４ O ｙ F ０．１ ) was obtained.

[0110] <Example 8> The same procedure as in Example 1 was carried out, except that barium carbonate, zirconium oxide, yttrium oxide, cobalt(II) oxide, and barium fluoride were weighed so that the molar ratio of Ba, Co, Zr, Y, and F was Ba:Co:Zr:Y:F = 1:0.6:0.2:0.2:0.1. ０．６ Zr ０．２ Y ０．２ O ｙ F ０．１ A composite acid fluoride having a starting composition of (2 ≤ y ≤ 4) is obtained, Na is supported on the obtained composite acid fluoride, and the catalyst composition of Example 8 (Na / BaCo ０．６ Zr ０．２ Y ０．２ O ｙ F ０．１ ) was obtained.

[0111] <Example 9> The same procedure as in Example 1 was carried out, except that barium carbonate, zirconium oxide, yttrium oxide, and cobalt(II) oxide were weighed so that the molar ratio of Ba, Co, Zr, and Y was Ba:Co:Zr:Y = 1:0.4:0.4:0.2. ０．４ Zr ０．４ Y ０．２ O ３ A composite oxide having the following composition is obtained, Na is supported on the obtained composite oxide, and the catalyst composition of Example 9 (Na / BaCo ０．４ Zr ０．４ Y ０．２ O ３ ) was obtained.

[0112] <Comparative Example 1> Cobalt nitrate hexahydrate was dissolved in 80 g of water to prepare a cobalt nitrate aqueous solution. 1000 g of water and 211.98 g of sodium carbonate aqueous solution were mixed to prepare a base aqueous solution for coprecipitation. 100 g of water was placed in a 1000 mL beaker, and the cobalt nitrate aqueous solution and the base aqueous solution for coprecipitation were added dropwise while stirring to maintain a pH of 8, and the coprecipitation treatment was carried out. After the addition was complete, the mixture was stirred for 1 hour, and then allowed to stand for 6 hours to allow the precipitate to mature. The obtained suspension was filtered by suction to collect the precipitate, and the precipitate was dispersed in pure water. The precipitate was washed by repeating the process of filtering the obtained dispersion by suction. Washing was repeated until the Na concentration of the filtrate was 2 ppm or less. The Na concentration was measured using an ion concentration meter (LAQUA twin-Na-11, Horiba, Ltd.). The washed precipitate was dried overnight in a 100°C drying oven (atmospheric atmosphere). The precipitate after drying was calcined at 400°C for 3 hours to obtain the catalyst composition (Na / Co) of Comparative Example 1. ３ O ４ ) was obtained.

[0113] <Comparative Example 2> The same procedure as in Example 1 was performed, except that zirconium oxide and cobalt(II) oxide were weighed so that the molar ratio of Co and Zr was Co:Zr = 1:1, and the oxide (ZrO ２ +Co ３ O ４ ) is obtained, and Na is supported on the obtained oxide, and the catalyst composition of Comparative Example 2 (Na / (ZrO ２ +Co ３ O ４ )) was obtained. Note that "ZrO ２ +Co ３ O ４ " is ZrO ２ and Co ３ O ４ It represents a mixture of [something].

[0114] <Comparative Example 3> A titanium dioxide dispersion was prepared by adding 100 g of titanium dioxide (JRC-TIO-17) to water and performing a dispersion treatment using an ultrasonic cleaner. An aqueous cobalt nitrate solution was prepared by dissolving 80 g of cobalt nitrate hexahydrate in water. The aqueous cobalt nitrate solution was added dropwise while stirring the titanium dioxide dispersion. After the addition was complete, the mixture was stirred for 30 minutes and then allowed to stand for 2 hours. The resulting suspension was reduced to 70 Pa using an evaporator and heated to 60°C using a water bath to obtain a powder. The obtained powder was dried overnight in a drying oven (at atmospheric temperature) at 100°C. The dried powder was calcined at 450°C for 5 hours to obtain the catalyst composition (Co / TiO) of Comparative Example 3. ２ ) was obtained.

[0115] <Comparative Example 4> 0.06 g of sodium nitrate, 1.87 g of barium carbonate, 0.49 g of zirconium oxide, 0.23 g of yttrium oxide, 0.30 g of cobalt(II) oxide, and 0.09 g of barium fluoride were mixed in an agate mortar to form the catalyst composition of Comparative Example 4 (NaNO ３ +BaCO ３ +ZrO ２ +CoOBaF ２ +Y ２ O ３ ) was obtained. ３ +BaCO ３ +ZrO ２ +CoO+BaF ２ +Y ２ O ３ " is NaNO ３ BaCO ３ , ZrO ２ CoO, BaF ２ and Y ２ O ３ It represents a mixture of [something].

