JPWO2018150823A1 - Method for producing structure catalyst, and method for producing hydrogen using structure catalyst - Google Patents

Abstract

A method for producing a structural catalyst using a clad material having an aluminum layer formed on the surface of a metal support includes performing an anodic oxidation step (S1) for converting the surface of the aluminum layer into an alumina layer, The first immersion treatment (S4) of immersing the clad substrate after the oxidation treatment in an aqueous solution containing a catalyst component is performed, and the clad substrate after the first immersion treatment is oxidized. A first baking process (S5) of baking in a temperature range of 120 to 500 ° C. is performed in an atmosphere, and the clad substrate after the first baking process is immersed in an aqueous solution containing the catalyst component. The second immersion treatment (S6) is performed, and the second immersion treatment (S7) is performed on the clad base material that has been subjected to the second immersion treatment, in an oxidizing atmosphere, in a temperature range of 500 to 700 ° C. .

Description

  The present invention relates to a method for producing a structure catalyst for generating hydrogen by a catalytic reaction from a raw material gas containing hydrocarbon and water, and a method for producing hydrogen using a structure catalyst obtained by the production method. .

  Hydrogen is a clean energy and has a wide range of uses such as industrial use as a reducing agent, and in recent years, it is particularly expected as a fuel for hydrogen automobiles and fuel cells. As one of the methods for producing hydrogen gas, a mixed gas containing hydrogen by a steam reforming reaction or carbon monoxide shift reaction using a catalyst and a hydrocarbon and water represented by city gas and natural gas as raw materials is used. The method of obtaining is well known. In general, as a catalyst used for a steam reforming reaction or a carbon monoxide shift reaction, a granular catalyst in which a metal or a metal compound as an active component is supported on the surface of a granular carrier is used.

  However, since the contact efficiency between the reaction gas, which is a raw material, and the catalyst component, which is an active component, is poor in a granular catalyst, to increase the reaction rate, the amount of contact of the granular catalyst in the reforming reactor is increased and the contact area is increased. Alternatively, a method of increasing the contact efficiency by reducing the size of the granular catalyst as much as possible may be employed. However, increasing the filling amount of the granular catalyst increases the gas flow resistance and increases the pressure loss. In addition, when the size of the granular catalyst is reduced, the contact efficiency increases, but since the ratio of the voids decreases, the pressure loss increases, the power for supplying the gas increases, and the efficiency decreases in terms of energy. .

  In recent years, as one of the solutions for the inconvenience related to such a granular catalyst, it has been proposed to use a structure catalyst instead of the granular catalyst (see, for example, Patent Document 1). However, in general, the structure catalyst has a property that the initial activity is higher than that of the granular catalyst, but the activity rapidly decreases with the lapse of time, so that it cannot be used for a long time. (For example, see Non-Patent Document 1).

JP-A-2005-211836

Journal of Chemical Engineering of Japan, Vol. 47, No. 7, pp. 536-541, 2014

  The present invention has been conceived under such circumstances, and relates to a structural catalyst used in a method of generating a mixed gas containing hydrogen by catalytic reaction from a raw material gas containing hydrocarbon and water. The main object is to provide a method for producing a structural catalyst suitable for suppressing a decrease in catalytic activity.

  The present inventors diligently studied a method for producing a structure catalyst used in a method of generating a mixed gas containing hydrogen from a raw material gas containing hydrocarbon and water by a catalytic reaction. As a result, when impregnating and supporting the catalyst component on the support after the anodic oxidation treatment, the immersion treatment in the catalyst component-containing aqueous solution and the firing treatment in an oxidizing atmosphere are divided into two times, and for each of the two firing treatments, The present invention has been completed by finding a calcining temperature range in which the resulting structure catalyst has a high catalytic activity and is suitable for further suppressing a decrease in catalytic activity.

