JP2008207070A - Method for producing catalyst for producing hydrogen - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a catalyst for producing hydrogen, which catalyst is not only high in catalytic activity at low temperature but also excellent in oxidation resistance and sintering resistance and high also in durability. <P>SOLUTION: The method for producing the catalyst for producing hydrogen, which is a Cu fine particle/α-Al<SB>2</SB>O<SB>3</SB>base material integrated type, comprises the steps of: sintering a mixture, in which CuO is mixed with Al<SB>2</SB>O<SB>3</SB>by 1-4 Cu/Al molar ratio, in a non-oxidizing atmosphere to produce a compound oxide (CuAlO<SB>2</SB>); and reducing the compound oxide by heat treatment, so that metal Cu particles are exposed on the surface of the compound oxide. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a method for producing a catalyst for producing hydrogen, and in particular, a reforming reaction for steam reforming of a hydrocarbon liquid fuel such as methanol or dimethyl ether (DME) or a shift reaction for reacting CO with steam. The present invention relates to a method for producing a catalyst used for hydrogen production by the method.

  Japan, an industrialized country, has a low self-sufficiency rate for energy resources, and most of them rely on foreign countries. For this reason, as one of the future energy resources, there is a high interest in hydrogen energy that can be easily converted into clean and high-quality electric energy. Stationary fuel cells have already been sold to households. Research and development is also underway for fuel cell vehicles, and hydrogen-related businesses are expected to grow significantly in the future. Recently, attempts have been made to produce hydrogen using a heat source of 300 ° C. or lower, which has been conventionally discarded as waste heat.

  For producing hydrogen, a method using steam reforming of a hydrocarbon fuel is known, and liquid fuel such as methanol or dimethyl ether is used as the fuel. Catalysts are used for steam reforming of hydrocarbon fuels. Cu-based catalysts are widely used because they can efficiently reform the liquid fuel at low temperatures and are inexpensive. In particular, Cu—Zn-based materials are prominent, have a large specific surface area, and are excellent in selectivity of product gas as well as activity, and thus are used as reforming catalysts and shift catalysts.

  However, these conventional Cu-based catalysts have the greatest drawback of inferior oxidation resistance and sintering resistance. That is, when a conventional Cu-based catalyst is exposed to the atmosphere, it is oxidized with rapid heat generation, and Cu particles are aggregated. In addition, grain growth occurs with time due to thermal factors, and as a result, the specific surface area decreases and the activity decreases. For these reasons, an initial reduction treatment in which the reduction is performed after the reactor is filled with the catalyst is indispensable. Also, during operation, it is necessary to thoroughly control temperature management and atmospheric contamination.

In Patent Document 1, fine particles containing a Cu-based oxide are supported on porous ceramics having a high specific surface area such as γ-Al ₂ O ₃ by a coprecipitation method or the like, and then reduced to deposit metal Cu fine particles. A method for producing a Cu-based catalyst is disclosed.

However, the catalyst obtained by such a method has a problem of low adhesion (bonding) between the Cu particles and the ceramic substrate containing γ-Al ₂ O ₃ . In addition, since the form immediately after generation is a fine particle of about several nm, there is a problem that grain growth and aggregation are likely to occur due to long-term use.

  On the other hand, Non-Patent Document 1 and Non-Patent Document 2 describe catalysts obtained by reducing spinel complex oxides. The metal particles deposited from the inside of the base material by the reduction treatment are considered to have excellent durability because they have good binding properties with the base material and can be highly dispersed. In this document, a catalyst obtained by reduction treatment of a Cu-Al-based, Cu-Mn-based, or Cu-Mn-Fe-based spinel-type composite oxide is evaluated, and a Cu-Mn-based or Cu-Mn-Fe-based catalyst is evaluated. It is described that the catalyst obtained by reducing spinel complex oxide has the highest activity.

