JP2019034259A - Catalyst for hydrogen production and method for producing the same, and hydrogen production device - Google Patents

Abstract

To provide a catalyst for hydrogen production having high catalytic activity even in a low temperature region, a method for producing the same, and a hydrogen production device.SOLUTION: A catalyst for hydrogen production has a metal foil, and a metal active layer supported on the surface of the metal foil and composed of metal particles. This structure ensures high catalytic activity even in a low temperature region. A method for producing a catalyst for hydrogen production includes forming a strong acid salt powder layer having a metal element on the surface of the metal foil. The strong acid salt powder layer is thermally decomposed, to form an oxide particle layer having the metal element. The oxide particle layer is reduced, to form a metal active layer having the metal element. This structure makes it possible to produce a catalyst for hydrogen production having high catalytic activity even in a low temperature region.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a hydrogen production catalyst, a production method thereof, and a hydrogen production apparatus.

  Hydrogen used as a fuel for a fuel cell is produced by, for example, reacting methane gas with water vapor at a high temperature by a steam reforming reaction. In recent years, a small-sized hydrogen production apparatus has been developed for the spread of fuel cell vehicles, and in conjunction with this, a hydrogen production catalyst exhibiting high catalytic activity even in a low temperature range is demanded.

  The metal honeycomb catalyst used for the steam reforming reaction has characteristics such as a smaller pressure loss, less hot spot generation, and excellent heat transfer properties than a conventionally used pellet catalyst. For this reason, development of a metal honeycomb catalyst with lower cost and higher efficiency has been made. Non-Patent Document 1 describes a honeycomb catalyst for hydrogen production using nickel foil.

Appl. Catal. A: General 507 (2015) 162-168

  However, the honeycomb catalyst of pure nickel foil of Non-Patent Document 1 has a problem that it is difficult to apply to a small hydrogen production apparatus because it exhibits low catalytic activity in a low temperature range.

  In view of the circumstances as described above, an object of the present invention is to provide a hydrogen production catalyst that exhibits high catalytic activity even in a low temperature range, a production method thereof, and a hydrogen production apparatus using the same.

In order to achieve the above object, a hydrogen production catalyst according to an embodiment of the present invention includes a metal foil and a metal active layer composed of metal particles supported on the metal foil.
With this configuration, high catalytic activity can be obtained even in a low temperature range.

  The metal active layer may include a first element selected from Ni, Ru, Rh, Pt, Pd, Ir, Fe, and Co.

  The first element may be Ni or Ru.

The metal active layer is selected from one or more of Ru, Re, Mn, Mo, W, Cr, Ta, Hf, Os, Sn, Zn, La, Ce, Rh, Pt, Mg, Al, Si, Cu, A second element different from the first element may be further included.
With this configuration, even higher catalytic activity can be obtained even in a low temperature range.

The second element may be selected from Re and Ru.
With this configuration, a hydrogen production catalyst having excellent heat resistance can be obtained.

  The metal particle is formed of an alloy including the first element and the second element, and the content of the first element in the metal particle is 1 wt% or more and less than 100 wt%, and the metal particle has the first element. The content of the two elements may be greater than 0 wt% and less than 99 wt%.

  The content of the first element in the metal particles may be 30 wt% or more and 92 wt% or less, and the content of the second element in the metal particles may be 8 wt% or more and 70 wt% or less.

  The metal foil may contain as a main component a material selected from the group consisting of Ni, stainless steel, and iron-based alloys.

  The metal foil may contain Ni as a main component.

  The metal foil may constitute a honeycomb structure or a spiral structure.

  The particle size of the metal particles may be 1 nm or more and 500 nm or less.

  The particle size of the metal particles may be 10 nm or more and 150 nm or less.

In the method for producing a catalyst for hydrogen production according to one embodiment of the present invention, a strong acid salt powder layer containing a metal element is formed on the surface of a metal foil. By thermally decomposing the strong acid salt powder layer, an oxide particle layer containing the metal element is formed. The metal active layer containing the metal element is formed by reducing the oxide particle layer.
With this configuration, high catalytic activity can be obtained even in a low temperature range.

  The strong acid salt powder layer may be formed using a strong acid solution of the metal element.

  The metal element may include a first element selected from Ni, Ru, Rh, Pt, Pd, Ir, Fe, and Co.

  The metal foil may contain the metal element as a main component, and the strong acid salt powder layer may be formed by acid-treating the surface of the metal foil.

  The metal element may be Ni.

  You may acid-treat the surface of the said metal foil using nitric acid.

  The strong acid salt powder layer, the oxide particle layer, and the metal active layer may further include a second element different from the first element as the metal element.

The second element may be one or more selected from Ru, Re, Mn, Mo, W, Cr, Ta, Hf, Os, Sn, Zn, La, Ce, Rh, Pt, Mg, Al, Si, and Cu. Good.
With this configuration, even higher catalytic activity can be obtained even in a low temperature range.

A hydrogen production apparatus according to an aspect of the present invention includes a supply unit that supplies a hydrogen source gas containing a hydrocarbon compound and a reaction gas containing water vapor, the hydrogen source gas supplied from the supply unit, and the above A catalytic reaction unit that reacts with a reaction gas to generate a steam reforming reaction, and the catalytic reaction unit includes the hydrogen production catalyst.
With this configuration, high catalytic activity can be obtained even in a low temperature range.

It is possible to provide a hydrogen production catalyst that exhibits high catalytic activity even in a low temperature range, a production method thereof, and a hydrogen production apparatus.
More specifically, the hydrogen production catalyst of the present invention comprises a metal foil and a metal active layer composed of metal particles supported on the surface thereof, thereby increasing the specific surface area and a low temperature of 1173 K or less. High catalytic activity can also be exhibited in the region. According to the production method of the present invention, the hydrogen production catalyst of the present invention can be produced without using a special apparatus or technique. Moreover, since the catalyst for hydrogen production of the present invention can exhibit high catalytic activity in a small amount, the hydrogen production apparatus can be miniaturized.

It is a perspective view of the catalyst for hydrogen production concerning one embodiment of the present invention. It is a fragmentary sectional view which expands and shows the cross section of the said catalyst for hydrogen production. It is a flowchart which shows manufacturing method A1 of the said catalyst for hydrogen production. It is a figure which shows an example of the preparation process of the base | substrate of the said catalyst for hydrogen production. It is a schematic diagram which shows an example of the base | substrate of the said catalyst for hydrogen production. It is a flowchart which shows manufacturing method B1 of the said catalyst for hydrogen production. It is a schematic diagram of the hydrogen production apparatus using the said catalyst for hydrogen production. It is the SEM image which imaged the fine structure of the surface of the catalyst for hydrogen production in an example. It is a graph which shows the catalyst characteristic by the temperature rising experiment of the catalyst for hydrogen production in an Example. It is a graph which shows the catalyst characteristic by the temperature rising experiment of the catalyst for hydrogen production in an Example. It is the SEM image which imaged the fine structure of the surface before the reduction process of the catalyst for hydrogen production in an example. It is the SEM image which imaged the fine structure of the surface before the reduction process of the catalyst for hydrogen production in an example. It is a graph which shows the catalyst characteristic by the temperature rising experiment of the catalyst for hydrogen production in an Example.