  According to the first aspect of the present invention, there is provided a method for producing a structural catalyst using a clad material in which an aluminum layer is formed on the surface of a metal support. According to the method, a first anodizing process is performed for converting the surface of the aluminum layer into an alumina layer, and the clad base material that has been subjected to the anodizing process is immersed in an aqueous solution containing a catalyst component. Immersion treatment was performed, and the first firing treatment was performed on the clad substrate that had been subjected to the first immersion treatment in a temperature range of 120 to 500 ° C. in an oxidizing atmosphere, and the first firing treatment was completed. The clad substrate is subjected to a second dipping treatment in which it is immersed in an aqueous solution containing the catalyst component, and the clad substrate that has been subjected to the second dipping treatment is 500 to 700 ° C. in an oxidizing atmosphere. A second baking process is performed in which the baking is performed in the temperature range.

  Preferably, the catalyst component is a metal containing nickel, and the metal support is made of a nickel chromium alloy.

  Preferably, the anodizing treatment is performed until all of the aluminum layer is changed to an alumina layer.

  Preferably, after the anodizing treatment and before the first immersion treatment, the clad substrate is treated in an acidic solution to enlarge pores formed in the alumina layer by the anodizing treatment. The pore enlargement process is further performed.

  Preferably, after the pore enlargement treatment and before the first immersion treatment, the clad substrate is treated with water vapor or liquid phase water to further hydrate the alumina. .

  Preferably, after the second baking treatment, a pore enlargement treatment is further performed in which the clad substrate is treated in an acidic solution to enlarge pores formed in the alumina layer by the anodizing treatment.

  According to the 2nd side surface of this invention, the manufacturing method of hydrogen performed using the structure catalyst obtained by the manufacturing method of the structure body catalyst which concerns on the 1st side surface of this invention is provided. In the method, the structural catalyst is disposed inside a reforming reactor, and a reforming reaction is performed in the reforming reactor with a raw material gas containing hydrocarbon and water while heating the reforming reactor. It is. From the viewpoint of economy, it is preferable that the metal support is made of a nickel chromium alloy, and the structure catalyst is heated by passing an electric current through the metal support when the reforming reactor is heated.

  Other features and advantages of the present invention will become more apparent from the detailed description given below with reference to the accompanying drawings.

It is a processing flow figure showing an example of a manufacturing method of a structure catalyst concerning the present invention. The schematic structure of the gas generator which can be used for performing the manufacturing method of hydrogen which concerns on this invention is represented.

  Hereinafter, preferred embodiments of the present invention will be specifically described with reference to the drawings.

  FIG. 1 is a process flow diagram showing an example of a method for producing a structural catalyst according to an embodiment of the present invention. As shown in the figure, in the production of the structure catalyst, the clad substrate is subjected to an anodizing treatment S1, a pore enlargement treatment S2, a hydration treatment S3, a first immersion treatment S4, a first firing treatment S5, The second immersion process S6 and the second baking process S7 are sequentially performed.

  The clad substrate is a carrier formed by forming an aluminum layer on the surface of a metal support. The shape of the clad substrate may be any shape such as a plate shape, a rod shape, a cylindrical shape, a ribbon shape, and a honeycomb shape, and is not particularly limited as long as it has a constant shape.

  The above-mentioned metal support capable of providing an aluminum layer on the surface is, for example, Mg (magnesium), Cr (chromium), Mo (molybdenum), W (tungsten), Mn (manganese), Fe (iron), Co (cobalt), Ni (nickel), Ti (titanium), Zr (zirconium), V (vanadium), Cu (copper), Ag (silver), Zn (zinc), Bi (bismuth), Sn (tin), A single metal or alloy selected from the group consisting of Pb (lead) and Sb (antimony), or a composite metal obtained by laminating these metals. The metal support is preferably stainless steel or nickel chrome alloy from the viewpoint of heat resistance.