However, base materials such as MnO produced by reduction are inferior in mechanical strength. Further, since Mn can take several valences, there is a concern about stability due to long-term use. Furthermore, it is described that a CuAl ₂ O ₄ based catalyst can be obtained by reduction at a temperature of 400 ° C. or lower. Although Cu precipitates even at this temperature, unlike other systems, all of the Cu component is reduced and does not precipitate, and remains in a state containing the Cu component in the substrate. As a result, depending on the situation such as actual use after filling the reactor, the precipitation of new Cu may be considered, and the structure may become uneven and the characteristics may become unstable.
JP 60-84142 A Appl. Catal. A: General, 242,287 (2003) Proceedings of the 94th Catalysis Conference, 390 (2004)

  Conventional catalysts using Cu-based materials are cheaper and easier to obtain than noble metal-based catalysts, and are expected to be used for reforming catalysts, CO shift catalysts, and the like. However, its oxidation resistance and sintering resistance (particle growth and coalescence resistance by sintering) are inferior, and the usage conditions are limited. In addition, the Cu-based spinel oxide is excellent in particle dispersibility and adhesion to a substrate, but there is a risk that composition stability and tissue uniformity may not be maintained over a long period of use.

  An object of the present invention is to provide a method for producing a catalyst for hydrogen production that has not only high catalytic activity at low temperatures, but also excellent oxidation resistance and sintering resistance, and high durability.

According to the present invention, a copper compound and an aluminum compound are mixed so that the molar ratio of Cu / Al is 1 to 4, and then the mixture is fired at a temperature of 900 to 1300 ° C. in a non-oxidizing atmosphere to obtain CuAlO _2. Or a step of producing a composite oxide composed of a mixed phase of CuAlO ₂ and Al ₂ O ₃ ;
Precipitating metal Cu particles having an average particle diameter of 5 to 500 nm on at least the surface portion of the base material of α-type Al ₂ O ₃ by heating and reducing the composite oxide in a reducing atmosphere. The manufacturing method of the catalyst for hydrogen production characterized by including is provided.

  According to the present invention, it is possible to produce a Cu-based hydrogen production catalyst having excellent oxidation resistance and sintering resistance and high low-temperature catalytic performance. Further, there is no need for a reduction treatment just before use as in the case of a conventional Cu-based catalyst, and it becomes possible to carry in the air after synthesis.

  Therefore, since the obtained catalyst for hydrogen production can sufficiently maintain the performance after oxidation, which is a disadvantage of the commercially available Cu-based catalyst, it is excellent as a low temperature reforming catalyst such as methanol and dimethyl ether, or a shift catalyst for shift reaction. Have good performance.

  Hereinafter, a method for producing a catalyst for hydrogen production according to an embodiment of the present invention will be described in detail.

(Composite oxide production process)
After mixing the copper compound and the aluminum compound so that the molar ratio of Cu / Al is 1 to 4, this mixture is fired at a temperature of 900 to 1300 ° C. in a non-oxidizing atmosphere to obtain CuAlO ₂ or CuAlO ₂ . A composite oxide composed of a mixed phase of Al ₂ O ₃ is generated.

As the copper compound and the aluminum compound, for example, CuO and Al ₂ O ₃ powders can be used. These powders preferably have an average particle size of submicron, for example an average particle size of 0.5 to 1.0 μm. The copper compound and the aluminum compound can be used in the form of a metal salt of copper or aluminum, for example, in addition to the oxide powder. In this case, each metal salt is dissolved and mixed in water and further subjected to a drying treatment before firing. As the copper salt, for example, copper nitrate, copper sulfate, or copper chloride can be used. As the aluminum salt, for example, aluminum nitrate, aluminum sulfate, or aluminum chloride can be used. From the viewpoint of handling, it is preferable to use copper nitrate and aluminum nitrate.

By setting the Cu / Al molar ratio at the time of mixing the copper compound and the aluminum compound to 1 to 4, it becomes possible to obtain a complex oxide having a uniform structure, and a catalyst having good performance by the reduction treatment described later Can be manufactured. When the molar ratio of Cu / Al is less than 1, the amount of Cu dissolved in the obtained composite oxide is insufficient, the production of the CuAlO ₂ phase is reduced, and many phases containing only Al ₂ O ₃ are mixed. . As a result, there is a possibility that the performance of the catalyst obtained by the reduction treatment described later is deteriorated. On the other hand, when the molar ratio of Cu / Al exceeds 4, CuO remains in the obtained composite oxide, Cu is precipitated at a low temperature in the subsequent reduction treatment, and a higher temperature (normal reduction temperature) And agglomerate with the precipitated Cu to locally produce aggregates of coarse Cu particles. As a result, there is a possibility that the performance of the catalyst obtained by the reduction treatment described later is deteriorated. A more preferable Cu / Al molar ratio is 2-3.

