JP7340143B1 - Methanation catalyst - Google Patents

Abstract

The present invention provides a catalyst that exhibits high activity at 300°C to 350°C in a reaction that produces hydrocarbon compounds from carbon dioxide and hydrogen. [Solution] A catalyst that promotes a reaction that produces a hydrocarbon compound from carbon dioxide and hydrogen, the catalyst that promotes a reaction that produces a hydrocarbon compound from carbon dioxide and hydrogen, which contains Ni, Ce, and Zr. The catalyst contains less than 82.5 atomic % of Ni, and contains Ce and Zr in an atomic ratio of Zr/Ce=0.4 to 1.5. Further, the catalyst may have a honeycomb structure. By doing so, it is possible to provide a catalyst that exhibits high activity with a CO2 conversion rate of 71% at 300°C to 350°C and high efficiency with a CH4 selectivity of 99% or more at 200°C to 400°C. [Selection diagram] Figure 1

Description

The present invention relates to catalysts used to produce methane from carbon dioxide and hydrogen.

As one method of reducing carbon dioxide, which is said to cause global warming, a technology has been proposed in which carbon dioxide and hydrogen are reacted to produce methane, which is used as energy. As catalysts used to carry out such reactions efficiently, alloys of ruthenium (Ru) and titanium oxide (TiO ₂ ), alloys of nickel (Ni), cerium (Ce), zirconium (Zr), etc. have been proposed. (Patent Document 1, Patent Document 2).
Furthermore, as catalyst structures, pellet catalysts, metal honeycomb catalysts, and the like are known.

Japanese Patent Application Publication No. 2009-34650 Japanese Patent Application Publication No. 2010-22944

The catalysts disclosed in Patent Documents 1 and 2 exhibit high activity at low temperatures of 250°C or lower, but the methanation reaction is generally an exothermic reaction, so the entire reaction system becomes high temperature. Rather, a catalyst that exhibits high activity in a high temperature range is desired. In this respect, the catalysts disclosed in Patent Documents 1 and 2 still have room for improvement.
Further, although the alloy of ruthenium (Ru) and titanium oxide (TiO ₂ ) has high activity at high temperatures, another problem is that it is very expensive.
In view of this problem, the present application aims to provide a methanation catalyst with high high temperature activity without using so-called noble metals.

The present invention
A catalyst that promotes a reaction that produces hydrocarbon compounds from carbon dioxide and hydrogen,
Contains Ni, Ce, Zr,
Ni less than 82.5 atomic%,
The catalyst may contain Ce and Zr in an atomic ratio of Zr/Ce of 0.4 or more and 1.5 or less.
As a result of experiments, it was confirmed that with this configuration, high activity could be obtained at high temperatures of 300°C to 350°C. In addition, the above-mentioned component proportions are atomic % when all the elements contained in the catalyst are taken as 100%. In the present invention, it means the proportion of each element when Ni, Ce, and Zr are all taken as 100%. Moreover, the above composition means a mixed composition (feeding composition) when producing a catalyst.

In the present invention,
It is more preferable that Ce and Zr are contained in an atomic ratio of Zr/Ce of 0.6 or more and 1.5 or less.

Further, the catalyst of the present invention is
It is preferable that it is produced by forming a strong salt powder layer containing all of Ni, Ce, and Zr on a metal foil base and thermally decomposing the layer.
As described later, when producing a catalyst, there are two methods: forming a strong salt powder layer containing Ni and then forming a strong salt powder layer containing one or both of Ce and Zr (sequential impregnation method); , Ce, and Zr (co-impregnation method), but according to the inventor's experiments, it has been confirmed that the co-impregnation method provides higher activity. Ta.

In the present invention,
Contains 32 atomic% or more of Ni,
It is more preferable that Ce and Zr are contained in an atomic ratio of Zr/Ce of 0.8 or more and 1.5 or less.

Furthermore,
It is more preferable that Ni be contained in an amount of 60 atomic % or more.

In the catalyst of the present invention,
Furthermore, Ru may be contained in an amount of less than any of Ni, Ce, and Zr.
For example, Ru may be about 0.6 atomic %.

The catalyst of the present invention is
It may also be supported on a honeycomb structure.
By doing so, the surface area of the catalyst can be increased and the activity can be increased.

