TW201940233A - Production method for structured catalyst and hydrogen production method using structured catalyst - Google Patents

Abstract

Provided is a production method for a structured catalyst that is for generating highly concentrated hydrogen gas from a gas that includes hydrogen and carbon monoxide by means of a water-gas shift reaction. The production method for a structured catalyst includes: an anodization step (S1) in which the surface of an aluminum substrate is anodized to form an alumina carrier; a first immersion step (S4) in which the alumina carrier is immersed in an aqueous solution that contains a catalyst component; a first firing step (S5) in which the alumina carrier, which is loaded with a partial amount of the catalyst component during the first immersion step, is fired in an oxidizing atmosphere at a temperature of 120 DEG C-500 DEG C; a second immersion step (S6) in which, after underdoing the first firing step, the alumina carrier is immersed in an aqueous solution that contains the catalyst component; and a second firing step (S7) in which the alumina carrier, which is loaded with a final amount of the catalyst component during the second immersion step, is fired in an oxidizing atmosphere at a temperature of 120 DEG C-500 DEG C.

Description

Method for producing structural catalyst and method for producing hydrogen

The invention relates to a method for manufacturing a structure catalyst using a water gas conversion reaction, in which carbon monoxide contained in a reaction gas reacts with water vapor to be converted into carbon dioxide and hydrogen, and the structure catalyst is obtained by using the structure catalyst obtained by the manufacturing method. Manufacturing method of hydrogen.

Hydrogen is a kind of green energy, which has a wide range of applications, such as industrial use as a reducing agent and so on. In recent years, hydrogen has been particularly desired as a fuel for hydrogen vehicles, fuel cells, and the like. As one of the methods for generating hydrogen, hydrocarbons and water, which are representative city gases, natural gas, etc., are used as raw materials. As shown in the following reaction formula, a well-known method is to use a catalyst. Steam reforming reaction, water gas shift reaction, etc. to obtain a hydrogen-containing mixed gas. In general, the shape of the catalyst used for the water-gas conversion reaction may be a granular catalyst that carries a metal, a metal compound, and the like having an active ingredient on the surface of the granular support.
C _m H _n + mH ₂ O → mCO + (m + n / 2) H ₂
CO + H ₂ O → CO ₂ + H ₂

Due to the poor contact efficiency between the granular catalyst as the raw material of the reaction gas and the active ingredient as the catalyst component, in order to increase the reaction rate, a method of improving the contact efficiency can be adopted, such as increasing the filling of the granular catalyst in the reactor Amount, or increase the contact point, or minimize the size of the granular catalyst and so on. However, increasing the amount of granular catalyst added will increase airflow resistance and increase pressure loss. In addition, although reducing the size of the granular catalyst increases the contact efficiency, the ratio of the void portion is reduced, which instead increases the pressure loss, and also increases the power to supply the gas. As a result, the problem of efficiency is reduced.

In the water gas conversion reaction, generally, the reaction temperature is about 150 ~ 230 ° C, using copper-zinc-aluminum catalyst, platinum / alumina catalyst, etc., the reaction temperature is about 350 ~ 450 ° At high temperatures of C, iron-chromium catalysts are used. Various copper-zinc-aluminum catalysts are known. Patent Document 1 discloses production of a copper-zinc-aluminum catalyst by an impregnation method, and Patent Document 2 discloses production of a copper-zinc-aluminum catalyst by a coprecipitation method using ammonia as a neutralizing agent. In addition, Patent Document 3 discloses the production of a copper-zinc-aluminum catalyst by firing a catalyst precursor material containing copper, zinc, and aluminum and having a specific X-ray diffraction pattern. These copper-zinc-aluminum catalysts have excellent activity and durability.

The copper-zinc catalysts described in Patent Documents 1 to 3 are less expensive and have excellent activity at low temperatures than precious metal catalysts that carry precious metals such as platinum on titanium oxide, cerium oxide, and the like. However, copper-zinc catalysts are turned on and off as frequently as fuel cells, and under conditions of repeated temperature rise and fall, oxidation accompanied by evaporation of water and reduction due to recombination gas are generated. As a result, copper sintering ( sintering) produces grain growth, the catalyst is easy to lose activity.