Firing is performed at a temperature of 900 to 1300 ° C., more preferably 1000 to 1200 ° C., in an atmosphere of a non-oxidizing gas such as argon or nitrogen. By such firing, a light blue color is obtained, and a composite oxide composed of CuAlO ₂ alone or a mixed phase of CuAlO ₂ and Al ₂ O ₃ is synthesized. When the firing is performed in the air (in an oxidizing atmosphere), the main component exhibiting a reddish brown color becomes a spinel-type composite oxide (CuAl ₂ O ₄ ).

(Reduction treatment process)
A reduction treatment is performed by heating the obtained composite oxide in a reducing atmosphere. At this time, substantially all of the Cu components are deposited as metal Cu particles from the CuAlO ₂ composite oxide. At the same time, the substrate is converted to α-Al ₂ O ₃ . The deposited metal Cu particles are present inside and on the surface of the α-Al ₂ O ₃ base material.

  The reducing atmosphere includes hydrogen alone or an inert gas containing hydrogen (for example, nitrogen gas, argon gas, etc.). It is also possible to embed the mixture in carbon packing powder to create a reducing atmosphere.

  In the reduction treatment of the composite oxide, the precipitation of the metal Cu particles starts from around 600 ° C. and is almost completed at around 700 ° C. Therefore, it is preferable to perform the heating during the reduction treatment at a temperature of 600 ° C. or higher. The upper limit of the heating temperature is preferably set to 1000 ° C. in order to avoid aggregation of the precipitated metal Cu particles. The heating temperature at the time of a more preferable reduction process is 650-800 degreeC. Since the heating temperature at the time of such reduction treatment is higher than the temperature (about 300 ° C.) when used as a reforming catalyst or CO shift reaction catalyst in a steam reforming reaction, thermal stability in each of the above reactions Can be secured.

  The deposited metal Cu particles have an average particle size of 5 to 500 nm. The average particle diameter of the metal Cu particles can be measured, for example, by counting the number of particles present in a specific field of view based on an image taken with an electron microscope. If the average particle diameter of the metal Cu particles exceeds 500 nm, the specific surface area of the catalyst surface containing the metal Cu particles may decrease, and the catalytic activity may decrease. A more preferable average particle diameter of the metal Cu particles is 10 to 100 nm.

By such a reduction treatment, a catalyst for hydrogen production, which is a composite material in which metal Cu particles are deposited on at least the surface portion of the α-Al ₂ O ₃ base material, is obtained.

  The hydrogen production catalyst according to the embodiment is preferably further subjected to the following oxidation treatment.

  The composite material is heated in an oxidizing atmosphere to be oxidized. At this time, the metal Cu particles are oxidized and a slight amount of heat is generated. However, since the metal Cu particles have a relatively large diameter of 5 to 500 nm, rapid exothermic → dissolution hardly occurs. The time for the oxidation treatment is sufficient if it is about 15 minutes, for example.

  In the oxidation treatment, metal Cu particles are oxidized to produce CuO. It is preferable that the production | generation of CuO is a part of metal Cu particle | grains. Most preferably, CuO is produced so as to cover the surface of the metal Cu particles.

  The oxidizing atmosphere in the oxidation treatment may be an atmosphere containing oxygen, and examples thereof include air (atmosphere) or forming gas such as nitrogen gas containing 5% by volume or less of oxygen.

  The oxidation treatment is preferably performed at a temperature of 150 to 350 ° C. If it is less than 150 degreeC, there exists a possibility that oxidation of metal Cu particle | grains may not fully be made | formed. On the other hand, when it exceeds 350 degreeC, it changes to CuO particle | grains etc. which the adjacent metal Cu particle | grains united and enlarged and there exists a possibility that catalyst activity may fall. A more preferable temperature for the oxidation treatment is 150 to 300 ° C.

  In the production of such a catalyst for hydrogen production, a method is adopted in which the composite oxide powder is subjected to reduction treatment, preferably further oxidation treatment. In addition to such a method, when a catalyst having a complicated shape is manufactured, a method of reducing the solidified material or honeycomb formed with the composite oxide powder, preferably further oxidizing may be employed.

  The catalyst for hydrogen production according to the embodiment is, for example, a reforming catalyst that takes out hydrogen by reacting a hydrocarbon fuel with water vapor using low-temperature waste heat of about 300 ° C., or CO that is by-produced in the reforming reaction, for example. It can be used as a shift catalyst that reacts with water vapor to remove CO and extract hydrogen.