[0116] <X-ray fluorescence analysis (XRF)> Compositional analysis and quantitative analysis were performed on samples obtained from each catalyst composition of Examples 1 to 9 using XRF. The conditions for compositional analysis and quantitative analysis using XRF were as follows.

[0117] [Conditions for composition analysis and quantitative analysis by XRF] - Equipment: XRF analyzer (Primus II manufactured by Rigaku Co., Ltd.) - X-ray source: Rh kα - Voltage: 50 kV - Current: 50 mA - Attenuator: 1 / 1・Slit: S2 (Ba-Lα, Co-Kα, Zr-Kα, Y-Kα, Ce-Lα, Na-Kα) ・Spectroscopic crystal: LiF (Ba-Lα, Co-Kα, Zr-Kα, Y-Kα, Ce-Lα) RX25 (Na-Kα)・Detector: SC (Ba-Lα, Co-Kα, Zr-Kα, Y-Kα, Ce-Lα) PC (Na-Kα) ・Measurement angle: 85-90°: Ba 50-55°: Co 20-25°: Zr 21–26°: Y 76–81°: Ce 44.718–50.718°: Na • Sampling width: 0.02 (Ba, Co, Zr, Y, Ce) 0.05 (Na)

[0118] <Quantitative Analysis of F by Fluoride Ion Electrode Method> Quantitative analysis of F was performed on samples obtained from each catalyst composition of Examples 1 to 9 using the fluoride ion electrode method. The fluoride ion electrode method is a method in which a sample to which a combustion aid (tungsten oxide) has been added is burned in an oxygen stream to volatilize F, and then the volatilized F is absorbed into an absorption solution and quantitatively analyzed by ion chromatography. The quantitative analysis of F by the fluoride ion electrode method was performed using an automated sample combustion device AQF-5000H (manufactured by Nitto Seikou Analytech).

[0119] From the XRF analysis results, the following ratios were determined: the ratio of the molar amount of Co to the molar amount of Ba (Co / Ba), the ratio of the molar amount of metal element M to the molar amount of Ba (M / Ba), the ratio of the total molar amounts of Co and metal element M to the molar amount of Ba ((Co+M) / Ba), the ratio of the molar amount of Zr to the total molar amount of Co and metal element M (Zr / (Co+M)), the ratio of the molar amount of Co to the total molar amount of Co and metal element M (Co / (Co+M)), and the ratio of the molar amount of Ba to the total molar amount of Ba, Co, and metal element M (Ba / (Ba+Co+M)). "Molar amount of metal element M" refers to the total molar amount of Zr, Y, and Ce. "Total molar amounts of Zr, Y, and Ce" means the total molar amount of Zr and Y if the molar amount of Ce is zero, the total molar amount of Zr and Ce if the molar amount of Y is zero, and the molar amount of Zr if both the molar amounts of Ce and Y are zero.

[0120] From the XRF analysis results and the quantitative results of F, the ratio of the molar amount of F to the molar amount of Ba (F / Ba) was determined.

[0121] The results are shown in Table 1.

[0122]

[0123] <X-ray diffraction (XRD)> Sample powders obtained by grinding each catalyst composition of Example 1 and Comparative Example 2 in an agate mortar, and BaZrO ３ BaCO ３ Co ３ O ４ and ZrO ２ XRD was performed on sample powders obtained by grinding each reference compound in an agate mortar. The XRD conditions were as follows:

[0124] [XRD Conditions] • Equipment: Powder X-ray diffractometer (Rigaku Corporation RINT-TTRIIII) • Tube voltage: 50kV • Tube current: 300mA • X-ray source: CuKα • Measurement range: 2θ = 5 to 80° • Step width: 0.02° • Scan speed: 5° / min • Receiving slit: Open • Scattering slit: Open • Diverging slit: 2 / 3°

[0125] The obtained XRD diffraction chart is shown in Figure 1. In Figure 1, "ref" represents the reference compound.