[Advanced technical literature]
[Patent Document 1] Japanese Patent Laid-Open No. 2005-034682
[Patent Document 2] Japanese Patent Laid-Open No. 2004-202310
[Patent Document 3] Japanese Patent Laid-Open No. 2012-139637

[Invention Summary]

The present invention was conceived in such a situation, and a method for providing a structured catalyst suitable for suppressing the low activity of a catalyst is provided by a method of using a catalyst to generate a high-concentration hydrogen gas from a gas containing hydrogen and carbon monoxide by a water gas conversion reaction. The manufacturing method is the main object of the present invention.

As a result of intensive studies by the present inventors, regarding the manufacture of a structure catalyst using a water gas conversion reaction, when the support after the anodizing treatment is impregnated with the catalyst component, the immersion treatment in an aqueous solution containing the catalyst component and The firing treatment under an oxidizing environment is divided into two times, and for each of the two firing treatments, a catalyst having a higher catalytic activity and further suppressing a low catalytic activity suitable for the obtained structural catalyst is found. The firing temperature range completes the present invention.

The method for manufacturing a structural catalyst provided by the first aspect of the present invention is characterized by performing an anodizing step of anodizing the surface of an aluminum substrate as a metal support, and performing a first immersion in an aqueous solution containing a catalyst component. The immersion step includes a first sintering step in which the sintering is performed at a temperature range of 120 to 500 ° C under an oxidizing environment, a second immersion step in which the catalyst is immersed in an aqueous solution containing a catalyst component, and an oxidizing environment. The second firing step of firing at a temperature range of 120 to 500 ° C.

Preferably, the catalyst component is a metal containing copper and zinc.

Preferably, the foregoing anodic oxidation step is performed by using a 2-6 wt% (wt%) oxalic acid aqueous solution at a temperature of 15-40 ° C.

Preferably, after the anodizing step and before the first dipping step, additional firing treatment is performed at 500 to 600 ° C.

Preferably, after the anodizing step and before the first dipping step, the method further includes performing a pore enlargement treatment with an acidic aqueous solution having a pH of 3 to 6.

Preferably, the acidic aqueous solution used in the aforementioned pore enlargement treatment is the same as the acidic aqueous solution used in the aforementioned anodizing step.

Preferably, after the pore enlargement treatment and before the first dipping step, the method further includes hydration treatment with water vapor or water at 40 to 100 ° C.

Preferably, the first dipping step and the second dipping step are performed by using a mixed solution of copper nitrate and zinc nitrate.

Preferably, the pH of the mixed solution is 10.0 to 11.4, the immersion temperature in the mixed solution is 20 to 40 ° C, and the immersion time in the mixed solution is 1 to 10 hours.

Preferably, the pH of the mixed solution is 10.0 to 11.4, the immersion temperature in the mixed solution is 25 to 30 ° C, and the immersion time in the mixed solution is 2 to 5 hours.

Preferably, the first firing step and the second firing step are performed at 300 to 500 ° C. for 1 to 3 hours.

The method for producing hydrogen provided by the second aspect of the present invention is characterized in that the method for producing hydrogen is performed using the structure catalyst obtained by the method for producing the structure catalyst of the first aspect of the present invention, wherein the aforementioned structure is contacted with The medium is disposed inside the water gas conversion reactor, and a mixed gas containing hydrogen and carbon monoxide is generated by a steam recombination reaction from a raw material gas containing hydrocarbon-based raw materials (hydrocarbons, alcohols, etc.) and water. A water gas conversion reaction is performed in the water gas conversion reactor.

Other features and advantages of the present invention will be made clearer with reference to the attached drawings and the following detailed description.

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

FIG. 1 is a processing flowchart showing an embodiment of a method for manufacturing a structural catalyst according to the present invention. As shown in the figure, in the manufacture of the structure catalyst of this embodiment, the aluminum substrate is sequentially subjected to anodizing treatment S1, pore enlargement treatment S2, hydration treatment S3, immersion treatment (first time) S4, and firing. Forming treatment (first time) S5, dipping treatment (second time) S6, and firing treatment (second time) S7.

In the aluminum substrate according to this embodiment, the aluminum oxide layer on the surface subjected to the oxidation treatment serves as a support. The shape of the aluminum substrate may be any shape such as a plate shape, a rod shape, a cylindrical shape, a strip shape, a honeycomb shape, and the like, and is not particularly limited as long as it is a fixed shape.

The anodization of the surface of the aforementioned aluminum substrate (anodizing treatment S1 in FIG. 1) can be easily performed by a known anodizing technique. In the anodization, it is preferable to use a highly oxidizing acid such as oxalic acid, chromic acid, sulfuric acid, or the like as the treatment liquid. Thereby, all of the aluminum becomes alumina, and oxygen atoms are diffused into the inside of the diffusion layer provided as necessary to easily perform anodization. In addition, the acid concentration of the treatment liquid may be appropriately determined. For example, when oxalic acid is used, a 2 to 6 wt% aqueous solution is preferred.