The present invention
A catalyst that promotes a reaction that produces hydrocarbon compounds from carbon dioxide and hydrogen,
One of the catalysts mentioned above is used as a first catalyst,
A catalyst containing Ru and TiO ₂ is used as a second catalyst,
The first catalyst and the second catalyst may be alternately stacked in one or more layers.

The catalyst containing Ru and TiO ₂ (second catalyst) is characterized by very high activity. Since the reaction of producing hydrocarbon compounds from carbon dioxide and hydrogen is an exothermic reaction, it may be very difficult to control the temperature of the reaction system if only a catalyst containing Ru and TiO ₂ is used. In the above embodiment, since not only the second catalyst but also the first catalyst containing Ni, Ce, and Zr are laminated, it is possible to suppress the reaction system from becoming too high temperature, and also to prevent the reaction system from becoming too high temperature. Another advantage is that the heat generated by the second catalyst is utilized for activating the first catalyst.
Further, by using the first catalyst in combination, there is an advantage that the cost can be suppressed compared to the case where the second catalyst containing a noble metal as a main component is used alone.

In the above embodiment, the shapes of the first catalyst and the second catalyst can be arbitrarily selected, but in order to prevent the two from being mixed, for example, the first catalyst is supported on a honeycomb, The second catalyst may be in the form of pellets. Further, the thickness of the first catalyst layer and the second catalyst layer, and the number of both layers can be arbitrarily determined. It is not necessary to limit the number of first catalyst layers and second catalyst layers to the same number, and either one may be increased.
Further, the order of stacking can be arbitrarily determined, but it is more preferable from the viewpoint of ensuring high activity that the stacking order is such that the mixed gas of carbon dioxide and hydrogen is supplied to the second catalyst layer first.

All of the various features described above do not necessarily need to be provided, and some of them may be omitted or combined as appropriate.
Further, the present invention may be applied not only to a catalyst but also to a method for producing a catalyst.
That is, a method for producing a catalyst that promotes a reaction that produces a hydrocarbon compound from carbon dioxide and hydrogen,
preparing a metal foil substrate;
forming a strong salt powder layer containing all of Ni, Ce, and Zr on the surface of the base;
forming an oxide particle layer containing the strong salt powder layer by thermally decomposing it;
The method for producing a catalyst may include the step of reducing the oxide particle layer.

When producing a catalyst containing multiple metal elements, there are two methods: forming a strong salt powder layer for each component (hereinafter referred to as the sequential impregnation method), and forming a strong salt powder layer containing multiple components at once. A method (hereinafter referred to as co-impregnation method) is considered. The catalyst of the present invention can be produced by any method, but according to the inventor's experiments, it has been found that the co-impregnation method can produce a highly active catalyst more efficiently.
The strong salt powder layer can be formed, for example, by immersing the substrate in an aqueous solution containing each component or its salt, or by applying these aqueous solutions to the surface of the substrate.
The metal foil constituting the base may be, for example, Ni foil.

FIG. 2 is an explanatory diagram showing the structure of a catalyst in an embodiment. FIG. 2 is an explanatory diagram showing a stacked structure of a catalyst in an embodiment. FIG. 2 is an explanatory diagram showing the state of the surface of the catalyst 2. FIG.

FIG. 1 is an explanatory diagram showing the structure of a catalyst in an embodiment. A perspective view of the catalyst 10 is shown in FIG. 1(a). The catalyst 10 is constructed by winding a base 11 in a spiral shape. The base body 11 is made up of a flat metal foil 11a and a wavy metal foil 11b. With this structure, the external appearance of the catalyst becomes a cylindrical honeycomb structure, and a gap is maintained inside by the corrugated metal foil 11b, thereby forming a flow path along the central axis direction.

FIG. 1(b) shows a partially enlarged view of the base 11. As shown in FIG. As shown in the figure, in the base 11, a wavy metal foil 11b is integrated on one side of a flat metal foil 11a. The metal active layer 12 functioning as a catalyst is supported on the surface of the base 11.
Various materials can be used for the metal foils 11a and 11b, but from the viewpoint that the metal active layer 12 can be supported well, the main component is one of Ni, stainless steel, and iron-based alloy, that is, 50% by weight or more. It is preferable that In addition, since the substrate itself can function as a catalyst by containing Ni as a main component, higher catalytic activity can be obtained.
The thickness of the metal foils 11a and 11b can be arbitrarily determined, but can be, for example, in the range of several μm to several hundred μm, particularly about several tens of μm.

