JP6257256B2 - Steam reforming reactor and fuel cell power generator - Google Patents

Description

The present invention is provided with a steam reforming reactor with a catalyst layer mainly composed of water vapor reforming catalyst, the catalyst layer on the hydrocarbon compounds gas supply and the oxygen supplying hydrocarbon compounds gas An oxygen-containing gas supply unit that supplies a gas containing gas and a water vapor supply unit that supplies water vapor are provided, and at least a part of the combustible gas discharged from the steam reforming reactor is combusted, whereby the steam reforming reaction is performed. The present invention relates to a steam reforming reaction apparatus provided with a combustion section for heating a vessel and a fuel cell power generation apparatus including the steam reforming reaction apparatus.

So-called hydrocarbon compounds that obtain hydrogen, carbon monoxide, carbon dioxide, methane, etc. by reacting hydrocarbon compounds with water vapor occupy the most important position in the hydrogen production process incorporated in fuel cell power generators, etc. This is a steam reforming technology. The steam reforming method is widely used because the equipment is cheaper than the partial oxidation (POX) method.
Conventional steam reforming catalysts are mainly nickel-based (see Patent Document 1). However, these catalysts are liable to cause carbon deposition and have the disadvantage that the activity decreases in a short time.

  Therefore, a ruthenium-based catalyst has been developed as a steam reforming catalyst in which carbon deposition is unlikely to occur. Among them, ruthenium and iridium and / or rhodium having a content of 0.1 to 5 times the content of ruthenium are treated with alumina. A catalyst for steam reforming of hydrocarbon compounds, which is supported on a carrier having a main component as a main component, has been developed as a highly durable ruthenium-based catalyst in which active metal aggregation is unlikely to occur (see Patent Document 2).

  On the other hand, when performing such a steam reforming reaction in a fuel cell, a steam reforming reactor having a catalyst layer mainly composed of the steam reforming catalyst is divided into a steam reforming method and a partial oxidation (POX). ) Method and autothermal (ATR) method are provided so that the system can be operated, and an optimum reforming method is selected according to the state of the reformer to perform highly efficient reforming. (See Patent Document 3).

Japanese Patent Laid-Open No. 04-363140 JP 2008-055552 A JP 2004-319420 A

  However, in the steam reforming catalyst of Patent Document 2, when the reaction system is exposed to an environment in which oxygen is present, the activity is still reduced, so that the oxygen-containing gas is not supplied to the steam reforming reactor. There was a circumstance that a steam reforming reaction had to be performed. For this reason, such a steam reforming reactor starts the steam reforming reaction at the start-up at a relatively low temperature, and it takes time to stabilize the operation state, or the steam reforming reaction at the initial start-up time. There was a problem that it took time to start up because the vessel had to be heated separately. Therefore, when such a steam reforming reactor is mounted on a fuel cell or the like, the start-up response is low.

  However, as described in Patent Document 3, if the steam reforming reactor performs POX at startup using an oxygen-containing gas to increase startup response, the steam reforming catalyst deteriorates quickly, Long-term durability cannot be expected.

  Therefore, in view of the above circumstances, the present invention is to provide a steam reforming reactor having high start-up response and high long-term durability. The object is to provide a battery power generator.

The characteristic configuration of the steam reforming reaction apparatus of the present invention includes a steam reforming reactor including a catalyst layer mainly composed of a steam reforming catalyst, and carbonization for supplying a hydrocarbon compound gas to the catalyst layer. A hydrogen compound gas supply unit, an oxygen-containing gas supply unit for supplying an oxygen-containing gas, and a steam supply unit for supplying water vapor are provided, and at least a part of the combustible gas discharged from the steam reforming reactor is combusted A steam reforming reaction apparatus comprising a combustion section for heating the steam reforming reactor,
The steam reforming catalyst is formed by supporting ruthenium and rhodium having a ruthenium content of 0.01 mass times or more and less than 0.1 mass times on a carrier mainly composed of alumina,
A POX step of causing a partial oxidation reaction between the hydrocarbon compound gas and the oxygen-containing gas in the catalyst layer and raising the temperature of the catalyst layer by the reaction heat;
In the catalyst layer, in addition to the hydrocarbon compound gas and the oxygen-containing gas, an ATR step of introducing water vapor to cause an autothermal reforming reaction and raising the temperature of the catalyst layer by the reaction heat; After going in order,
The catalyst layer is supplied from a hydrocarbon compound gas supply unit, an oxygen-containing gas supply unit, and a steam supply unit so as to perform a steam reforming process in which a steam reforming reaction is performed using a hydrocarbon compound gas and steam. It is in the point provided with the control device which controls each gas quantity .

When the present inventors use a catalyst for ruthenium and rhodium supported on a carrier as a steam reforming catalyst provided in the steam reforming reactor, a catalyst layer having high activity for the steam reforming reaction is formed. . Furthermore, the catalyst layer is surprisingly combined with the POX process and the ATR process in this order, and then when the steam reforming process is performed, the steam reforming catalyst does not deteriorate so much and can be used for a long time. It became clear to endure.