  As a method for forming the aluminum layer on the surface of the metal support, any of known methods such as non-water plating, pressure bonding, vapor deposition, dripping, thermal spraying, rolling (clad method) may be used. Among these, from the viewpoint of thickness uniformity and manufacturability, it is preferable to use a rolling method and attach an aluminum plate or aluminum foil to the surface of the metal support. The thickness of the aluminum layer may be 5 μm or more, but is preferably 10 to 300 μm, and more preferably 30 to 200 μm. However, the aluminum referred to in this specification includes an aluminum alloy that can be anodized. A clad substrate having a cylindrical shape, a honeycomb shape or the like can be obtained by processing a plate-like clad substrate into such a shape.

  Anodization of the surface of the aluminum layer in the clad material (anodization treatment S1 in FIG. 1, anodization step) can be easily performed using a known anodization technique. When anodizing the surface of the aluminum layer, it is preferable to use a highly oxidizing acid such as oxalic acid, chromic acid, sulfuric acid, etc. as the treatment liquid (electrolytic solution). This makes it easy to change all the aluminum layers to alumina layers and to advance anodic oxidation to the inside of the diffusion layer provided as necessary, thereby diffusing oxygen atoms to the inside of the diffusion layer. What is necessary is just to determine the acid concentration of a process liquid suitably, for example, when using oxalic acid, it is preferable to set it as 2-6 wt% aqueous solution.

The conditions for anodization may be set as appropriate so that the BET specific surface area of the alumina layer is increased, but the treatment liquid temperature for anodization is preferably 0 to 50 ° C., particularly preferably room temperature to 40 ° C. When the temperature of the anodizing treatment solution is less than 0 ° C., the BET specific surface area is not so large, and when it exceeds 50 ° C., the dissolution of aluminum into the electrolytic solution becomes intense, making it difficult to efficiently form an oxide film. . The treatment time for this anodization varies depending on other treatment conditions. For example, when a 4.0 wt% oxalic acid aqueous solution is used as the electrolyte, the electrolyte temperature is 30 ° C., and the current density is 65.0 A / m ² , it is preferably 2 hours or more, particularly 4 hours or more.

  After the anodizing treatment, post-baking is preferably further performed at 350 ° C. or higher for 1 hour or longer, preferably 450 ° C. to 550 ° C., if necessary. This makes the anodic oxide film a γ-alumina layer, which is preferable as the surface of the catalyst carrier, and can reduce the change in the concentration of oxygen atoms in the diffusion layer.

  Further, after the anodizing treatment, in order to increase the BET specific surface area of the anodized film surface and improve the heat resistance, a pore enlarging treatment (pore enlarging treatment S2 in FIG. 1) may be performed. The pore enlargement treatment is a treatment for expanding pores in the anodized film using an acidic aqueous solution. As the acidic aqueous solution used here, the same treatment solution as used in the anodic oxidation can be used. Therefore, after the anodization, the pore enlargement process can be continued in the same processing solution. The treatment conditions (temperature and time) for this pore enlargement treatment may be appropriately set according to the type and concentration of the acid used as the treatment liquid. The concentration of the treatment liquid is preferably set so that the pH of the treatment liquid is 3-6. For example, when 4.0 wt% oxalic acid is used at 20 ° C., it is appropriate that the treatment time is about 90 to 120 minutes.

  Furthermore, you may perform a hydration process (hydration process S3 of FIG. 1) after a pore expansion process. The hydration treatment is performed using water vapor or liquid phase water, and the temperature of the water is, for example, 5 to 100 ° C., preferably 40 to 100 ° C. The treatment time of the hydration treatment is appropriately set according to the temperature of water, but is preferably set to about 1 to 2 hours, for example. The water used for the hydration treatment is preferably distilled water or ion exchange water.

  A catalyst body can be obtained by supporting a metal catalyst on the surface of the alumina support thus obtained. The catalyst component to be supported is at least one selected from the group consisting of nickel, lanthanum, copper and cerium, and alloys and compounds thereof, or a mixture containing one or more of them. Among these, nickel is preferable from the viewpoint of economy and catalytic activity.