  Examples of the hydrocarbon fuel include liquid fuels such as methanol, ethanol, dimethyl ether (DME) and the like. The steam reforming reaction using methanol and ethanol as raw materials is represented by the following formulas (1) and (2).

CH ₃ OH + H ₂ O 3H ₂ + CO ₂ (1)
C ₂ H ₅ OH + 3H ₂ O⇔6H ₂ + 2CO ₂ (2)
The CO shift reaction is represented by the following formula (3).

CO + H ₂ O⇔H ₂ + CO ₂ (3)
The composition of the reformed gas produced by the steam reforming reaction of methanol can be analyzed using, for example, a test apparatus shown in FIG. In the test apparatus of FIG. 1, a syringe pump 1 containing a mixed liquid of methanol and water is connected to a vaporizer 3 through a pipe 2. The supply pipe 4 for nitrogen gas is connected to the pipe 2 and supplies nitrogen gas to the vaporizer 3 together with the mixed liquid supplied from the syringe pump 1. The vaporizer 3 is connected to the reformer 6 through a pipe 5. The reformer 6 is filled with the aforementioned hydrogen production catalyst. The reformed gas in the reformer 6 is discharged from the pipe 9 via the pipe 7 and the water cooling trap 8. A gas chromatography 10 is connected in the middle of the pipe 9. The gas chromatography 10 samples the reformed gas flowing through the tube 9 and detects its gas composition.

In order to obtain a high-performance Cu-based catalyst, the present inventors mixed a copper compound and an aluminum compound at a specific Cu / Al molar ratio, and calcined at a specific temperature in a non-oxidizing atmosphere as a catalyst precursor. When a composite oxide composed of CuAlO ₂ or a mixed phase of CuAlO ₂ and Al ₂ O ₃ is produced and reduced using this composite oxide, a reforming catalyst having excellent stability and high low-temperature activity is obtained. I found out that The CuAlO ₂ phase is a phase generated when baked in a non-oxidizing atmosphere. When the composite oxide of CuAlO ₂ is reduced, substantially all of the Cu component is precipitated as metal Cu particles (diameter: 5 to 500 nm), and at the same time, the base material is converted to α-Al ₂ O ₃ to form Cu as a catalyst. A fine particle-supported composite material is obtained. The obtained composite material is dispersed and present in such a manner that fine Cu particles are partially embedded on the surface of the base α-Al ₂ O ₃ , and adhesion between the Cu particles and the base material (bonding property). ) Having a high Cu fine particle / base material integrated structure. Such a composite material (catalyst) exhibits high catalytic activity at low temperatures due to metal Cu particles, and in addition to oxidation resistance, has excellent sintering resistance (particle growth and coalescence resistance due to sintering). Have. When the oxidation treatment is actually performed, the surface properties of the Cu particles are changed to form CuO, but the separation of the particles from the substrate and the coalescence and growth of adjacent particles are hardly observed. That is, unlike the conventional Cu-based catalyst, there is no need for a reduction treatment immediately before use, and a catalyst that can be transported and transported in the air after synthesis can be obtained.

  In addition, the present inventors have found a catalyst for producing hydrogen, in which reforming performance shows high activity on a lower temperature side by further oxidizing the composite material.

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

(Examples 1-4 and Comparative Examples 1-2)
CuO powder was mixed with Al ₂ O ₃ powder at a Cu / Al molar ratio of 0.8 to 4.4, press-molded, and then fired at 1150 ° C. for 2 hours in an Ar stream of 2 L / min. Yui was done.

  The composition of the obtained sintered body was identified with an X-ray diffractometer. The results are shown in Table 1 below.

  Next, each sintered body was coarsely pulverized, sieved using a 200 μm mesh sieve, and the crushed pieces remaining on the sieve were subjected to reduction treatment at 700 ° C. for 5 minutes in hydrogen to produce 6 types of catalysts. The reduction in weight at this time is shown in Table 1 below.

  The average particle diameter of the metal Cu particles deposited on the surface of each obtained catalyst was measured by the method described above. The specific surface area of each catalyst was measured by a chemical adsorption method using hydrogen gas. The results are shown in Table 1 below.

(Comparative Example 3)
After CuO powder was mixed with Al ₂ O ₃ powder at a Cu / Al molar ratio of 2.0 and press-molded, it was sintered in air (in an oxidizing atmosphere) at 1150 ° C. for 2 hours. .

  The composition of the obtained sintered body was identified with an X-ray diffractometer. The results are shown in Table 1 below.