In order to increase the BET specific surface area of the alumina layer, the conditions of anodization can be appropriately set. In this embodiment, the temperature of the anodizing treatment liquid is preferably set to 0 ~ 50 ° C, especially 15 ~ 40 ° C. When the temperature of the anodizing treatment liquid is less than 0 ° C, the BET specific surface area does not become too large, and when it exceeds 50 ° C, the dissolution is intense, and it becomes difficult to economically form an oxide film. In addition, although this anodizing treatment time varies depending on the treatment conditions, such as a 4.0wt% oxalic acid aqueous solution as the treatment liquid, the treatment liquid temperature is 25 ° C, and the current density is 50.0A / m ² in the case of 2 hours It is preferably at least 4 hours.

In this embodiment, after the anodizing treatment, post-firing is preferably performed at 350 ° C or more for 1 hour or more, preferably 500 to 600 ° C, if necessary. Therefore, the anodic oxide film is preferably used as the γ-alumina layer, and is preferably used as the surface of the catalyst support, and the change in the concentration of the diffused atoms in the diffusion layer can be made gentler.

In this embodiment, in order to increase the BET specific surface area of the surface of the anodized film and improve heat resistance, a pore enlargement treatment (a pore enlargement treatment S2 in FIG. 1) may be performed. The pore enlargement process is a process of expanding the pores in the anodized film with an acidic aqueous solution. The acidic aqueous solution used here can be appropriately selected and used from the same aqueous solution as the treatment liquid used in the aforementioned anodization. Therefore, after anodic oxidation, the pore enlargement treatment can be continued in the same treatment solution. The processing conditions (temperature and time) of this pore expansion processing can be appropriately set according to the type or concentration of the acid used as the processing liquid, and the like. The concentration conditions of the treatment liquid are preferably pH 3 to 6. For example, when 4.0% by weight of oxalic acid is used at 25 ° C, the treatment time needs about 90 minutes or more, but 120 minutes is sufficient.

In this embodiment, the hydration treatment may be performed after the pore enlargement treatment (hydration treatment S3 in FIG. 1). The aforementioned hydration treatment may be performed with water vapor or water, and the temperature of this water is set to, for example, 5 to 100 ° C, preferably 40 to 100 ° C. The treatment temperature and treatment time of the hydration treatment can be appropriately set. The water used for the hydration treatment is preferably distilled water or ion-exchanged water.

By carrying a metal catalyst on the surface of the alumina support obtained in this way, a catalyst can be obtained. The supported catalyst component is at least one selected from the group consisting of nickel, lanthanum, platinum, copper, zinc, and cerium, and alloys and compounds thereof, or a mixture containing more than one type. In this embodiment, copper and zinc are preferred from the viewpoints of economy and catalyst activity.

A method of carrying a metal catalyst on the surface of an alumina support by dipping and firing. In this embodiment, immersion and firing are repeated twice. Regarding the immersion treatment, for example, when the catalyst components are copper and zinc, an aqueous solution containing copper and zinc components is used as the processing liquid, such as a mixed aqueous solution of copper nitrate and zinc nitrate, or a mixed aqueous solution of copper acetate and zinc acetate. Wait. As the processing conditions for the first immersion treatment (the immersion treatment S4 in the first figure, the first immersion step), for example, the total concentration of copper and zinc in the aqueous solution containing the copper and zinc components is 0.1 to 10 mol / L, and the pH is 10.0 to 11.4, immersion temperature is 20 to 40 ° C, and immersion time is 1 to 10 hours. However, from the viewpoint of obtaining high activity as a catalyst, the total concentration of copper and zinc is preferably 0.1 to 1 mol. / L, pH is 10.0 ~ 11.4, immersion temperature is 25 ~ 30 ° C, immersion time is 2 ~ 5 hours.

The drying after removing the water after the immersion treatment is performed by natural drying for 10 to 24 hours or heat drying at an upper limit of 100 ° C. Here, since the rapid drying in a short period of time may peel off the supported copper and zinc components, it is preferable to take time to dry at 50 ° C.