  The method for supporting the metal catalyst on the surface of the alumina support includes dipping and firing. In this embodiment, immersion and baking are repeated twice. For the immersion treatment, for example, when the catalyst component is nickel, a nickel-containing aqueous solution such as a nickel nitrate aqueous solution or a nickel acetate aqueous solution is used as the treatment liquid. As processing conditions of the first immersion treatment (immersion treatment S4 in FIG. 1), for example, the nickel-containing concentration of the nickel-containing aqueous solution is 1 to 10 mol / L, the pH is 5.0 to 6.0, and the immersion temperature is 20 to 40 ° C. The immersion time is 1 to 10 hours. From the viewpoint of obtaining high activity as a catalyst, it is preferable that the nickel-containing concentration is 2 to 4 mol / L, the pH is 5.0 to 5.5, the immersion temperature is 25 to 30 ° C., and the immersion time is 2 to 5 hours. .

  About the drying which removes the water | moisture content after a 1st immersion process, natural drying or heat drying to 100 degreeC is implemented for 10 to 24 hours. Here, since rapid drying in a short time may cause peeling of the supported nickel component, drying over 50 ° C. or less is preferable.

After drying, a first firing process (firing process S5 in FIG. 1) is performed for reacting the nickel component with alumina to change it into nickel aluminate (NiAl ₂ 0 ₄ ). The said baking process is performed in the air, and a baking temperature is 120-500 degreeC, for example, and it is preferable to set it as 400-500 degreeC from a viewpoint of producing | generating nickel aluminate effectively after a process. The firing time can be selected, for example, from 1 to 10 hours, but is preferably 3 to 5 hours from the viewpoint of sufficient reaction progress and economy.

After the first baking process, a second dipping process, drying, and a second baking process are performed. The process conditions of the second immersion process (immersion process S6 in FIG. 1) are, for example, the same conditions as the first immersion process. In the second firing treatment (firing treatment S7 in FIG. 1), the firing temperature is, for example, 500 to 700 ° C., and preferably 600 to 700 ° C. from the viewpoint of sufficiently generating nickel oxide (NiO _x ). The firing time is, for example, 1 to 10 hours, but is preferably 3 to 5 hours from the viewpoint of sufficient reaction progress and economy. In addition, after 2nd baking process, by reducing hydrogen oxide to nickel by performing hydrogen reduction process for 0.5 hours-2 hours using a hydrogen gas stream at the temperature of 600-900 degreeC, catalytic activity is carried out. An enhanced structure catalyst is obtained.

  According to this embodiment, regarding the production of a structural catalyst used in a method for generating a mixed gas containing hydrogen from a raw material gas containing hydrocarbon and water by a catalytic reaction, the support after anodization is impregnated with a catalyst component. A structure in which the catalytic activity is high and the decrease in catalytic activity is reduced by carrying out the immersion treatment in the catalyst component-containing aqueous solution and the firing treatment in the oxidizing atmosphere in two times and carrying out the firing at a predetermined firing temperature. A body catalyst can be obtained.

  Next, the usefulness of the present invention will be described with reference to examples and comparative examples.

[Example 1]
<Production of structure catalyst>
In Example 1, a nickel chromium alloy (Ni content ratio ≧ 77 wt%, Cr content ratio 19 to 21 wt%, thickness 50 μm) was used as a core (metal support), and aluminum foil having a thickness of 50 μm was laminated on both surfaces of the core. A nickel chrome alloy core / aluminum clad substrate was obtained using a rolling mill. This clad substrate was cut out into a clad substrate having a planar size of 3.5 cm × 12.5 cm. The cut out clad substrate was anodized using a 4.0 wt% oxalic acid aqueous solution at a liquid temperature of 30 ° C. and a current density of 65.0 A / m ² for 6.5 hours. Thereafter, using a 4.0 wt% oxalic acid aqueous solution, a pore enlargement treatment was performed at a liquid temperature of 30 ° C. for 2 hours, followed by baking in air at 350 ° C. for 1 hour, and then immersed in ion exchange water at 80 ° C. for 1 hour. The hydration process was performed by doing. Further, it was fired in air at 500 ° C. for 3 hours to obtain a plate-like alumina carrier having a nickel chromium alloy as a core.