[0126] As shown in Figure 1, the XRD pattern of the catalyst composition of Example 1 shows peaks originating from the perovskite structure of the space group (Pm-3m) (peaks located at 2θ = 29.96°±0.50°, 36.94°±0.40°, 42.88°±0.60°, 53.2°±0.75°, 62.32°±0.80°, and 70.62°±0.95°) and BaCO ３ A peak originating from (a peak located at 2θ = 24.10° ± 0.65°) was identified, but Co ３ O ４ Peaks originating from (peaks located at 2θ = 31.4°±0.05°, 59.50°±0.05°, and 65.4°±0.05°) and ZrO ２ No peaks originating from (peaks located at 2θ = 28.30°±0.05° and 31.56°±0.05°) were observed. From these findings, it can be concluded that the oxide (BaCo) contained in the catalyst composition of Example 1 is not ０．４ Zr ０．４ Y ０．２ O ｙ F ０．１ It was confirmed that it is a composite oxide.

[0127] As shown in Figure 1, the XRD pattern of the catalyst composition of Comparative Example 2 is BaZrO ３ No peaks originating from Co were observed, ３ O ４ Peaks originating from ZrO ２ A peak originating from was observed. From this, it was determined that the oxide contained in the catalyst composition of Comparative Example 2 is not a composite oxide, but ZrO ２ and Co ３ O ４ It was confirmed to be a mixture of [the two substances].

[0128] <H ２ -TPR (Temperature Programmed Reduction)> For samples obtained from each catalyst composition, H is applied as follows. ２ - TPR was implemented. H ２- For TPR, a catalyst analyzer (BELCAT II, ​​Microtrac-Bell Co., Ltd.) and a gas analyzer (BELMASS, Microtrac-Bell Co., Ltd.) were used. The sample mass was 0.05 g. H ２ - In TPR measurement, the reaction gas (H ２ :2.96vol%,N ２ While flowing the remaining solution at 30 mL / min, the sample was heated from 50°C to 800°C at a heating rate of 10°C / min. The change in hydrogen gas concentration associated with the reduction reaction was detected using a semi-diffusive four-element thermal conductivity detector (TCD) [tungsten-rhenium filament].

[0129] The CO reduction initiation temperature (°C) was determined using the following formula. The CO reduction initiation temperatures are shown in Table 2.

[0130]

[0131] I ｍａｘ : Maximum value of TCD response value (absolute intensity relative to the baseline of TCD voltage value corresponding to hydrogen concentration change) in the temperature range of 100 to 800°C when measuring the same sample. ｒｅｄ : TCD response value at the Co reduction initiation temperature

[0132]

[0133] <Catalyst Activity Test A for Direct FT Reaction> Test Examples A1 to A15 were conducted as Catalyst Activity Test A for the Direct FT reaction. In Test Examples A1 to A15, the catalyst compositions shown in Table 3 were used. For samples obtained from each catalyst composition, the catalyst activity test was performed as follows. The samples were pretreated. In the pretreatment, 1 cc of the sample was packed into the reaction tube and pure H ２ The reaction tube was heat-treated at 400°C for 2 hours under a gas atmosphere, and then the temperature inside the reaction tube was cooled to room temperature (25°C). The reaction tube used was made of SUS316 with an inner diameter of 10.22 mm. After cooling, a catalyst activity test was performed by flowing gas through the reaction tube. At this time, the gas composition was H ２ / CO ２ =3, total pressure was 3.0 MPaG, temperature was 380°C, and processing time was 1.5 hours. The gas space velocity (SV) was 10,000 h for test examples A1 to A10.－１ In test examples A11 to A15, 40,000 hours －１ The online gas at the outlet of the reaction tube was quantified using GC-FID (Gas Chromatography-Flame Ionization Detector), and the CH4 selectivity (%) and C5+ selectivity (%) were determined using the following formulas. The results for test examples A1 to A15 are shown in Table 3.

[0134] CH4 selectivity (%) = (100 - CO selectivity) × (of the generated hydrocarbons CH4) ４ (Percentage) C5+ selectivity (%) = (100 - CO selectivity) × (Percentage of hydrocarbons with 5 or more carbon atoms among the generated hydrocarbons)

[0135] The "CO selectivity rate" is the CO that has been converted to CO. ２ and CO converted into hydrocarbons ２ Of the total amount, the amount of CO that was converted to CO ２ This represents the percentage (%) and was calculated using the following formula: CO selectivity (%) = (Number of moles of CO in the outlet gas per unit time) / { (Number of moles of CO in the source gas per unit time) ２ (Number of moles) - (CO in the outlet gas per unit time) ２ (Number of moles) × 100