According to the catalyst 10 of the embodiment, a mixed gas containing carbon dioxide and hydrogen flows along the flow path formed by the honeycomb structure, and the reaction is promoted by contacting the metal active layer 12. In particular, by forming a honeycomb structure, the surface area where the mixed gas and the metal active layer 12 come into contact can be increased, so that good catalytic activity can be obtained. Furthermore, since the honeycomb structure has low pressure loss, it has the advantage of being able to efficiently flow mixed gas and promote reaction.

The shape of the catalyst 10 is not limited to a cylindrical shape, and can take various shapes such as a prismatic shape or a polygonal shape. Furthermore, the structure is not limited to the honeycomb structure, and various structures capable of ensuring a flow path can be used, such as a spiral structure in which only the flat metal foil 11a is wound.

Next, the metal active layer 12 will be explained.
The metal active layer 12 is composed of fine metal particles having a particle size of 1 μm or less supported on the surface of the base 11. By using such fine metal particles, the surface area of the catalyst 10 can be further increased. By setting the particle size to 1 nm or more, stable catalytic properties can be easily obtained.

The metal fine particles in the embodiment include Ni, Ce, and Zr.
Further, the above catalyst may further contain Ru. However, in order to reduce the cost of the catalyst, it is preferable that Ru be set at a lower atomic % than any of Ni, Ce, and Zr.

The catalyst 10 can be manufactured by the following procedure.
First, the base 11 constituting the catalyst 10 is prepared. As shown in FIG. 1(b), a flat metal foil 11a and a wavy metal foil 11b may be prepared and then integrated. The waveform of the metal foil 11b can be various shapes such as a triangular wave, a rectangular wave, and a trapezoidal wave. For example, an adhesive or the like can be used to integrate the two. Then, by winding this base body 11 as shown in FIG. 1(a), a honeycomb structure can be constructed.

Next, metal is supported on the honeycomb structure to form the metal active layer 12 in the following procedure.
First, the substrate 11 is ultrasonically cleaned with acetone and dried. Then, a strong acid salt aqueous solution containing all of the metal elements constituting the catalyst is applied to the surface of the substrate 11 to form a strong acid salt aqueous solution layer. Here, since the catalyst of the embodiment contains Ni, Ce, and Zr, strong acid salts containing each of these metals may be prepared and mixed to produce a strong salt aqueous solution for coating. Instead of coating, the substrate 11 may be immersed in a strong salt aqueous solution.
The amount of the strong salt aqueous solution layer can be adjusted by adjusting the concentration of the strong salt aqueous solution, the immersion time, etc.

As described above, this embodiment is characterized by using a method of forming a strong salt aqueous solution layer containing all the components, that is, a co-impregnation method. The catalyst itself can be manufactured using a method of forming a strong salt aqueous solution layer for each component, that is, a sequential impregnation method, but as described later, a highly active catalyst can be obtained by using a co-impregnation method. It is.

When the substrate 11 on which the strong acid salt aqueous solution layer has been formed is dried, a strong acid salt powder layer consisting of powders of the strong acid salts (or hydrates thereof) of each component is formed on the surface of the substrate 11. Depending on the desired thickness of the catalyst layer, the formation and drying of the strong acid aqueous solution layer may be repeated.
Note that drying can be carried out under various conditions; for example, the first stage of drying is performed at a drying temperature of 60°C for 6 hours, and then the second stage is performed at a drying temperature of 120°C for 6 hours. Alternatively, drying may be performed.

After forming the strong salt powder layer, the base 11 is heated to sinter the strong salt powder layer, and the strong salt powder is thermally decomposed to produce oxide fine particles with a particle size of several nm to several hundred nm. . The sintering conditions can be set in various ways, and for example, in an air atmosphere, the sintering temperature is 400 to 600° C., and the sintering time is 5 to 12 hours.

Finally, the substrate 11 on which the oxide fine particle layer is formed is heated in a reducing atmosphere to reduce the oxide fine particles. As a result, metal fine particles of each element are generated and a metal active layer 12 is formed. The reduction conditions can be set in various ways, for example, under a hydrogen atmosphere, with a reduction temperature of 400 to 600° C., and a reduction time of 1 hour or more.

According to the above method, there is an advantage that the catalyst 10 in which the metal active layer 12 is formed on the surface of the base body 11 can be obtained by a relatively simple method without using any special equipment or technique.