  Next, the sintered body was coarsely pulverized, sieved using a 200 μm mesh sieve, and the crushed pieces remaining on the sieve were subjected to reduction treatment at 700 ° C. for 5 minutes in hydrogen to produce a catalyst. The reduction in weight at this time is shown in Table 1 below.

  The average particle diameter of the metal Cu particles deposited on the surface of the obtained catalyst was measured by the method described above. The specific surface area of the catalyst was measured by a chemical adsorption method using hydrogen gas. The results are shown in Table 1 below.

In addition, the above-mentioned crushed pieces were used for the sintered bodies obtained in Example 2 and Comparative Example 3 in which the Cu / Al molar ratio when mixing Al ₂ O ₃ powder and CuO powder was the same as 2.0. The thermogravimetric change due to TG was measured in a hydrogen stream of 100 mL / min. The result is shown in FIG.

As is clear from Table 1, the sintered body that is a precursor of catalyst production in Examples 1 to 4 is CuAlO ₂ , or a complex oxide composed of a mixed phase of CuAlO ₂ and Al ₂ O ₃ , and production. It can be seen that each of the catalysts produced has a specific surface area of at most about 1 m ² / g.

On the other hand, in Comparative Example 1 in which the Cu / Al molar ratio at the time of forming the sintered body is less than the lower limit (1.0) of the present invention, the composite oxide has a larger amount of Al ₂ O ₃ than CuAlO _2. . In Comparative Example 2 in which the Cu / Al molar ratio at the time of forming the sintered body exceeds the upper limit (4.0) of the present invention, a composite oxide in which CuO is present together with CuAlO ₂ is obtained.

Further, in Comparative Example 3 in which the atmosphere at the time of forming the sintered body is an oxidizing atmosphere, the main component is a spinel type composite oxide (CuAl ₂ O ₄ ).

Further, as is apparent from FIG. 2, the composite oxide containing CuAlO ₂ used in Example 2 has only one reduction near 600 ° C. As a result, the precipitated metal Cu particles became uniform in diameter and dispersion state. Such thermogravimetric change during reduction is the same for the composite oxides used in Examples 1, 3, and 4 other than Example 2. On the other hand, the reduction of the composite oxide containing the spinel type composite oxide (CuAl ₂ O ₄ ) used in Comparative Example 3 is greatly advanced in two stages, around 350 ° C. and around 600 ° C. For this reason, the deposited metal Cu particles were enlarged, and the dispersion state thereof became non-uniform.

  Next, a methanol reforming reaction test was performed using the catalysts of Examples 1 to 4 and Comparative Examples 1 to 3 and the test apparatus of FIG. 1 described above.

  All reactors and piping shown in FIG. 1 are made of stainless steel. First, the catalyst obtained in Example 2, the catalyst obtained by further oxidizing this catalyst, the catalyst obtained in Comparative Example 3 and the commercially available Cu—Zn-based catalyst (Comparative Example 4) were introduced into the reformer 6 in about 2 g (about 1.8 cc) was charged.

  The oxidation treatment of the catalyst obtained in Example 2 was performed by heating for 15 minutes in a simulated atmosphere using an oxygen-nitrogen mixture (oxygen flow rate: nitrogen flow rate = 1: 4) at 250 ° C. As a result of analyzing the surface of the catalyst after the oxidation treatment by XPS, the presence of Cu together with CuO was recognized. Moreover, as a result of measuring the specific surface area of the catalyst after the oxidation treatment by the chemical adsorption method using hydrogen gas, it was confirmed that the specific surface area was about 3 to 5 times larger than that before the oxidation treatment.

  The Cu—Zn-based catalyst of Comparative Example 4 was charged in the reformer 6, then reduced at 250 ° C. for 30 minutes while introducing 100% hydrogen gas, and never exposed to the atmosphere. .

  Next, methanol and water were mixed so that the molar ratio was 1: 2 after vaporization, and the solution was sent in a fixed amount by the syringe pump 1. The liquid feeding speed was 50 mL / min of methanol and 100 mL / min of water vapor at the flow rate when vaporized. The temperature of the vaporizer 3 was 140 ° C., and 50 mL / min of nitrogen gas was supplied from the supply pipe 4 as a standard gas in order to quantify the outlet gas concentration. The temperature of the reformer 6 is set to 250 and 300 ° C. with a heater (not shown), held at each temperature for about 1 hour until the outlet gas composition is stabilized, and then the gas chromatograph 10 is used to circulate the pipe 9 Then, the reformed gas was sampled, and the reformed gas composition was analyzed.