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

[Hydrogen production catalyst 10]
(overall structure)
FIG. 1 is a perspective view of a hydrogen production catalyst 10 according to an embodiment of the present invention.
FIG. 2 is an enlarged partial cross-sectional view of the hydrogen production catalyst 10 of FIG.
The catalyst 10 for hydrogen production in the present invention is a catalyst that generates hydrogen by a steam reforming reaction using a hydrogen source gas and steam.

  The hydrogen production catalyst 10 includes a substrate 11 and a metal active layer 12.

  The base 11 is constituted by winding a flat metal foil 11a and a corrugated metal foil 11b integrally. Thereby, the base | substrate 11 is comprised as a cylindrical honeycomb structure which has the flow path formed along the central-axis direction. Although shown in FIG. 1 as a cylinder, it may be wound according to the shape of the reaction tube in which the hydrogen production catalyst 10 such as a prism or polygonal injection is installed.

  The metal active layer 12 is supported on the surface of the substrate 11. The metal active layer 12 functions as a catalyst for the steam reforming reaction. FIG. 2 shows a state in which the metal foils 11a and 11b are not wound for convenience of explanation.

The hydrogen production catalyst 10 can pass a gas such as a hydrogen source gas or water vapor along the flow path of the substrate 11 because the substrate 11 is a honeycomb structure.
Further, the hydrogen production catalyst 10 can exhibit good catalytic activity when the gas contacts the metal active layer 12 formed in the honeycomb structure having a large surface area. Furthermore, the hydrogen production catalyst 10 can efficiently generate hydrogen by allowing the gas to pass through the honeycomb structure having a low pressure loss.

(Details of the substrate 11)
It is preferable that the metal foils 11a and 11b have, for example, any one of Ni, stainless steel, and iron-based alloy as a main component. Thereby, the metal active layer 12 is favorably supported on the metal foils 11a and 11b.
In particular, the metal foils 11a and 11b are more preferably composed mainly of Ni. High catalytic activity is obtained because Ni itself constituting the metal foils 11a and 11b acts as a catalyst.
Here, the main component refers to a component having a content of 50 wt% or more and 100 wt% or less in the metal foils 11a and 11b.

  The thickness of the metal foils 11a and 11b may be, for example, several tens of μm, or about several μm to several hundreds of μm, and is not limited thereto.

The substrate 11 is not limited to the honeycomb structure, and may be a spiral structure in which only the flat metal foil 11a is wound without using the corrugated metal foil 11b.
The base 11 is manufactured by winding the metal foils 11a and 11b, but may be manufactured by other methods.

(Details of the metal active layer 12)
The metal active layer 12 is made of fine metal particles carried on the surface of the substrate 11.
When the metal active layer 12 is made of fine metal particles, the surface area of the hydrogen production catalyst 10 is increased. For this reason, the hydrogen production catalyst 10 can exhibit high catalytic activity even in a low temperature region of 1173K or less. Moreover, even if the catalyst 10 for hydrogen production is a small quantity, it can show high catalyst activity.

Metal fine particles refer to fine metal particles having a particle size of 1 μm or less. In the metal active layer 12, the particle size of the metal fine particles is preferably 1 nm or more and 500 nm or less, more preferably 10 nm or more and 150 nm or less, and further preferably 50 nm or more and 150 nm or less. In this specification, a particle size is calculated based on the image of a scanning electron microscope (SEM), for example.
By setting the particle size to 500 nm or less, the surface area of the hydrogen production catalyst 10 can be increased, and a particularly high catalytic activity can be obtained even in a low temperature range. By setting the particle size to 1 nm or more, stable catalyst characteristics can be easily obtained.

  The metal fine particles contain at least one or more of Group 4 to Group 11 transition metal elements. The metal fine particles preferably contain a first element selected from Ni, Ru, Rh, Pt, Pd, Ir, Fe, and Co, and more preferably contain Ni or Ru. Thereby, higher catalytic activity can be obtained even in a low temperature range. Moreover, high catalytic activity can be maintained for a long time.

  The metal fine particles are selected from one or more of Ru, Re, Mn, Mo, W, Cr, Ta, Hf, Os, Sn, Zn, La, Ce, Rh, Pt, Mg, Al, Si, and Cu. It is preferable that a second element different from the one element is further included. The second element is more preferably selected from Re and Ru. Thereby, even higher catalytic activity can be obtained even in a low temperature range. In addition, high catalytic activity can be maintained for a longer time.

The metal fine particles are formed of an alloy containing a first element and a second element.
The content of the first element in the metal fine particles is preferably 1 wt% or more and less than 100 wt%, and the content of the second element in the metal fine particles is preferably more than 0 wt% and 99 wt% or less.
More preferably, the content of the first element in the metal fine particles is 30 wt% or more and 92 wt% or less, and the content of the second element in the metal fine particles is 8 wt% or more and 70 wt% or less.
Thereby, higher catalytic activity can be obtained even in a low temperature range.

  In particular, in the metal fine particles, it is more preferable that the first element is Ni and the second element is Re. Thereby, metal fine particles are formed of an alloy of Ni and Re, and the metal active layer 12 is further stabilized. For this reason, the catalyst 10 for hydrogen production excellent in heat resistance is obtained. In addition, high catalytic activity can be maintained for a longer time.

  The metal fine particles may include metal fine particles formed only from the first element and metal fine particles formed only from the second element.

[Production method A1 of catalyst 10 for hydrogen production]
FIG. 3 is a flowchart showing a manufacturing method A1 of the catalyst 10 for hydrogen production.
Hereinafter, the production method A1 using the hydrogen production catalyst 10 will be described with reference to FIG.

(Step S101: Preparation of the substrate 11)
In step S101, the base 11 is prepared. FIG. 4 is a diagram illustrating an example of a manufacturing process of the substrate 11.

First, as shown to Fig.4 (a), the flat metal foil 11a and the corrugated metal foil 11b are prepared.
The flat metal foil 11a is obtained by rolling a metal material.
The flat metal foil 11b is obtained by processing the flat metal foil 11a into a wave shape. The corrugated metal foil 11b is not limited to the corrugated shape shown in FIG. 4A, and may be a corrugated shape such as a triangular wave, a rectangular wave, or a trapezoidal wave. Further, the wave interval and the wave height can be set as appropriate.

  Next, as shown in FIG. 4B, the flat metal foil 11a and the corrugated metal foil 11b are joined. For example, an adhesive can be used to join the flat metal foil 11a and the corrugated metal foil 11b.