The catalyst 10 shown in FIG. 1 may be used alone, but it can also be used in a stacked manner with other catalysts as shown below.
FIG. 2 is an explanatory diagram showing the stacked structure of the catalyst in the embodiment. This catalyst 30 uses the catalyst 10 described in FIG. 1 as a first catalyst in the main body container (catalysts 10[1] to 10[4] in the figure). Further, second catalysts 20[1] to 20[4] are stacked thereon. The second catalyst 20 is a catalyst made of Ru--TiO ₂ and is in the form of pellets. As the second catalyst, a catalyst other than Ru-TiO ₂ may be used as long as it contains a noble metal and has high activity. Further, the second catalyst may also have a shape other than a pellet shape, for example, a honeycomb structure.

When a mixed gas of carbon dioxide and hydrogen is supplied to the catalyst 30 from above in the figure, a reaction occurs first at the second catalyst 20[4]. Since the second catalyst 20 [4] is a highly active catalyst made of Ru-TiO ₂ , the reaction occurs quickly, and since this reaction is an exothermic reaction, it generates heat. The generated heat is transferred to the first catalyst 10[4] and promotes the reaction there. Furthermore, since the first catalyst 10[4] is placed below the second catalyst 20[4], the reaction progresses more efficiently than when the entire catalyst is composed of Ru- _TiO2 . It also becomes possible to suppress the amount of heat generated.
Thereafter, in the same manner, the reactions at the second catalysts 20[3] to 20[1] and the reactions at the first catalysts 10[3] to 10[1] are mutually promoted and suppressed while the overall reaction is carried out. Progress is made by balancing heat generation.

In the embodiment, a configuration in which four layers each of the first catalyst and the second catalyst are provided is illustrated, but the number of layers may be smaller than this, or the total number may be larger. Further, the number of layers of the first catalyst and the second catalyst may be different. For example, by omitting the first catalyst 10[1], the number of layers of the first catalyst and the number of layers of the second catalyst can be changed. It may have four layers. The thickness of each layer can also be arbitrarily determined.
However, it is preferable that the first catalyst to which the mixed gas is supplied be the second catalyst 20[4] in order to smoothly start the reaction.

Examples of the catalyst of the present invention are shown below.
Catalysts 1 to 11 as examples were produced by the following method.
First, a honeycomb structure of nickel foil was used as the base, and the diameter was 8 mm, the height was 10 mm, the average wall thickness was 0.03 mm, and the average cell density was 2311 cpsi. Then, using this substrate, a catalyst was manufactured by the manufacturing method described above.
Catalyst 1 contains nickel (II) nitrate hexahydrate (Ni(NO ₃ ) _{2.6H 2} O), zirconium dinitrate in a ratio of Ni:Ce:Zr=65.3:13.7:21 atomic %. Prepare an aqueous solution (30-50% concentration) of hydrate (ZrO(NO ₃ ) _2.2 H ₂ O) and cerium(III) nitrate hexahydrate (Ce(NO ₃ ) _3.6 H ₂ O). After immersing the substrate in this, it was dried in air at 60 to 70°C for 6 hours or more and at 90°C for 12 hours or more to remove excess solvent. Then, this was set in an electric box furnace and sintered in air at 500°C for 5 to 6 hours, and then set in an electric tube furnace and reduced in a hydrogen atmosphere at 430°C for 1 hour. In catalyst 1, Zr/Ce=1.5.