This plate-like carrier was immersed in an aqueous nickel nitrate solution (3 mol / L, pH = 5.1) for 3 hours as a first immersion treatment. Next, after natural drying, a first baking treatment was carried out in air at 500 ° C. for 3 hours to impregnate and carry a nickel component. Further, the plate-like carrier after the first baking treatment was immersed in an aqueous nickel nitrate solution (3 mol / L, pH = 5.1) for 3 hours as a second immersion treatment. Next, after natural drying, a second baking treatment was performed in air at 700 ° C. for 3 hours to impregnate and support the nickel component. In the obtained structure catalyst, the amount of nickel supported as a catalyst component was measured by ICP emission spectroscopy (high frequency inductively coupled plasma emission spectroscopy, ICP-OES / CP-AES). The supported amount was 15.0 g / m ^{2, and} the supported amount was 18.0 wt% with respect to alumina as the carrier component of the structural catalyst.

  Next, as a pretreatment for carrying out the steam reforming reaction of hydrocarbon, the structure catalyst is subjected to hydrogen reduction treatment by heating at 800 ° C. for 1 hour under a hydrogen gas stream, and nickel oxide is catalytically activated. It was converted into metallic nickel as a component to obtain a final structure catalyst.

<Production of hydrogen>
In the steam reforming reaction test, methane gas was used as the hydrocarbon, and a raw material gas of this and water (steam) was introduced into the reforming reactor. The volume ratio of introduced gas between methane gas and water was 1: 3, and the reaction temperature was 750 ° C. The pressure was performed under atmospheric pressure.

  One hour after the start of the test, the hydrogen-containing mixed gas obtained by the reaction was cooled with a water-cooled gas cooler, excess water vapor was removed as condensed water, and the composition was analyzed with a gas analyzer. The gas composition converted to the dry state excluding water was 76.0% for hydrogen, 7.0% for carbon dioxide, 17.0% for carbon monoxide, and methane was not detected below the detection limit.

  24 hours after the start of the test, the gas composition converted to a dry state excluding water was 76.0% for hydrogen, 7.0% for carbon dioxide, 17.0% for carbon monoxide, and methane detected below the detection limit. No decrease in catalytic activity was observed.

[Comparative Example 1]
In Comparative Example 1, the same plate-like alumina carrier as in Example 1 was used. The treatment (immersion treatment and firing treatment) for supporting the catalyst component on the plate-like carrier was performed twice in Example 1, but was performed once in Comparative Example 1 as described below.

  In Comparative Example 1, the plate-like carrier was immersed in an aqueous nickel nitrate solution (3 mol / L, pH = 5.1) for 6 hours as an immersion treatment. Next, after natural drying, a calcination treatment was performed in air at 500 ° C. for 3 hours to impregnate and carry a nickel component. In this way, a structure catalyst for use in the production of hydrogen by a steam reforming reaction was produced. In the obtained structure catalyst, the supported amount of nickel as the catalyst component was the same as in Example 1. The subsequent hydrogen reduction treatment and steam reforming reaction test conditions were the same as in Example 1.

  One hour after the start of the test, the hydrogen-containing mixed gas obtained by the reaction was cooled with a water-cooled gas cooler, excess water vapor was removed as condensed water, and the composition was analyzed with a gas analyzer. The gas composition converted to the dry state excluding water was 76.0% for hydrogen, 7.0% for carbon dioxide, 17.0% for carbon monoxide, and methane was not detected below the detection limit. This was the same as Example 1.