  Further, as shown in FIG. 4C, the joined metal foils 11a and 11b are wound. Thereby, a substrate 11 of a honeycomb structure as shown in FIG. 1 is manufactured.

  FIG. 5 is a schematic view showing an example of the base 11 of the hydrogen production catalyst 10. A substrate 11 having a spiral structure as shown in FIG. 5 may be produced by winding only the flat metal foil 11a. Further, the base 11 is not limited to a regular spiral structure wound at regular intervals as shown in FIG. 5, but may be a distorted spiral structure wound irregularly.

(Step S102: Formation of Strong Salt Aqueous Solution Layer)
In step S102, a strong salt aqueous solution layer made of a strong salt aqueous solution containing the first element is formed on the surface of the base 11 prepared in step S101.

First, before forming the strong acid salt aqueous solution layer, the substrate 11 is ultrasonically cleaned with acetone and then dried.
Next, a strong acid salt aqueous solution layer is formed by applying a strong acid salt aqueous solution containing the first element to the surface of the substrate 11.
The amount of the strong salt aqueous solution layer applied to the substrate 11 can be adjusted by, for example, the concentration of the strong salt aqueous solution, the immersion time, and the like.
The strong acid salt aqueous solution layer is composed of, for example, a nickel (II) nitrate hexahydrate aqueous solution or a nitrosyl ruthenium (III) nitrate aqueous solution.

(Step S103: drying)
In step S103, the substrate 11 on which the strong acid salt aqueous solution layer is formed in step S102 is dried. As a result, the strong acid salt aqueous solution is concentrated, and a strong acid salt powder layer made of a strong acid salt (or hydrate thereof) of the first element is formed on the surface of the substrate 11.
Further, by repeating steps S102 and S103, the amount of the strong acid salt powder layer formed on the substrate 11 can be increased.
In the drying process, for example, drying can be performed in two stages. As drying conditions, for example, in the first stage, the drying temperature is 60 ° C., the drying time is 6 hours, and in the second stage, the drying temperature is 120 ° C., and the drying time is 6 hours.
The strong acid salt powder layer is composed of, for example, nickel (II) nitrate hexahydrate powder or ruthenium (III) nitrosyl nitrate powder.

(Step S104: Sintering)
In step S104, the strong acid salt powder layer is sintered by heating the base 11 on which the strong acid salt powder layer is formed in step S103. Thereby, the oxide fine particles having a particle size of several nm to several hundred nm are generated by thermally decomposing the strong acid salt powder. As a result, an oxide fine particle layer composed of oxide fine particles of the first element is formed.
As sintering conditions, for example, the sintering atmosphere is an air atmosphere, the sintering temperature is 400 to 600 ° C., and the sintering time is 5 to 12 hours.
The oxide fine particle layer is composed of, for example, nickel oxide metal fine particles or ruthenium oxide metal fine particles.

(Step S105: Reduction)
In step S105, the base 11 on which the oxide fine particle layer is formed in step S104 is heated in a reducing atmosphere to reduce the oxide fine particles of the first element. Thereby, metal fine particles of the first element are generated, and the metal active layer 12 made of the metal fine particles of the first element is formed.
As reducing conditions, for example, the reducing atmosphere is a hydrogen atmosphere, the reducing temperature is 400 to 600 ° C., and the reducing time is 1 hour or more.
The metal active layer 12 is composed of, for example, Ni metal fine particles or Ru metal fine particles.

  As described above, in the production method A1, the hydrogen production catalyst 10 in which the metal active layer 12 made of the metal fine particles of the first element is formed on the surface of the substrate 11 is obtained. Further, according to the production method A1 of the present invention, the hydrogen production catalyst 10 of the present invention can be produced by a simple method without using a special apparatus or technique.

[Production Method A2 for Hydrogen Production Catalyst 10]
In the production method A2 of the hydrogen production catalyst 10, the hydrogen production catalyst 10 is produced by a method different from the production method A1 in steps S101 to S103. Steps S101 ′ to S103 ′ of manufacturing method A2 described below correspond to steps S101 to S103 of manufacturing method A1.

(Step S101 ′: Preparation of Base 11)
In step S101 ′ for preparing the substrate 11, a metal foil containing Ni as a main component (hereinafter referred to as nickel foil) is used. The method for manufacturing the substrate 11 is the same as that in step S101.

(Step S102 ′: Formation of Strong Salt Aqueous Solution Layer)
In S102 ′, the surface of the substrate 11 made of nickel foil is acid-treated to form a strong acid salt aqueous solution layer.
As the acid used for the acid treatment, nitric acid, sulfuric acid, or the like can be used.
For example, the substrate 11 is immersed in nitric acid as an acid treatment. Thereby, as shown in Formula (1), nickel nitrate (II) is produced on the surface of the substrate 11.
Ni + 2HNO ₃ → Ni (NO ₃ ) ₂ + H ₂ (1)
Since nickel (II) nitrate is readily soluble in water, a strong acid salt aqueous solution layer composed of a nickel (II) nitrate aqueous solution is formed on the surface of the substrate 11.

(Step S103 ′: Drying)
In step S103 ′, the nickel foil on which the strong acid salt aqueous solution layer has been formed in step S102 ′ is dried. As a result, the nickel (II) nitrate aqueous solution is concentrated, and nickel (II) nitrate hexahydrate precipitates on the surface of the nickel foil. As a result, a strong acid salt powder layer made of nickel (II) nitrate hexahydrate powder is formed.
As drying conditions, for example, the drying temperature is 60 ° C. and the drying time is 6 hours.

(Steps S104 and S105)
Steps S104 and S105 after step S103 ′ are the same as in manufacturing method A1.
In step S104, the base 11 on which the strong acid salt powder layer is formed is heated to form an oxide fine particle layer made of nickel oxide fine particles.
Subsequently, in step S105, the metal active layer 12 made of Ni metal fine particles is formed by reducing the nickel oxide fine particles.

  As described above, in the production method A2, the hydrogen production catalyst 10 in which the metal active layer 12 made of Ni metal fine particles is formed on the surface of the nickel foil is obtained. Moreover, according to the production method A2 of the present invention, the hydrogen production catalyst 10 of the present invention can be produced by a simple method without using a special apparatus or technique. Furthermore, unlike the manufacturing method A1, the manufacturing method A2 can generate Ni metal fine particles by a simpler method by acid treatment without using the strong salt aqueous solution of the first element.

[Production Method B1 of Catalyst 10 for Hydrogen Production]
FIG. 6 is a flowchart showing a production method B1 of the catalyst 10 for producing hydrogen. The production method B1 of the hydrogen production catalyst 10 further includes steps S204 and S205 different from the production method A1.
Hereinafter, steps S201 to S207 of the production method B1 using the hydrogen production catalyst 10 will be described.