Catalyst 2 was produced in the same manner with a ratio of Ni:Ce:Zr=48.5:20.3:31.2 at%. Zr/Ce=1.5.
Catalyst 3 was produced in the same manner with a ratio of Ni:Ce:Zr=32:26.9:41.1 at%. Zr/Ce=1.5.
Catalyst 4 was produced in the same manner at a ratio of Ni:Ce:Zr:Ru=64.3:13.5:20.7:1.5 at%. For Ru, an aqueous solution (concentration 30-50%) of ruthenium (III) nitrosyl nitrate solution (HN ₄ O10Ru, density 1.07 g/ml) was used. Catalyst 4 also has Zr/Ce=1.5.
Catalyst 5 was manufactured in a ratio of Ni:Ce:Zr=65.3:13.7:21 atomic %. Zr/Ce=1.5. However, for catalyst 5, the sequential impregnation method was used instead of the co-impregnation method. That is, first, the substrate is immersed in an aqueous solution of nickel (II) nitrate hexahydrate containing Ni and dried, and then zirconium nitrate dihydrate and cerium (III) nitrate hexahydrate containing Ce and Zr are added. The substrate is immersed in the aqueous solution and dried. Then, the manufacturing method involves sintering the entire product and reducing it.
Catalyst 6 was produced in the same manner with a ratio of Ni:Ce:Zr=68.3:22.9:8.8 at%. Zr/Ce=0.4. Catalyst 6, like Catalysts 1 to 4, was produced by the co-impregnation method.
Catalyst 7 was produced by a co-impregnation method in a ratio of Ni:Ce:Zr=56.8:28.6:14.6 at%. Zr/Ce=0.5.
Catalyst 8 was produced by a co-impregnation method in a ratio of Ni:Ce:Zr=59.7:25.0:15.3 at%. Zr/Ce=0.6.
Catalyst 9 was manufactured by a co-impregnation method in a ratio of Ni:Ce:Zr=62.8:21.0:16.2 at%. Zr/Ce=0.8.
Catalyst 10 was produced by a co-impregnation method in a ratio of Ni:Ce:Zr=66.3:16.7:17.1 at%. Zr/Ce=1.0.
Catalyst 11 was produced by a co-impregnation method in a ratio of Ni:Ce:Zr=17.4:46.7:35.9 at%. Zr/Ce=0.8.

Comparative Example 1 was produced in the same manner using a ratio of Ni:Zr=82.3:17.7 at%. Since it does not include Ce, Zr/Ce cannot be defined.
Comparative Example 2 was produced in the same manner with a ratio of Ni:Ce=87.7:12.3 at%. Since Zr is not included, Zr/Ce=0.
Comparative Example 3 was produced in the same manner using Ni:Ce:Zr=82.5:6.9:10.6 at%. Zr/Ce=1.5.
Comparative Example 4 was produced in a ratio of Ni:Ce:Zr=43:7.2:49.8 at%. Zr/Ce=6.9. Comparative Example 6 was also produced by the sequential impregnation method.

FIG. 3 is a photograph of the surface of the catalyst 2 taken with a scanning electron microscope (SEM). The magnification increases in the order of FIG. 3(a), FIG. 3(b), and FIG. 3(c). At high magnifications, such as in Figures 3(b) and 3(c), differences in surface conditions are visible, but when viewed at low magnifications, as in Figure 3(a), the overall state is generally uniform. You can understand what is happening. Therefore, the catalytic function is expected to exhibit generally uniform activity as a whole, although there may be slight local fluctuations.

The compositions and CO ₂ conversion rates at 300° C. of Catalysts 1 to 11 and Comparative Examples 1 to 4 produced above are shown in Table 1. The CO ₂ conversion rate was determined under atmospheric pressure by setting the volume of the honeycomb catalyst to 0.5 cm ³ and supplying a mixed gas of hydrogen (24 ml/min), carbon dioxide (6 ml/min), and nitrogen (30 ml/min). These are the results under the catalytic reaction experimental conditions (ie, carbon dioxide: hydrogen = 1:4, total pressure of reaction gas (hydrogen and carbon dioxide) = 0.05 MPa). The CO ₂ conversion rate (Table 2) and CH 4 selectivity (Table 3) at other temperatures are also the results obtained under the same experimental conditions.

According to the above table, it is confirmed that the CO ₂ conversion rates of Comparative Examples 1 to 4 are 41 to 68%, while those of Catalysts 1 to 11 are significantly higher at 71% or more.
First, considering that Comparative Examples 1 and 2 contain only two of Ni, Ce, and Zr, it is preferable to include all of Ni, Ce, and Zr. Furthermore, it was confirmed that Zr/Ce=0.4 to 1.5 is preferable.
Second, in all catalysts 1 to 5, Zr/Ce=1.5. On the other hand, Comparative Example 3 also has Zr/Ce=1.5, but differs in that it contains more Ni than Catalysts 1 to 5 at 82.5 atomic %. Therefore, it was confirmed that high activity can be obtained by setting Ni to less than 82.5% and Zr/Ce=1.5.

Although Catalyst 1 and Catalyst 5 have the same components, the activity of Catalyst 5 was slightly inferior to that of Catalyst 1, so it was confirmed that higher activity was obtained by the co-impregnation method than by the sequential impregnation method.

Furthermore, considering that Catalysts 1 to 4 show a CO ₂ conversion rate of 80% or more, it is considered preferable that Zr/Ce=1.5.
Furthermore, as shown in Catalyst 4, it is also suitable to contain a small amount of Ru.