After the drying, a firing process is performed to change the copper and zinc components into oxides (firing process S5 in FIG. 1 and a first firing step). This firing treatment is performed in the air, and the firing temperature is, for example, 120 to 500 ° C. From the viewpoint of removing impurities such as acid during impregnation, it is preferably 300 to 500 ° C. The firing time is, for example, 1 to 10 hours, and from the viewpoint of sufficiently performing the oxidation reaction and economy, it is preferably 1 to 3 hours.

After the first firing treatment, a second immersion treatment, drying, and firing treatment are performed. The processing conditions of the second immersion treatment (the immersion treatment S6 in FIG. 1 and the second immersion step) are, for example, the same as the conditions of the first immersion treatment. The conditions of the second firing process (the firing process S7 in the first figure, and the second firing step) are, for example, 120 to 500 ° C. From the viewpoint of sufficiently generating copper and zinc oxide, the conditions are preferably 300 ~ 500 ° C. The firing time is, for example, 1 to 10 hours, and from the viewpoint of sufficiently performing the oxidation reaction and economy, it is preferably 1 to 3 hours.

According to this embodiment, regarding the production of a structural catalyst used when a gas containing hydrogen and carbon monoxide is produced by a water-gas conversion reaction to produce a high concentration of hydrogen, an aluminum substrate is anodized, When the catalyst component is immersed, the immersion treatment in an aqueous solution containing the catalyst component and the sintering treatment in an oxidizing environment are divided into two repetitions. By firing at a set sintering temperature, high catalyst activity can be obtained. And fewer structural catalysts with low catalyst activity.
[Example]

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

[Example 1]
In this example, an aluminum substrate (a planar size of 6.5 cm × 6.0 cm and a thickness of 300 μm) was used as a metal support, and a 4.0 wt% aqueous oxalic acid solution was used at a liquid temperature of 25 ° C and a current density of 50.0 A / m ^2. Next, this aluminum substrate was anodized for 20 hours. Then, a 4.0 wt% oxalic acid aqueous solution was used at a liquid temperature of 25 ° C for 2 hours to expand the pores, followed by firing in air at 350 ° C for 1 hour, and then immersed in ion-exchanged water at 80 ° C for 1 hour. For hydration. Furthermore, it baked at 500 ° C in the air for 3 hours to obtain a plate-like alumina support based on an aluminum substrate.

This plate-shaped support was immersed in a mixed aqueous solution of copper nitrate and zinc nitrate (containing a copper concentration of 0.46 mol / L, containing a zinc concentration of 0.04 mol / L, and pH = 10) as the first immersion treatment. Next, after being naturally dried, as the first firing treatment, the firing treatment was performed at 350 ° C. for 1 hour in the air to impregnate and carry the copper and zinc components. Furthermore, the plate-shaped support that had undergone the first firing treatment was immersed in a mixed aqueous solution of copper nitrate and zinc nitrate (containing a copper concentration of 0.46 mol / L, containing a zinc concentration of 0.04 mol / L, and pH = 10). Hours as the second immersion treatment. Next, after being naturally dried, as a second firing treatment, a firing treatment was performed in air at 350 ° C. for 1 hour to impregnate and support the copper and zinc components. In this manner, a structure catalyst was produced for producing hydrogen by a water gas conversion reaction described later. In the obtained structural catalyst, when the loading amount of copper and zinc of the catalyst component was measured by ICP emission spectrometry (high frequency inductively coupled plasma atomic emission spectrum, ICP-OES / ICP-AES), The area of the board has a bearing capacity of 6.69g / m ² for copper and 6.51g / m ² for zinc, and the bearing ratio of copper is 1.48% by weight and the bearing ratio of zinc is relative to the alumina of the catalyst component of the structure catalyst. 1.44wt%.

Using this structure catalyst, and using a gas generator X having a schematic structure as shown in FIG. 2, an experiment was performed to produce hydrogen and carbon dioxide from a water gas conversion reaction. The gas generator X shown in the same figure includes a water-gas conversion reactor 1, and the structure catalyst 2 is arranged inside the water-gas conversion reactor 1. As a material of the water gas conversion reactor 1, stainless steel SUS304 was used. In addition, a temperature regulator (not shown) provided in the water-gas conversion reactor 1 can adjust the internal reaction temperature.