From the analysis of the reformed gas composition, the methanol conversion rate and CO production rate at 250 ° C. and 300 ° C. for each catalyst were determined. The results are shown in Table 2 below.

  As apparent from Table 2, the catalyst of Example 2 (after the reduction treatment) had methanol as compared with the catalyst of Comparative Example 3 in which the Cu / Al molar ratio during the formation of the composite oxide was the same as 2.0. It can be seen that high catalytic activity is exhibited on the low temperature side during the reforming reaction. It can also be seen that further oxidation treatment of the catalyst of Example 2 shows higher catalytic activity on the low temperature side during the methanol reforming reaction than in the reduction treatment alone.

  The Cu—Zn-based catalyst of Comparative Example 4 shows a very high catalytic activity on the low temperature side during the methanol reforming reaction, but not only requires a reduction treatment before the reforming reaction, but is not exposed to the atmosphere. There are complicated reforming reaction operations and handling.

Further, the catalysts obtained in Examples 1, 3 and 4, the catalysts obtained by oxidizing these catalysts under the same conditions as in Example 2 described above, and the catalysts obtained in Comparative Examples 1 and 2 are shown in FIG. A methanol steam reforming reaction is performed under the same conditions as described above except that about 2 g (about 1.8 cc) is charged in the reformer 6 of the test apparatus, and the reformed gas composition is analyzed by the gas chromatography 10. And methanol conversion and CO production at 250 ° C. and 300 ° C. were determined. The results are shown in Table 3 below.

  As is apparent from Table 3, the catalysts of Examples 1, 3 and 4 (after reduction treatment) were compared in which the Cu / Al molar ratio when producing the sintered body was outside the range (1 to 4) of the present invention. Compared to the catalysts of Examples 1 and 2 (after reduction treatment), it can be seen that the catalyst activity is higher on the low temperature side during the reforming reaction of methanol. This is because the catalyst of Comparative Example 1 having a Cu / Al molar ratio of less than 1 in producing a sintered body has low activity, and Comparative Example 2 in which the Cu / Al molar ratio in producing a sintered body exceeds 4 This catalyst is considered to be because the effective specific surface area was reduced due to aggregation of adjacent metal Cu particles.

  It can also be seen that further oxidation treatment of the catalyst of Example 2 shows higher catalytic activity on the low temperature side during the methanol reforming reaction than in the reduction treatment alone.

The schematic diagram which shows a methanol reforming test apparatus. The figure which shows the result of the thermogravimetric analysis at the time of the reduction | restoration of the complex oxide of Example 2 and Comparative Example 3 of this invention.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 ... Syringe pump, 3 ... Vaporizer, 6 ... Reformer, 10 ... Gas chromatography.

Claims (5)

After mixing the Cu compound and the aluminum compound so that the molar ratio of Cu / Al is 1 to 4, this mixture is fired at a temperature of 900 to 1300 ° C. in a non-oxidizing atmosphere to obtain CuAlO ₂ or CuAlO ₂ . Producing a composite oxide composed of a mixed phase of Al ₂ O ₃ ;
Precipitating metal Cu particles having an average particle diameter of 5 to 500 nm on at least the surface portion of the base material of α-type Al ₂ O ₃ by heating and reducing the composite oxide in a reducing atmosphere. A method for producing a hydrogen production catalyst, comprising: The composite oxide is produced by mixing Al ₂ O ₃ powder and CuO powder so that the molar ratio of Cu / Al is 1 to 4, and then mixing the mixture in a non-oxidizing atmosphere at 900 to 1300 ° C. The method for producing a catalyst for hydrogen production according to claim 1, wherein the method is carried out by a method of calcining at a temperature.   The method for producing a catalyst for hydrogen production according to claim 1, wherein the reduction treatment of the composite oxide is performed at a temperature of 600 ° C to 1000 ° C in a reducing atmosphere.   2. The method for producing a catalyst for hydrogen production according to claim 1, wherein the base material having the metal Cu particles is further heated in an oxidizing atmosphere to be oxidized.   The method for producing a catalyst for hydrogen production according to claim 4, wherein the oxidation treatment is performed at a temperature of 150 to 350 ° C. in an oxygen-containing atmosphere.

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