Table 2 shows the CO ₂ conversion rates at temperatures of 200°C to 500°C for Catalysts 1 to 11 and Comparative Examples 1 to 4.

According to the above results, it can be seen that Catalysts 1 to 11 exhibit a high CO ₂ conversion rate of 71% or more in the high temperature range of 300 to 350°C. Although Comparative Examples 2 and 3 show a CO ₂ conversion rate of 75% or more at 350°C, it rapidly drops to 68% or less at 300°C.

Furthermore, from the results of catalysts 1 to 5 and 8 to 11, by setting Zr/Ce to 0.6 or more and 1.5 or less, a high CO ₂ conversion rate of 70% or more at a temperature of 300°C and 80% or more at 350°C can be achieved. It was found that it was possible to secure
From the results of catalysts 1 to 4 and 9, by containing 32% or more of Ni and setting Zr/Ce to 0.8 or more and 1.5 or less, a high CO of 80% or more can be achieved in the high temperature range of 300 to 350°C. It was found that a conversion rate of ₂ could be ensured.
From the results of Catalysts 1, 4, and 9, it was found that by further containing 60% or more of Ni, a high CO ₂ conversion rate of 82% or more could be ensured in the high temperature range of 300 to 350°C.

Table 3 shows the CH ₄ selectivity at temperatures of 200° C. to 500° C. for Catalysts 1 to 11 and Comparative Examples 1 to 4. CH ₄ selectivity refers to the proportion of CH ₄ in the substances produced by the reaction. The experiment shown in Table 3 was conducted under conditions where a mixed gas of carbon dioxide:hydrogen=1:4 was supplied and the pressure was 0.05 MP.

As shown in Table 3, Catalysts 1 to 11 showed a CH ₄ selectivity of 99% or more in the high temperature range of 300 to 350°C, which indicates high activity, and methane was produced very efficiently. I understand.

Although the embodiments of the present invention have been described above, the present invention is not limited to the above-described embodiments, and it goes without saying that various changes can be made without departing from the gist of the present invention.
For example, although the embodiments illustrate catalysts that produce methane, these catalysts are also useful for producing hydrocarbons other than methane.

10 (first) catalyst 11 Substrate 11a, 11b Metal foil 12 Metal active layer 20 Second catalyst 30 Catalyst

Claims (8)

A catalyst that promotes a reaction that produces hydrocarbon compounds from carbon dioxide and hydrogen,
a metal foil base;
a metal active layer containing fine metal particles of a plurality of elements formed on the surface of the base,
The elements include Ni, Ce, and Zr,
Ni at 32 atomic % or more and less than 82.5 atomic %,
A catalyst containing Ce and Zr in an atomic ratio of Zr/Ce of 0.6 or more and 1.5 or less. The catalyst according to claim 1,
A catalyst manufactured by forming a strong salt powder layer containing all of Ni, Ce, and Zr on a metal foil base and thermally decomposing the layer. The catalyst according to claim 2,
A catalyst containing Ce and Zr in an atomic ratio of Zr/Ce of 0.8 or more and 1.5 or less. The catalyst according to claim 3,
A catalyst containing 60 atomic percent or more of Ni. The catalyst according to claim 1,
Furthermore, a catalyst containing less atomic % of Ru than any of Ni, Ce, and Zr. The catalyst according to claim 1,
Catalyst supported on a honeycomb structure. A catalyst that promotes a reaction that produces hydrocarbon compounds from carbon dioxide and hydrogen,
The catalyst according to any one of claims 1 to 6 is used as a first catalyst,
A catalyst containing Ru and TiO ₂ is used as a second catalyst,
A catalyst in which one or more layers of the first catalyst and the second catalyst are alternately stacked. A method for producing a catalyst that promotes a reaction that produces a hydrocarbon compound from carbon dioxide and hydrogen, the method comprising:
preparing a metal foil substrate;
forming a strong salt powder layer containing all of Ni, Ce, and Zr on the surface of the base;
pyrolyzing the strong salt powder layer to form an oxide particle layer;
A step of reducing the oxide particle layer so that the Ni content is 32 atomic % or more and less than 82.5 atomic %, and the atomic ratio of Ce and Zr is such that Zr/Ce is 0.6 or more and 1.5 or less. A method for producing a catalyst.