(Step S201: Preparation of the substrate 11)
In step S201, the base 11 is prepared in the same manner as in step S101 of the manufacturing method A1.

(Step S202: Formation of first strong acid salt aqueous solution layer)
In step S202, a first strong acid salt aqueous solution layer is formed on the surface of the substrate 11 prepared in step S201, as in step S102 of the manufacturing method A1. The first strong acid salt aqueous solution layer corresponds to the strong acid salt aqueous solution layer made of the strong acid salt aqueous solution containing the first element in Step S102 of the manufacturing method A1.

(Step S203: Drying 1)
In step S203, the substrate 11 on which the first strong salt aqueous solution layer has been formed in step S202 is dried, similarly to step S103 of the manufacturing method A1. Thereby, the strong acid salt powder layer which consists of powder of the strong acid salt (or its hydrate) of the 1st element is formed.

(Step S204: Formation of second strong acid salt aqueous solution layer)
In step S204, a second strong acid salt aqueous solution layer is further formed on the surface of the substrate 11 on which the strong acid salt powder layer has been formed in step S203. By applying a strong acid salt aqueous solution containing the second element to the surface of the substrate 11, a second strong acid salt aqueous solution layer made of the strong acid salt aqueous solution containing the second element is formed.
The second strong acid salt aqueous solution layer is composed of, for example, an ammonium perrhenate aqueous solution or a nitrosyl ruthenium (III) nitrate aqueous solution.

(Step S205: Drying 2)
In step S205, the substrate 11 on which the second strong acid salt aqueous solution layer has been formed in step S204 is dried. As a result, the second strong acid salt aqueous solution is concentrated, and a strong acid salt powder layer made of a strong acid salt of the second element (or a hydrate thereof) is formed on the surface of the substrate 11. As a result, a strong acid salt powder layer composed of a powder of a strong acid salt (or a hydrate thereof) of the first element and the second element is formed.
A drying process is performed on the conditions similar to step S103 of manufacturing method A1, for example.
Examples of the strong acid salt powder of the second element constituting the strong acid salt powder layer include ammonium perrhenate powder and ruthenium (III) nitrosyl nitrate powder.
The strong acid salt powder layer includes, for example, nickel (II) nitrate hexahydrate and ammonium perrhenate strong acid salt powder, nickel nitrate (II) hexahydrate and nitrosyl ruthenium nitrate (III) strong acid salt powder. Consists of.

(Step S206: Sintering)
In step S206, the strong acid salt powder layer is sintered by heating the substrate 11 on which the strong acid salt powder layer is formed in step S205, as in step S104 of the manufacturing method A1. Thereby, the strong acid salt powder which consists of a 1st element and a 2nd element is thermally decomposed, and the oxide microparticles | fine-particles of a 1st element and a 2nd element are produced | generated. As a result, an oxide fine particle layer composed of oxide fine particles of the first element and the second element is formed.
The oxide fine particle layer includes, for example, oxide fine particles made of nickel oxide and rhenium oxide, and oxide fine particles made of nickel oxide and ruthenium oxide.

(Step S207: Reduction)
In step S207, as in step S105 of the manufacturing method A1, the substrate 11 on which the oxide fine particle layer is formed in step S206 is heated in a reducing atmosphere, whereby the oxide fine particles of the first element and the second element are obtained. Reduce. Thereby, metal fine particles of the first element and the second element are generated, and the metal active layer 12 composed of the metal fine particles of the first element and the second element is formed. Further, the first element and the second element can be alloyed in the heating process. As a result, a metal active layer 12 made of metal fine particles of the first element and the second element is formed.
The metal active layer 12 is composed of, for example, metal fine particles made of Ni and Re, and metal fine particles made of Ni and Ru.

  As described above, in the production method B1, the hydrogen production catalyst 10 in which the metal active layer 12 composed of the metal fine particles of the first element and the second element is formed on the surface of the substrate 11 is obtained. Further, according to the production method B1 of the present invention, the hydrogen production catalyst 10 of the present invention can be produced by a simple method without using a special apparatus or technique.

(Modification)
Manufacturing method B1 is not limited to the said structure.
For example, the formation of the first strong acid salt aqueous solution layer (step S202) and the formation of the second strong acid salt aqueous solution layer (step S204) may be interchanged.
That is, after the preparation of the base body 11 (step S201), a second strong acid salt aqueous solution layer may be formed on the surface of the base body 11 (step S204). Thereafter, a first strong acid aqueous solution layer may be formed on the surface of the substrate 11 on which the strong acid salt powder layer containing the second element has been formed through drying 1 (step S203) (step S202).
Moreover, a sintering process may be further included between the drying 1 (step S203) and the formation of the second strong acid salt aqueous solution layer (step S204).
That is, after the strong acid salt powder layer containing the first element is formed by drying 1 (step S203), the strong acid salt powder layer may be sintered. Thereafter, a second strong acid salt aqueous solution layer may be formed on the surface of the substrate 11 on which the oxide fine particle layer containing the first element is formed by sintering (step S204).

[Production Method B2 of Hydrogen Production Catalyst 10]
In the production method B2 of the hydrogen production catalyst 10, steps S101 ′ to S103 ′ of the production method A2 are applied to steps S201 to S203 of the production method B1.
About step S204-S207, it carries out similarly to manufacturing method B1.

  As described above, in the production method B2, the hydrogen production catalyst 10 in which the metal active layer 12 composed of the metal fine particles of Ni and the second element is formed on the surface of the nickel foil is obtained. Moreover, according to the production method A2 of the present invention, the hydrogen production catalyst 10 of the present invention can be produced by a simple method without using a special apparatus or technique. Further, in the production method B2, unlike the production method B1, Ni metal fine particles can be generated by a simpler method by acid treatment without using a strong salt aqueous solution of the first element.

[Hydrogen production apparatus 100]
(overall structure)
FIG. 7 is a schematic diagram of a hydrogen production apparatus 100 using the hydrogen production catalyst 10.
The hydrogen production apparatus 100 is typically a fixed bed flow type catalytic reaction apparatus. The hydrogen production apparatus 100 includes a supply unit 101 and a catalytic reaction unit 102.
In the hydrogen production catalyst 100, the catalyst capacity can be reduced by using the hydrogen production catalyst 10 showing high catalytic activity in a small amount, and the hydrogen production apparatus 100 can be downsized.
The hydrogen production apparatus 100 is not limited to the configuration described below.

(Supply unit 101)
The supply unit 101 supplies a mixed gas necessary for the reaction to the catalyst reaction unit 102.
The supply unit 101 includes an evaporator 103, the water storage unit 104 includes a pump 105, and a weight scale 106.