[0136] "Of the hydrocarbons produced, CH ４ The "proportion of CH" is the percentage of the total amount of hydrocarbons produced. ４ This represents the percentage of the amount of hydrocarbon produced, and was calculated using the following formula. Of the hydrocarbons produced, CH ４ The percentage (%) = (CH in the outlet gas per unit time) ４ (Number of moles of) / (Total number of moles of all hydrocarbons in the outlet gas per unit time) × 100

[0137] The "percentage of hydrocarbons with 5 or more carbon atoms among the generated hydrocarbons" refers to the percentage of hydrocarbons with 5 or more carbon atoms generated out of the total amount of hydrocarbons generated, and was calculated using the following formula: Percentage of hydrocarbons with 5 or more carbon atoms among the generated hydrocarbons (%) = (Total number of moles of hydrocarbons with 5 or more carbon atoms in the outlet gas per unit time) / (Total number of moles of all hydrocarbons in the outlet gas per unit time) × 100

[0138] <Catalyst Activity Test B for FT Reaction> As a catalyst activity test B for the FT reaction, Test Example B1 was carried out. In Test Example B1, the catalyst composition of Example 1 was used. The catalyst activity test was carried out on the sample obtained from the catalyst composition of Example 1 as follows. As a pretreatment, 1 cc of the sample was packed into the reaction tube and pure H ２ The catalyst was heat-treated at 400°C for 2 hours under a gas atmosphere, and then the temperature inside the reactor was cooled to room temperature (25°C). A reaction tube made of SUS316 with an inner diameter of 10.22 mm was used. After cooling, a catalyst activity test was performed by flowing gas through the reaction tube. At this time, the gas composition was H ２ CO = 2, total pressure is 3 MPaG, and gas space velocity (SV) is 10,000 h. －１ The temperature was set to 380°C and the processing time to 1.5 hours. The online gas at the outlet of the reaction tube was quantified using GC-FID, and the C5+ selectivity (%) and CH4 selectivity (%) were determined using the following formulas. The results of Test Example B1 are shown in Table 3.

[0139] CH4 selectivity (%) = (100 - CO ２ Selectivity) × (of the generated hydrocarbons, CH ４ (Percentage) C5 + Selectivity (%) = (100 - CO ２ (Selectivity) × (Percentage of hydrocarbons with 5 or more carbon atoms among the generated hydrocarbons)

[0140] "CO ２ "Selection rate" is CO ２ Of the total amount of CO that has been converted into CO and CO that has been converted into hydrocarbons, CO ２ This represents the percentage of CO that changed, and was calculated using the following formula: CO ２ Selectivity (%) = (CO₂ in the outlet gas per unit time) ２ (Number of moles) / {(Number of moles of CO in the source gas per unit time) - (Number of moles of CO in the outlet gas per unit time)} × 100

[0141] "Of the hydrocarbons produced, CH ４ The meaning of "the proportion of hydrocarbons with 5 or more carbon atoms among the generated hydrocarbons" is the same as above and was calculated from the above formula. The meaning of "the proportion of hydrocarbons with 5 or more carbon atoms among the generated hydrocarbons" is the same as above and was calculated from the above formula.

[0142]

[0143] <Effect of Ba> The results for the catalyst compositions of Example 3 and Comparative Example 1 are summarized in Table 4.

[0144]

[0145] As shown in Table 4, Ba is CH ４ It has the effect of decreasing selectivity and increasing C5+ selectivity. These effects are thought to be related to the action of Ba in suppressing the reduction of Co and the action of Ba in raising the Co reduction initiation temperature.

[0146] The catalyst composition of Comparative Example 2 is similar to the catalyst composition of Example 5 in that it contains Co and Zr, but differs from the catalyst composition of Example 5 in that it does not contain Ba. The oxide contained in the catalyst composition of Comparative Example 2 is not a composite oxide, but ZrO ２ and Co ３ O ４ While the mixture is in a certain state, the oxide contained in the catalyst composition of Example 5 is a complex oxide. Therefore, Ba has the effect of assisting in the formation of complex oxides or complex acid fluorides. That is, complex oxides or complex acid fluorides containing Co and Zr but not Ba are difficult to form, but complex oxides or complex acid fluorides containing Co and Zr as well as Ba are easily formed.

[0147] <Effect of Zr> The results for the catalyst compositions of Examples 1 and 8 are summarized in Table 5-1.

[0148]

[0149] The results for the catalyst compositions of Examples 4 and 7 are summarized in Table 5-2.