In addition, the steam recombination reaction performed before the water-gas conversion reaction uses catalysts to generate hydrocarbon-based raw materials (hydrocarbons such as methane and the like or alcohols such as methanol and ethanol) and water and the like using a catalyst. Hydrogen and carbon monoxide. In this embodiment, for example, a methane gas that is a hydrocarbon compound and a raw material gas of water (water vapor) are subjected to a vapor recombination reaction. Here, the volume ratio of the introduced gas of methane gas to water is set to 1: 3, the reaction temperature is set to 750 ° C, and the pressure is set to atmospheric pressure. Regarding the mixed gas obtained by this steam recombination reaction, the gas composition converted in a dry state excluding water is 76.2% hydrogen, 7.2% carbon dioxide, 14.2% carbon monoxide, and 2.4% methane (hydrocarbon).

In the water gas conversion reaction test, for a mixed gas containing hydrogen and carbon monoxide (excluding water) generated by the aforementioned steam recombination reaction, 0.2 times the amount of nitrogen was added and introduced into the water gas conversion reactor 1. The reaction temperature outside the water-gas conversion reactor 1 was 280 ° C. Pressure is implemented at atmospheric pressure.

200 minutes after the start of the test, the hydrogen-containing gas obtained by the reaction was cooled in a water-cooled gas cooler 3, and excess water vapor was removed as condensed water, and the composition was analyzed by a gas analyzer. The converted gas composition in the dry state without water is 54.5% hydrogen, 5.0% carbon dioxide, 6.3% carbon monoxide, 1.2% methane, and 32.3% nitrogen. In addition, the CO conversion rate after 3 minutes from the start of the test was 35.0%. The change of the CO conversion rate with time in this example is shown in FIG. 3.

After 1040 minutes from the start of the test, the gas composition converted in the dry state without water was 54.1% hydrogen, 7.6% carbon dioxide, 7.6% carbon monoxide, 1.6% methane, and 32.8% nitrogen. In addition, the CO conversion rate was 21.1% after 1040 minutes from the start of the test.

[Comparative Example 1]
In this comparative example, the same plate-like alumina support as in Example 1 was used. The treatment (impregnation treatment and firing treatment) for carrying the catalyst component on the plate-shaped support was carried out in two times in Example 1, but in this comparative example, it was once.

In this comparative example, a plate-shaped support was immersed in a mixed aqueous solution of copper nitrate and zinc nitrate (containing a copper concentration of 0.46 mol / L, containing a zinc concentration of 0.04 mol / L, and pH = 10) as an immersion treatment. Next, after being naturally dried, as a firing treatment, a firing treatment was performed in the air at 350 ° C. for 1 hour to impregnate and carry the copper and zinc components. In this manner, a structural catalyst for producing hydrogen by a water gas conversion reaction was produced. In the obtained structural catalyst, when the loading amount of copper and zinc of the catalyst component was measured by ICP emission spectrometry (high frequency inductively coupled plasma atomic emission spectrum, ICP-OES / ICP-AES), The area of the board has a bearing capacity of 2.85 g / m ^{2 for} copper and 2.00 g / m ² for zinc, and the bearing ratio of copper is 0.64 wt% and the bearing ratio of zinc is relative to the alumina of the catalyst component of the structure catalyst. 0.45wt%. The conditions of the subsequent water gas conversion reaction test were the same as those in Example 1.

200 minutes after the test was started, the mixed gas containing hydrogen obtained by the reaction was cooled in a water-cooled gas cooler, and excess water vapor was removed as condensed water, and the composition was analyzed by a gas analyzer. The converted gas composition in the dry state without water is 53.9% hydrogen, 4.3% carbon dioxide, 7.5% carbon monoxide, 1.3% methane, and 32.3% nitrogen. In addition, the CO conversion rate was 21.7% 200 minutes after the start of the test. This is 13.3% lower than the CO conversion of Example 1. The change of the CO conversion rate with time in this comparative example is shown in FIG. 3.

In addition, after 1040 minutes from the start of the test, the gas composition converted in the dry state without water was 53.6% hydrogen, 6.1% carbon dioxide, 8.8% carbon monoxide, 1.6% methane, and 31.7% nitrogen. The CO conversion rate after 1040 minutes from the start of the test was 8.2%. This is 12.9% lower than the CO conversion of Example 1. From this, it can be seen that the catalyst activity was clearly recognized to be low in this comparative example.