The water storage unit 104 stores water that is a raw material for water vapor. The water storage unit 104 is connected to the evaporator 103 via the pump 105.
The pump 105 pumps the water sent from the water storage unit 104 to the evaporator 103.
The evaporator 103 is connected to a cylinder (not shown). The evaporator 103 is connected to the catalyst reaction unit 102. The evaporator 103 converts water into water vapor.
The evaporator 103 supplies a mixed gas containing a gas supplied from a cylinder and water vapor to the catalytic reaction unit 102. The components of the gas supplied from the cylinder are methane, nitrogen, and hydrogen, and the supply amount of each component can be adjusted as appropriate.
The weight scale 106 measures the amount of water in the water storage unit 104. Thereby, the supply amount of the water supplied to the evaporator 103 can be grasped. The supply unit 101 may not have the weight scale 106.

(Catalytic reaction part 102)
The catalytic reaction unit 102 includes a reaction tube 107, a hydrogen production catalyst 10, an electric furnace 109, and quartz wool 108.
Further, the catalytic reaction unit 102 may include a gas chromatograph 110, a cold trap 111, and a flow meter 112. These may be provided as an external configuration of the hydrogen production apparatus 100.

  The reaction tube 107 has a hollow cylindrical shape inside. As shown in FIG. 7, the reaction tube 107 is arranged with the cylindrical central axis direction as the vertical direction. The upper part of the reaction tube 107 is connected to the supply unit 101. The reaction tube 107 circulates the mixed gas supplied from the supply unit 101 inside.

The hydrogen production catalyst 10 is disposed inside the reaction tube 107 and promotes a reaction for generating hydrogen.
The quartz wool 108 is arranged above and below the hydrogen production catalyst 10 arranged inside the reaction tube 107 and fixes the hydrogen production catalyst 10.
The electric furnace 109 has an electric heater and adjusts to a predetermined reaction temperature.

The gas chromatograph 110 is connected to the lower part of the reaction tube 107. The gas chromatograph 110 measures the composition of the exhaust gas exhausted from the reaction tube 107.
The cold trap 111 is connected to the gas chromatograph 110. The cold trap 111 removes water vapor in the exhaust gas discharged from the reaction tube 107 through the gas chromatograph 110.
The flow meter 112 is connected to the cold trap 111. The flow meter 112 measures the flow rate of the exhaust gas discharged from the reaction tube 107 through the gas chromatograph 110 and the cold trap 111.

(Operation by the hydrogen production apparatus 100)
First, the hydrogen production catalyst 10 is reduced by introducing hydrogen into the catalyst reaction unit 102. This step may be omitted as appropriate.
The reaction tube 107 is adjusted to a predetermined reaction temperature by the electric furnace 109.
Next, methane and water vapor are supplied to the reaction tube 107 together with an inert gas such as nitrogen as a carrier gas. Thereby, hydrogen is produced | generated by the steam reforming reaction shown to Formula (2).
CH ₄ + H ₂ O → CO + 3H ₂ (2)
Simultaneously with the steam reforming reaction, the shift reaction shown in the formula (3) proceeds.
CO + H ₂ O → CO ₂ + H ₂ (3)
Through the above reaction, hydrogen is discharged from the reaction tube 107. Hydrogen is discharged together with exhaust gas containing CO and CO ₂ products, residual methane, residual water vapor and the like.

  Methane is not limited to this as long as it is a hydrogen source gas capable of generating hydrogen by a steam reforming reaction. For example, the hydrogen source gas may be a hydrocarbon compound such as ethane or propane.

  As the reaction gas, the water vapor that reacts with the hydrogen source gas is generated by vaporizing water in the evaporator 103 and introduced into the reaction tube 107, but the method of supplying the water vapor is not limited to this. For example, water vapor may be generated by supplying liquid water directly to the reaction tube 107.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and embodiment of this invention is described further more concretely, this invention is not limited to the range of these Examples.

[Production of hydrogen production catalyst 10]
In Examples 1-1 to 1-12, Examples 2-1, 2-2, and Comparative Examples, each hydrogen production catalyst 10 was produced by the following method.

(Examples 1-1 to 1-9 and comparative examples)
In Examples 1-1 to 1-9 and the comparative example, a honeycomb structure of nickel foil was used as the substrate 11. The nickel foil honeycomb structure had a diameter of 8 mm, a height of 10 mm, an average wall thickness of 0.03 mm, and an average cell density of 2311 cpsi.

  In Examples 1-1 and 1-5, the catalyst 10 for hydrogen production having the metal active layer 12 containing Ni was produced by the production method A1.

More specifically, in Examples 1-1 and 1-5, a nickel foil honeycomb structure (substrate 11) ultrasonically washed with acetone and dried was treated with nickel (II) nitrate hexahydrate at room temperature. It was immersed in an aqueous solution (concentration 50%) to form a nickel (II) nitrate hexahydrate aqueous solution layer. Ni in the nickel (II) nitrate hexahydrate aqueous solution layers of Examples 1-1 and 1-5 was 5 wt% and 10 wt%, respectively, with respect to the substrate 11.
Next, the substrate 11 coated with the nickel (II) nitrate hexahydrate aqueous solution was dried at 60 ° C. for 6 hours and then at 120 ° C. for 6 hours to remove excess solvent, and the nickel (II) nitrate hexahydrate The substrate 11 was coated with Japanese powder.
Next, this was set in an electric box furnace and sintered in air at 500 ° C. for 6 to 8 hours to convert nickel nitrate (II) hexahydrate powder into nickel oxide.
Next, the base body 11 carrying nickel oxide was set in an electric tubular furnace and reduced in a hydrogen atmosphere at 430 ° C. for 1 hour to change the nickel oxide to Ni.

  In Examples 1-2 to 1-4, 1-6, and 1-7, hydrogen having the metal active layer 12 containing Ni (first element) and Re (second element) having different composition ratios by the manufacturing method B1. A production catalyst 10 was produced.

Specifically, in Examples 1-2 to 1-4, the base 11 carrying nickel oxide was obtained in the same procedure as in Example 1-1, and then immersed in an aqueous ammonium perrhenate solution (concentration 5%). To form an aqueous ammonium perrhenate aqueous solution layer. Re in the ammonium perrhenate aqueous solution layers of Examples 1-2 to 1-4 was 0.5 wt%, 5 wt%, and 10 wt%, respectively, with respect to the substrate 11.
Next, the nickel oxide-coated substrate 11 coated with an aqueous ammonium perrhenate solution is dried at 60 ° C. for 6 hours and then at 120 ° C. for 6 hours to remove excess solvent, and the ammonium perrhenate powder and nickel oxide are used. A coated substrate 11 was obtained.
Next, this was set in an electric box furnace and sintered in the air at 500 ° C. for 6 to 8 hours to convert the ammonium perrhenate powder to rhenium oxide.
Next, the substrate 11 carrying nickel oxide and rhenium oxide was set in an electric tubular furnace and reduced in a hydrogen atmosphere at 430 ° C. for 1 hour to make nickel oxide and rhenium oxide an alloy of Ni and Re.