[0150]

[0151] As shown in Tables 5-1 and 5-2, Zr is CH ４ It has the effect of decreasing selectivity and increasing C5+ selectivity. These effects are thought to be related to the action of Zr in suppressing the reduction of Co and the action of Zr in raising the Co reduction initiation temperature. These effects improve as the amount of Zr increases.

[0152] <Effect of Y> The results for the catalyst compositions of Examples 1 and 4 are summarized in Table 6-1.

[0153]

[0154] The results for the catalyst compositions of Examples 7 and 8 are summarized in Table 6-2.

[0155]

[0156] The results for the catalyst compositions of Examples 5 and 9 are summarized in Table 6-3.

[0157]

[0158] As shown in Tables 6-1 and 6-2, Y present in composite oxides containing F (i.e., composite acid fluorides) is CH ４ It has the effect of reducing selectivity and increasing C5+ selectivity. These effects are thought to be related to the action of Y in suppressing the reduction of Co and the action of Y in raising the Co reduction initiation temperature.

[0159] As shown in Table 6-3, Y present in composite oxides that do not contain F is CH ４ It does not have the effect of decreasing selectivity or increasing C5+ selectivity.

[0160] <Effect of Ce> The results for the catalyst compositions of Examples 2 and 4 are summarized in Table 7-1.

[0161]

[0162] The results for the catalyst compositions of Examples 1 and 2 are summarized in Table 7-2.

[0163]

[0164] As shown in Table 7-1, Ce is similar to Y, CH ４ It has the effect of decreasing selectivity and increasing C5+ selectivity. These effects are thought to be related to the action of Ce suppressing the reduction of Co and the action of Ce raising the Co reduction initiation temperature.

[0165] As shown in Table 7-2, the effect of Ce is inferior to that of Y.

[0166] <Effect of F> The results for the catalyst compositions of Examples 4 and 5 are summarized in Table 8-1.

[0167]

[0168] The results for the catalyst compositions of Examples 6 and 9 are summarized in Table 8-2.

[0169]

[0170] The results for the catalyst compositions of Examples 1 and 6 are summarized in Table 8-3.

[0171]

[0172] As shown in Tables 8-1 and 8-2, F is CH ４ It has the effect of decreasing selectivity and increasing C5+ selectivity. These effects are thought to be related to the effect of F stabilizing the oxidation state of Co and the effect of F raising the Co reduction initiation temperature.

[0173] As shown in Table 8-3, when the amount of F is appropriate, the effect of F increases.

Claims

1. A catalyst composition for catalyzing a Fischer-Tropsch reaction or a direct Fischer-Tropsch reaction, comprising the following components: (a) an oxide comprising Ba and Co, and possibly F; and (b) one or more selected from oxides, carbonates, and nitrates of Group 1 elements.

2. The catalyst composition according to claim 1, wherein the ratio of the molar amount of Co to the molar amount of Ba is 0.20 or more and 1.20 or less.

3. The catalyst composition according to claim 1, wherein the ratio of the molar amount of F to the molar amount of Ba is 0.010 or more and 0.150 or less.

4. The catalyst composition according to claim 1, wherein component (a) comprises one or more additional elements selected from Group 3 elements, Group 4 elements, and Group 5 elements.

5. The catalyst composition according to claim 4, wherein the one or more additional elements are selected from Group 3 and Group 4 elements.

6. The catalyst composition according to claim 4, wherein the ratio of the molar amount of the one or more additional elements to the molar amount of Ba is 0.40 or more and 0.85 or less.

7. The catalyst composition according to claim 4, wherein the ratio of the total molar amounts of Co and the one or more additional elements to the molar amount of Ba is 0.70 or more and 1.30 or less.

8. The catalyst composition according to claim 4, wherein the ratio of the molar amount of Co to the total molar amount of Co and the one or more additional elements is 0.20 or more and 0.99 or less.

9. The catalyst composition according to claim 4, wherein the one or more additional elements include one or more Group 4 elements, and the ratio of the molar amount of the one or more Group 4 elements to the total molar amount of Co and the one or more additional elements is 0.01 or more and 0.70 or less.

10. The catalyst composition according to claim 4, wherein component (a) comprises one or more selected from Y, Ce, and La.

11. The catalyst composition according to claim 4, wherein component (a) contains Zr.

12. The catalyst composition according to any one of claims 1 to 11, wherein at least a portion of component (b) is supported on component (a).

13. The catalyst composition according to any one of claims 1 to 11, wherein component (b) comprises one or more selected from sodium oxides, carbonates, and nitrates.

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