  However, after 24 hours from the start of the test, the gas composition converted to a dry state excluding water is 72.0% for hydrogen, 10.0% for carbon dioxide, 10.0% for carbon monoxide, and 8.8% for methane. 0% and unreacted methane was detected. From this, in the comparative example 1, the fall of catalyst activity was recognized clearly.

[Comparative Example 2]
In Comparative Example 2, the same plate-like alumina carrier as in Example 1 was used. The treatment (soaking treatment and firing treatment) for supporting the catalyst component on the plate-like carrier was the same as in Example 1 in that the treatment was carried out in two steps, but the temperature conditions for the firing treatment were implemented as described below. It was different from Example 1.

  In Comparative Example 2, the plate-shaped carrier was immersed in an aqueous nickel nitrate solution (3 mol / L, pH = 5.1) for 3 hours as an immersion treatment. Next, after natural drying, a first baking treatment was carried out in air at 700 ° C. for 3 hours to impregnate and carry a nickel component. Further, the plate-like carrier after the first baking treatment was immersed in an aqueous nickel nitrate solution (3 mol / L, pH = 5.1) for 3 hours as a second immersion treatment. Next, after natural drying, a second baking treatment was carried out in air at 500 ° C. for 3 hours to impregnate and carry the nickel component. In the obtained structure catalyst, the supported amount of nickel as the catalyst component was the same as in Example 1. The conditions for the subsequent hydrogen reduction treatment and steam reforming reaction test were also the same as in Example 1.

  One hour after the start of the test, the hydrogen-containing mixed gas obtained by the reaction was cooled with a water-cooled gas cooler, excess water vapor was removed as condensed water, and the composition was analyzed with a gas analyzer. The gas composition converted to the dry state excluding water was 76.0% for hydrogen, 7.0% for carbon dioxide, 17.0% for carbon monoxide, and methane was not detected below the detection limit. This was the same as Example 1.

  However, after 24 hours from the start of the test, the gas composition converted to a dry state excluding water is 72.0% for hydrogen, 10.0% for carbon dioxide, 10.0% for carbon monoxide, and 8.8% for methane. 0% and unreacted methane was detected. From this, in this comparative example, the fall of the catalyst activity was recognized clearly.

[Example 2]
In Example 2, the same structure catalyst as that used in Example 1 was used for producing hydrogen by the steam reforming reaction. In Example 2, the steam reforming reaction was performed using the gas generator X having the schematic configuration shown in FIG. The gas generator X shown in the figure includes a reforming reactor 1, a power source 2, and a controller 3. As the material of the reforming reactor 1, SUS304 material which is stainless steel was used. Electrodes 5 and 6 are connected to both ends of the structure catalyst 4 arranged in the reforming reactor 1, and a current flows through the structure catalyst 4 via the electrodes 5 and 6. The reforming reactor 1 itself can be heated by an external heater (not shown).

  In Example 2, the current value and the energization time are controlled so that the surface temperature of the structure catalyst 4 becomes 750 ° C. optimum for the reaction by energizing the structure catalyst 4 (nickel chromium alloy which is a metal support). In order to enhance the heat retention effect of the reaction temperature, heating was performed at 500 ° C. as external heating. The pressure was carried out under the same atmospheric pressure as in Example 1.

  One hour after the start of the test, the hydrogen-containing mixed gas obtained by the reaction was cooled with a water-cooled gas cooler 7, excess water vapor was removed as condensed water, and composition analysis was performed with a gas analyzer. The gas composition converted to the dry state excluding water was 76.0% for hydrogen, 7.0% for carbon dioxide, 17.0% for carbon monoxide, and methane was not detected below the detection limit.

  24 hours after the start of the test, the gas composition converted to a dry state excluding water was 76.0% for hydrogen, 7.0% for carbon dioxide, 17.0% for carbon monoxide, and methane detected below the detection limit. No decrease in catalytic activity was observed.