  In Examples 1-6 and 1-7, after obtaining the base 11 carrying nickel oxide in the same procedure as in Example 1-5, 1 wt% and 2 wt% of Re were carried with respect to the base 11. The procedure was the same as in Examples 1-2 to 1-4 except that the aqueous ammonium perrhenate layer was formed.

  In Example 1-8, the hydrogen production catalyst 10 having the metal active layer 12 containing Ni (first element) and Ru (second element) was produced by the production method B1.

In detail, in Example 1-8, after obtaining the base | substrate 11 which carry | supported nickel oxide in the same procedure as Example 1-1, it was immersed in nitrosyl ruthenium nitrate (III) aqueous solution (concentration 10%), An aqueous layer of ruthenium (III) nitrosyl nitrate was formed. At this time, Ru in the aqueous solution of ruthenium (III) nitrosyl nitrate was 0.5% by weight with respect to the substrate 11.
Next, the nickel oxide coated substrate 11 coated with an aqueous solution of ruthenium (III) nitrosyl nitrate is dried at 60 ° C. for 6 hours and then at 120 ° C. for 6 hours to remove excess solvent, and the ruthenium (III) nitrosyl nitrate powder The substrate 11 was coated with nickel oxide.
Next, this was set in an electric box furnace and sintered in air at 500 ° C. for 6 to 8 hours to convert ruthenium (III) nitrosyl nitrate powder into ruthenium oxide. The substrate 11 supporting nickel oxide and ruthenium oxide was set in an electric tubular furnace and reduced in a hydrogen atmosphere at 430 ° C. for 1 hour to make nickel oxide and ruthenium oxide an alloy of Ni and Ru.

  In Example 1-9, the catalyst 10 for hydrogen production having the metal active layer 12 containing Ru was produced by the production method A1.

  Specifically, in Example 1-9, a nitrosyl ruthenium (III) nitrate aqueous solution layer (however, a nitrosyl ruthenium (III) nitrate aqueous solution (concentration 10%) was used instead of the nickel (II) nitrate hexahydrate aqueous solution (however, The same procedure as in Example 1-1 was performed except that Ru in the ruthenium (III) nitrosyl nitrate aqueous solution layer was 2.5% by weight with respect to the substrate 11.

  In the comparative example, a nickel foil honeycomb structure without the metal active layer 12 was used.

Table 1 shows the composition ratio of the metal active layer 12 of the produced hydrogen production catalyst 10 according to Examples 1-1 to 1-9 and the weight of each composition of the metal active layer 12 per geometric surface area of the substrate 11 ( Composition amount). The composition was measured by energy dispersive X-ray analysis (EDS) attached to a scanning electron microscope (SEM) described later.

(Examples 1-10 to 1-12)
In Examples 1-10 to 1-12, the base 11 used was a metal foil having a length of 219 mm, a width of 10 mm, and a thickness of 0.03 mm wound in a spiral shape.
In Example 1-10, nickel foil was used as the metal foil.
In Example 1-11, a stainless steel foil was used as the metal foil.
In Example 1-12, Fe-Cr-Al foil was used as the metal foil.
In Examples 1-10 to 1-12, the hydrogen production catalyst 10 having the metal active layer 12 containing Ni (first element) and Re (second element) was produced by the production method B1.
In Examples 1-10 to 1-12, the metal active layer 12 having the same composition ratio and composition amount ratio was formed on each of the metal foils in the same procedure as in Example 1-6.

(Examples 2-1 and 2-2)
In Examples 2-1 and 2-2 and the comparative example, the same nickel foil honeycomb structure as that of Example 1-1 was used as the substrate 11.

  In Example 2-1, the hydrogen production catalyst 10 having the metal active layer 12 containing Ni was produced by the production method A2.

Specifically, in Example 2-1, as the acid treatment, the substrate 11 was immersed in a 10% nitric acid aqueous solution, and a nickel (II) nitrate aqueous solution layer was formed on the surface of the substrate 11.
Next, the substrate 11 on which the nickel (II) nitrate aqueous solution layer was formed was dried at 60 ° C. for 6 hours to remove excess solvent, whereby a substrate 11 coated with nickel (II) nitrate hexahydrate powder was obtained.
Next, this was set in an electric box furnace and sintered in air at 500 ° C. for 6 to 8 hours to convert nickel nitrate (II) hexahydrate powder into nickel oxide.
Next, the base body 11 carrying nickel oxide was set in an electric tubular furnace and reduced in a hydrogen atmosphere at 430 ° C. for 1 hour to change the nickel oxide to Ni.

  In Example 2-2, the hydrogen production catalyst 10 having the metal active layer 12 containing Ni (first element) and Re (second element) was produced by the production method B2.

  Specifically, in Example 2-2, after obtaining the base 11 carrying nickel oxide in the same procedure as in Example 2-1, the perrhenium was carried so as to carry 1% by weight of Re on the base 11. The same procedure as in Example 1-6 was performed except that an ammonium acid aqueous solution layer was formed.

[Evaluation method]
(Surface observation by scanning electron microscope (SEM))
The surface observation by SEM was performed about the catalyst 10 for hydrogen production produced in the said Examples 1-1 to 1-12 and Examples 2-1 and 2-2.

(Measurement of BET specific surface area)
The BET specific surface area of the hydrogen production catalyst 10 produced in Examples 1-1 to 1-12, Examples 2-1 and 2-2, and Comparative Example was measured.

(Measurement of catalyst characteristics by methane steam reforming reaction)
Using the hydrogen production apparatus 100, the catalyst characteristics of the hydrogen production catalyst 10 were measured. Here, hydrogen was produced by a methane steam reforming reaction using methane and steam.
After the methane steam reforming reaction in the reaction tube 107, the composition and flow rate of the exhaust gas containing hydrogen, residual methane, and the like were measured by the gas chromatograph 110 and the flow meter 112.
From the values measured by the gas chromatograph 110 and the flow meter 112, the methane conversion rate was determined by the equation (4).
Methane conversion [%] = 100 × (supplied methane−residual methane) / supplied methane (4)
Here, the methane conversion rate refers to the ratio of the amount of methane that has contributed to the generation of hydrogen with respect to the amount of methane supplied during the steam reforming reaction.
The catalyst characteristics were evaluated from the obtained methane conversion.

(1) Measurement of catalyst characteristics by temperature increase experiment About catalyst for hydrogen production 10 according to Examples 1-1 to 1-12, Examples 2-1, 2-2, and Comparative Example, It was measured.
In the measurement of the catalyst characteristics by the temperature increase experiment, the reaction temperature was raised within a predetermined range, and the product composition and gas flow rate at each temperature were measured. Thereby, the relationship between the methane conversion rate and the reaction temperature was determined.
Each measurement was carried out after holding at each temperature for a predetermined time and stabilizing the temperature.