[Evaluation]
It can be seen from Comparative Example 1 and Comparative Example 1 that in the immersion treatment, although the same mixed aqueous solution of copper nitrate and zinc nitrate is used (containing copper concentration of 0.46 mol / L, zinc concentration of 0.04 mol / L, pH = 10) And using the same immersion time (4 hours: 2 hours + 2 hours in Example 1), the amount of copper and zinc carried in Example 1 was increased to more than twice the amount of Comparative Example 1. Therefore, in Example 1, the The addition rate of carbon monoxide in the water gas conversion reaction was also increased to twice or more that of Comparative Example 1. This is because when manufacturing a copper-zinc-aluminum-based structural catalyst for a water gas conversion reaction, it has been shown that the immersion treatment and the firing treatment are carried out twice in order to carry copper and zinc on the alumina layer. The method is excellent.

X‧‧‧Gas generator

1‧‧‧Water gas conversion reactor

2‧‧‧ Structural Catalyst

3‧‧‧Gas cooler

S1‧‧‧Anodizing

S2‧‧‧ Fine hole enlargement

S3‧‧‧hydration treatment

S4‧‧‧Immersion treatment (1st time)

S5‧‧‧Baking treatment (first time)

S6‧‧‧Immersion treatment (second time)

S7‧‧‧Baking treatment (second time)

FIG. 1 is a processing flowchart showing an embodiment of a method for manufacturing a structural catalyst according to the present invention.

FIG. 2 shows a schematic structure of a gas generator that can be used to implement a hydrogen production method.

FIG. 3 is a graph showing changes in the CO conversion rate with time in Example 1 and Comparative Example 1. FIG.

Claims (12)

A manufacturing method of a structure catalyst includes: Performing an anodizing step to anodize the surface of the aluminum substrate as a metal support to form an alumina support; Performing a first dipping step, dipping the alumina support in an aqueous solution containing a catalyst component; Performing a first firing step, and firing the alumina support that carries a part of the catalyst component in the first dipping step in a temperature range of 120 to 500 ° C. in an oxidizing environment; Performing a second impregnation step, immersing the alumina support that has undergone the first firing step in an aqueous solution containing the catalyst component; and A second firing step is performed, and the alumina support carrying the catalyst component in a final amount in the second dipping step is fired in a temperature range of 120 to 500 ° C. in an oxidizing environment. The method for manufacturing a structural catalyst according to item 1 of the scope of patent application, wherein the catalyst component is a metal containing copper and zinc. The manufacturing method of the structure catalyst as described in the first item of the patent application scope, wherein the anodizing step is performed by using a 2 to 6 wt% oxalic acid aqueous solution at a temperature of 15 to 40 ° C. The manufacturing method of the structure catalyst as described in the first item of the patent application scope, wherein after the anodizing step and before the first dipping step, additional firing treatment is performed at 500 to 600 ° C. The manufacturing method of the structure catalyst as described in the first item of the patent application scope, wherein after the anodizing step and before the first dipping step, the method further includes performing pore expansion treatment with an acidic aqueous solution having a pH of 3 to 6. According to the method for manufacturing a structure catalyst described in item 5 of the scope of patent application, wherein the acidic aqueous solution used in the aforementioned pore expansion treatment is the same as the acidic aqueous solution used in the aforementioned anodizing step. The method for manufacturing a structure catalyst as described in item 5 of the scope of patent application, wherein after the aforementioned pore enlargement treatment and before the aforementioned first dipping step, the method further comprises hydration treatment with water vapor or water at 40 to 100 ° C. . The manufacturing method of the structure catalyst as described in the first item of the patent application scope, wherein the first dipping step and the second dipping step are performed by using a mixed solution of copper nitrate and zinc nitrate. The method for manufacturing a structure catalyst as described in item 8 of the scope of the patent application, wherein the pH of the mixed solution is 10.0 to 11.4, the immersion temperature in the mixed solution is 20 to 40 ° C, and the immersion time in the mixed solution For 1 to 10 hours. The method for manufacturing a structure catalyst as described in item 8 of the scope of the patent application, wherein the pH of the mixed solution is 10.0 to 11.4, the impregnation temperature in the mixed solution is 25 to 30 ° C, and the impregnation in the mixed solution is The time is 2 ~ 5 hours. The method for manufacturing a structure catalyst as described in the first item of the patent application scope, wherein the first firing step and the second firing step are performed at 300 to 500 ° C. for 1 to 3 hours. A method for producing hydrogen using a structure catalyst obtained by the method for manufacturing a structure catalyst described in any one of claims 1 to 11 of the scope of application for a patent, wherein the structure catalyst is disposed in water gas Inside the reforming reactor, a water-gas reforming reaction is performed in the water-gas reforming reactor by generating a mixed gas containing hydrogen and carbon monoxide by a steam recombination reaction from a raw material gas containing a hydrocarbon-based raw material and water.