Example 3
In Example 3, the same structure catalyst as that used in Examples 1 and 2 was used for the production of hydrogen by the steam reforming reaction. Example 3 differs from Example 2 in that, firstly, the material of the reforming reactor is Inconel (registered trademark) 800, which has high heat resistance but is expensive, and secondly, steam reforming. In the reaction, no electric heating operation was performed, and heating was performed at 800 ° C. as external heating so that the reaction temperature in the reforming reactor was 750 ° C. The other operating conditions in Example 3 were the same as in Example 2. The gas composition of the hydrogen-containing mixed gas (dry state) obtained by the reaction was the same as that of Example 2 after 1 hour and 24 hours from the start of the test.

  As understood from Examples 2 and 3, in the case of Example 2, the structure catalyst 4 itself is caused to generate heat by energizing the structure catalyst 4 (metal support which is the core of the structure catalyst). The heat energy required for external heating can be greatly reduced. As a result, the overall thermal energy efficiency for appropriately performing the steam reforming reaction can be increased, which contributes to the reduction of hydrogen production costs.

X Gas generator 1 Reforming reactor 2 Power source 3 Controller 4 Structure catalyst 5 Electrode 6 Electrode 7 Gas cooler

Claims (9)

A method for producing a structural catalyst using a clad substrate having an aluminum layer formed on the surface of a metal support,
Anodizing for converting the surface of the aluminum layer into an alumina layer,
For the clad substrate that has been subjected to the anodization treatment, a first immersion treatment is performed in which the clad substrate is immersed in an aqueous solution containing a catalyst component,
For the clad substrate that has completed the first immersion treatment, a first firing treatment is performed in a temperature range of 120 to 500 ° C. in an oxidizing atmosphere,
For the clad substrate that has finished the first baking treatment, a second immersion treatment is performed in which the clad substrate is immersed in an aqueous solution containing the catalyst component,
The manufacturing method of a structure catalyst which performs the 2nd calcination process which calcinates in the temperature range of 500-700 ° C in the oxidizing atmosphere to the clad base material which finished the 2nd immersion treatment.   The method for producing a structural catalyst according to claim 1, wherein the catalyst component is a metal containing nickel.   The said metal support body is a manufacturing method of the structure catalyst of Claim 1 or 2 which consists of a nickel chromium alloy.   The method for producing a structural catalyst according to any one of claims 1 to 3, wherein the anodic oxidation treatment is performed until all of the aluminum layer is changed to an alumina layer.   After the anodizing treatment and before the first dipping treatment, the clad substrate is treated in an acidic solution to expand pores formed in the alumina layer by the anodizing treatment. The manufacturing method of the structure catalyst in any one of Claims 1-4 which further performs an expansion process.   The hydration treatment is further performed by hydrating the alumina by treating the clad substrate with water vapor or liquid phase water after the pore enlargement treatment and before the first immersion treatment. 6. A process for producing the structure catalyst according to 5.   2. The pore enlargement treatment is further performed after the second firing treatment, in which the clad substrate is treated in an acidic solution, and the pores formed in the alumina layer by the anodization treatment are enlarged. The manufacturing method of the structure catalyst in any one of -4. A method for producing hydrogen using the structure catalyst obtained by the method for producing a structure catalyst according to claim 1,
Production of hydrogen, wherein the structural catalyst is disposed inside a reforming reactor, and the reforming reactor is heated and a raw material gas containing hydrocarbon and water is reformed in the reforming reactor. Method. A method for producing hydrogen using the structure catalyst obtained by the method for producing a structure catalyst according to claim 3,
The structural catalyst is disposed inside the reforming reactor, and current is passed through the metal support to heat the structural catalyst, and a raw material gas containing hydrocarbon and water is introduced into the reforming reactor. A method for producing hydrogen by reforming reaction.

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