As a pretreatment, before the steam reforming reaction, a reduction treatment for 1 hour was performed at 703 K with a gas in which hydrogen and nitrogen were mixed.
As reaction conditions, the flow rate of methane was 10 ml (STP) / min, the flow rate of water vapor was 13.63 ml (STP) / min, and the flow rate of nitrogen was 30 ml (STP) / min.
The ratio of the number of molecules in water vapor to the number of carbon atoms in methane (steam carbon ratio: S / C) was 1.36. The space velocity of the mixed gas of methane, water vapor, and nitrogen supplied to the reaction tube 107 was 6406 h ⁻¹ .

In Examples 1-1 to 1-12 and the comparative example, the reaction temperature range was set to 773 to 1173K. In addition, it hold | maintained for 30 minutes at each temperature every 50K.
In Examples 2-1 and 2-2, the reaction temperature range was 673 to 1173K. The temperature was kept for 20 minutes at each temperature.
In the comparative example, the reaction temperature range was 873 to 1173K. In the comparative example, since the catalytic activity was not shown in a temperature range lower than 873 K, the reaction temperature range was set.

(2) Measurement of catalyst characteristics by isothermal experiment The catalyst characteristics of Examples 2-1 and 2-2 were measured by an isothermal experiment.
The reaction temperature was kept constant at 973 K, and the composition of the product and the gas flow rate after a predetermined elapsed time of reaction were measured. Thereby, the relationship between the methane conversion rate and the elapsed reaction time was determined.
The reaction conditions were the same as those in the temperature increase experiment, and the reaction conditions were stricter than normal hydrogen production conditions. The reaction time was 140 minutes.

[Evaluation results]
The evaluation results of Examples 1-1 to 1-12, 2-1, 2-2 and the hydrogen production catalyst 10 according to the comparative example are shown below.

(Evaluation results of Examples 1-1 to 1-9)
FIG. 8 is an SEM image obtained by imaging the microstructure of the surface of the hydrogen production catalyst 10 according to Example 1-7. As shown in FIG. 8, it was confirmed that many metal fine particles having a particle diameter of 50 nm or more and 150 nm or less were formed. In addition, the same metal fine particle was confirmed also about the catalyst 10 for hydrogen production of Examples 1-1 to 1-6, 1-8, 1-9.

Table 2 shows the measurement results of the BET specific surface area in Examples 1-1 to 1-9 and the comparative example.
As shown in Table 2, the value of the BET specific surface area in Examples 1-1 to 1-9 was significantly higher than the value of the BET specific surface area in the comparative example. In the hydrogen production catalyst 10 according to Examples 1-1 to 1-9, the surface area was increased, and it was confirmed that metal fine particles were formed on the surface.

FIG. 9 is a graph showing catalyst characteristics of the hydrogen production catalyst 10 according to Examples 1-1 to 1-9 and the comparative example, as a result of a temperature increase experiment. FIG. 9 also shows the calculation result of the equilibrium conversion rate of methane under the same reaction conditions. The equilibrium conversion rate is a theoretical value of the methane conversion rate when the reactions shown in the equations (2) and (3) reach equilibrium at each temperature under a constant pressure.
In the comparative example, the catalyst activity was not shown in a temperature range lower than 873 K, whereas in Examples 1-1 to 1-9, it was confirmed that the catalyst activity was shown even in a temperature range lower than 873.
Moreover, in Examples 1-1 to 1-9, the methane conversion rate showed a higher value than the methane conversion rate in the comparative example even in a low temperature region of 1073 K or less. Thus, in Examples 1-1 to 1-9, it was confirmed that higher catalytic activity was obtained even in a lower temperature range than in the comparative example.
In particular, in Examples 1-1 and 1-5 made of Ni metal fine particles and Examples 1-2 to 1-4, 1-6 and 1-7 made of Ni and Re metal fine particles, the methane conversion was 1073K. Even in the following low temperature range, the value was close to the equilibrium conversion rate. Thus, in Examples 1-1 to 1-7, it was confirmed that higher catalytic activity was obtained in a low temperature range.

(Evaluation results of Examples 1-10 to 1-12)
Table 3 shows the measurement results of the BET specific surface area in Examples 1-10 to 1-12.
As shown in Table 3, the value of the BET specific surface area in Examples 1-10 to 1-12 was significantly higher than the value of the BET specific surface area in the comparative example. In the hydrogen production catalyst 10 according to Examples 1-10 to 1-12, the surface area was increased, and it was confirmed that fine metal particles were formed on the surface of the substrate 11.

  FIG. 10 is a graph showing the catalyst characteristics of the hydrogen production catalyst 10 according to Examples 1-10 to 1-12 according to a temperature increase experiment. FIG. 10 also shows the calculation result of the equilibrium conversion rate of methane at each reaction temperature under the same reaction conditions. Moreover, in FIG. 10, the result of the methane conversion rate of Example 1-6 is also shown as a reference.

  In Examples 1-10 to 1-12, as in Example 1-6 in which the substrate 11 is a nickel foil honeycomb structure, the methane conversion rate is close to the equilibrium conversion rate even in a low temperature range of 1073 K or less. Indicated. From this, it was confirmed that even when the substrate 11 is a spiral structure, high catalytic activity can be obtained. It was also confirmed that high catalytic activity was obtained even when the substrate 11 was made of a metal foil other than the nickel foil.

(Evaluation results of Examples 2-1 and 2-2)
FIG. 11 is an SEM image obtained by imaging the fine structure of the surface of the substrate 11 before the reduction treatment in Example 2-1. FIG. 12 is an SEM image obtained by imaging the fine structure of the surface of the substrate 11 before the reduction treatment in Example 2-2.
In Example 2-1, as shown in FIG. 11, an oxide fine particle layer containing Ni was formed on the substrate 11 by acid treatment, and it was confirmed that the particle size of the oxide fine particles was 50 nm or more and 150 nm or less. .
In Example 2-2, as shown in FIG. 12, an oxide fine particle layer containing Ni (first element) and Re (second element) is formed, and the particle diameter of the oxide fine particles is 10 nm or more and 100 nm. Was confirmed. In Example 2-2, it was confirmed that the oxide fine particle layer according to Example 2-1 was further refined than the particles.
It was confirmed that the particle size was maintained as metal fine particles after the reduction treatment.

Table 4 shows the measurement results of the BET specific surface area in Examples 2-1 and 2-2 and the comparative example.
As shown in Table 4, the value of the BET specific surface area in Examples 2-1 and 2-2 was significantly higher than the value of the BET specific surface area in the comparative example. In the hydrogen production catalyst 10 according to Examples 2-1 and 2-2, the surface area was increased, and it was confirmed that metal fine particles were formed on the surface of the substrate 11. Moreover, in the hydrogen production catalyst 10 according to Example 2-2, it was confirmed that the value of the BET specific surface area was larger than that of the hydrogen production catalyst 10 according to Example 2-1, and further refinement was promoted. It was.

FIG. 13 is a graph showing the catalyst characteristics of the hydrogen production catalyst 10 according to Examples 2-1 and 2-2 and the comparative example, as a result of temperature increase experiments.
In the comparative example, the catalyst activity was not shown in a temperature range lower than 873 K, whereas in Examples 2-1 and 2-2, it was confirmed that the catalyst activity was shown even in a temperature range lower than 873.
In Examples 2-1 and 2-2, the methane conversion rate was significantly higher than the methane conversion rate in the comparative example even in a low temperature range of 1073 K or less. Thus, in Examples 2-1 and 2-2 by acid treatment, it was confirmed that high catalytic activity was obtained even in a low temperature range.

In addition, as a result of measurement of the catalyst characteristics by an isothermal experiment, the hydrogen production catalyst 10 according to Example 2-1 in which the metal active layer 12 made of Ni metal fine particles was formed had 140 minutes even under severe hydrogen production conditions. The methane conversion decreased only by about 10%. It was confirmed that a high methane conversion rate was maintained for a long time by forming Ni metal fine particles on the nickel foil. This is considered to be because, for example, the metal foil and the metal fine particles have the same component, thereby suppressing the peeling of the metal active layer 12 due to the difference in the coefficient of thermal expansion.
Further, in the hydrogen production catalyst 10 according to Example 2-2 in which the metal active layer 12 made of Ni and Re metal fine particles was formed, the methane conversion rate was reduced only by about 3%. It was confirmed that heat resistance is improved and high methane conversion is maintained for a longer time by alloying Ni metal fine particles and Re metal fine particles. This is considered to be because, for example, the Ni metal fine particles and the Re metal fine particles are alloyed to suppress the coarsening of the metal fine particles.

The embodiment of the present invention has been described above, but the present invention is not limited to the above-described embodiment, and it is needless to say that various modifications can be made without departing from the gist of the present invention.

DESCRIPTION OF SYMBOLS 10 ... Hydrogen production catalyst 11 ... Base | substrate 11a, 11b ... Metal foil 12 ... Metal active layer 100 ... Hydrogen production apparatus 101 ... Supply part 102 ... Catalyst reaction part 103- ..Evaporator 104 ... Water container 105 ... Pump 106 ... Weigh scale 107 ... Reaction tube 108 ... Quartz wool 109 ... Electric furnace 110 ... Gas chromatograph 111 ... Cold trap 112 ... Flow meter

Claims (21)

Metal foil,
A metal active layer composed of metal particles carried on the metal foil;
A catalyst for hydrogen production comprising: The hydrogen production catalyst according to claim 1,
The metal active layer includes a first element selected from Ni, Ru, Rh, Pt, Pd, Ir, Fe, and Co. A hydrogen production catalyst. The hydrogen production catalyst according to claim 2,
The first element is Ni or Ru. A catalyst for hydrogen production. The hydrogen production catalyst according to claim 2 or 3,
The metal active layer is selected from one or more of Ru, Re, Mn, Mo, W, Cr, Ta, Hf, Os, Sn, Zn, La, Ce, Rh, Pt, Mg, Al, Si, Cu, A hydrogen production catalyst further comprising a second element different from the first element. The hydrogen production catalyst according to claim 4,
The second element is selected from Re and Ru. A hydrogen production catalyst. A catalyst for hydrogen production according to claim 4 or 5,
The metal particles are formed of an alloy including the first element and the second element,
The content of the first element in the metal particles is 1 wt% or more and less than 100 wt%,
The catalyst for hydrogen production, wherein the content of the second element in the metal particles is more than 0 wt% and not more than 99 wt%. The hydrogen production catalyst according to claim 6,
The content of the first element in the metal particles is 30 wt% or more and 92 wt% or less,
The catalyst for hydrogen production, wherein the content of the second element in the metal particles is 8 wt% or more and 70 wt% or less. A catalyst for hydrogen production according to any one of claims 1 to 7,
The metal foil is a hydrogen production catalyst whose main component is a material selected from the group consisting of Ni, stainless steel, and iron-based alloys. The hydrogen production catalyst according to claim 8,
The metal foil is a hydrogen production catalyst having Ni as a main component. A catalyst for hydrogen production according to any one of claims 1 to 9,
The metal foil constitutes a honeycomb structure or a spiral structure. Hydrogen production catalyst. A catalyst for hydrogen production according to any one of claims 1 to 10,
The metal particles have a particle size of 1 nm to 500 nm. Hydrogen production catalyst. The hydrogen production catalyst according to claim 11,
The metal particle has a particle size of 10 nm to 150 nm. Hydrogen production catalyst. Form a strong acid salt powder layer containing a metal element on the surface of the metal foil,
By thermally decomposing the strong acid salt powder layer, an oxide particle layer containing the metal element is formed,
A method for producing a catalyst for hydrogen production, wherein the metal active layer containing the metal element is formed by reducing the oxide particle layer. A method for producing a catalyst for hydrogen production according to claim 13,
The manufacturing method of the catalyst for hydrogen production which forms the said strong acid salt powder layer using the strong acid salt aqueous solution of the said metal element. A method for producing a catalyst for hydrogen production according to claim 13 or 14,
The method for producing a catalyst for hydrogen production, wherein the metal element includes a first element selected from Ni, Ru, Rh, Pt, Pd, Ir, Fe, and Co. A method for producing a catalyst for hydrogen production according to claim 13,
The metal foil has the metal element as a main component,
The manufacturing method of the catalyst for hydrogen production which forms the said strong acid salt powder layer by acid-treating the surface of the said metal foil. A method for producing a catalyst for hydrogen production according to claim 16,
The metal element is Ni. A method for producing a catalyst for hydrogen production. A method for producing a catalyst for hydrogen production according to claim 16 or 17,
The manufacturing method of the catalyst for hydrogen manufacture which acid-treats the surface of the said metal foil using nitric acid. A method for producing a catalyst for hydrogen production according to claim 15,
The method for producing a catalyst for hydrogen production, wherein the strong acid salt powder layer, the oxide particle layer, and the metal active layer further include a second element different from the first element as the metal element. A method for producing a catalyst for hydrogen production according to claim 19,
The second element is at least one selected from Ru, Re, Mn, Mo, W, Cr, Ta, Hf, Os, Sn, Zn, La, Ce, Rh, Pt, Mg, Al, Si, and Cu. A method for producing a catalyst for production. A supply unit for supplying a hydrogen source gas containing a hydrocarbon compound and a reaction gas containing water vapor;
A catalytic reaction unit that reacts the hydrogen source gas supplied from the supply unit with the reaction gas to generate a steam reforming reaction, and
The said catalyst reaction part has a catalyst for hydrogen production as described in any one of Claim 1 to 12. The hydrogen production apparatus.