  That is, it has been clarified that even a steam reforming catalyst that is inherently weak in an atmosphere in which oxygen is present stably maintains its activity over a long period of time depending on the specific use environment.

  Therefore, prior to the steam reforming reaction, the POX process and the ATR process are performed using a catalyst obtained by supporting ruthenium and rhodium on a support as the steam reforming catalyst provided in the steam reforming reactor. Thus, the steam reforming reactor can efficiently perform the temperature raising operation using the oxidation reaction. Therefore, the steam reforming reactor can be started quickly. Moreover, since the steam reforming catalyst whose temperature has been raised is a highly active catalyst containing ruthenium, the steam reforming reaction is still carried out with a high activity.

According to the above knowledge, a hydrocarbon compound gas supply unit for supplying a hydrocarbon compound gas to the catalyst layer and oxygen are provided, including a steam reforming reactor including a catalyst layer mainly composed of a steam reforming catalyst. Since the oxygen-containing gas supply unit for supplying the containing gas and the water vapor supply unit for supplying the water vapor are provided, the gas component supplied to the catalyst layer is introduced into the state in which the oxygen-containing gas is introduced together with the hydrocarbon compound gas, Either a state in which a hydrogen compound gas, an oxygen-containing gas and water vapor are introduced, or a state in which a hydrocarbon compound gas and water vapor are introduced can be set. That is, the reaction form in the catalyst layer can be set to any of the POX process, the ATR process, and the steam reforming process.

  In addition, since the reaction mode can be appropriately switched by the control device, the temperature of the catalyst layer and the generation efficiency of hydrogen gas are optimally controlled by appropriately controlling the reaction occurring in the catalyst layer. The catalyst filled in the catalyst layer can be used for a long period of time in an operating environment that is difficult to deteriorate, and a highly active steam reforming reaction can be performed stably over a long period of time.

  Here, since the steam reforming catalyst is mainly composed of a catalyst in which ruthenium and rhodium are supported on a carrier, a catalyst layer having high activity for the steam reforming reaction is formed. Furthermore, it has been clarified from the above knowledge that the catalyst layer does not deteriorate so much and can withstand long-term use in an operation in which the POX step, the ATR step, and the steam reforming step are sequentially performed.

  Therefore, according to the steam reforming reaction apparatus of the present invention, a highly durable steam reforming process can be performed over a long period of time.

The steam reforming catalyst of these, be used as a ruthenium on a carrier mainly composed of alumina, carrying a rhodium less than 0.1 mass times 0.01 times the content of the ruthenium catalyst The As long as each metal is supported on the carrier, ruthenium and rhodium can be dispersed on the carrier in the form of fine particles, and the activity can be improved by dispersing ruthenium and rhodium with a high surface area.

  The use of ruthenium and rhodium as a catalyst carrying rhodium that is 0.01 to 0.1 mass times the ruthenium content is because the rhodium content is 0.1 mass times the ruthenium content. When the amount is large, the ratio of ruthenium appearing on the surface is extremely reduced, which is not preferable. On the other hand, when the amount is less than 0.01 times by mass, the effect of suppressing the ruthenium aggregation of rhodium is insufficient, which is not preferable. In addition, when each metal is supported on the support while maintaining these ratios, the partial oxidation reaction becomes difficult to proceed if the concentration of the noble metal is too low, and the noble metal is not uniformly dispersed on the surface of the support if the concentration is too high. Since a lot of useless precious metals that do not contribute to the reaction increase, it is possible to maintain a good balance when rhodium, which is 0.01 to 0.1 times the ruthenium content, is supported.

Further, as the carrier, particularly when using alumina, heat resistance, high mechanical strength, Ru can be increased activity of ruthenium and rhodium are supported. Such a steam reforming catalyst is preferably used in the form of tablets, spheres, rings, or molded into a honeycomb.

Before SL steam reforming catalyst, the ruthenium and rhodium may be those which had been carried in a metallic state on a support.

Method for supporting each metal in charge of body, can be supported by various known methods, manufacturing steps, it is preferred impregnation method in terms of cost, it is widely. In addition, the material supported on the inorganic oxide support is converted into metallic ruthenium and rhodium by thermal decomposition, hydrazine reduction, and the like by post-treatment in the impregnation method. In the present invention, ruthenium and rhodium need to be supported on a carrier, so that post-treatment should be performed in a reducing atmosphere, and the generated fine particles are dispersed in a fine state without agglomeration and growth. From the viewpoint of being preferable, it is preferably converted to a metal state of ruthenium or rhodium by hydrazine reduction and supported .

  The impregnation method is to impregnate a material to be supported on the substrate by impregnating the substrate with an aqueous solution of the material to be supported, drying, and firing as necessary. According to this impregnation method, the inorganic oxide used as the base material does not change before and after the impregnation, but the material to be supported has different properties depending on the state of the aqueous solution and the supported state. In the present invention, ruthenium and rhodium need to be impregnated in a salt state and supported in a metal state. In the case of a noble metal salt, although it exists stably in an aqueous solution state, it is known that the carrier surface is thermally decomposed into metal fine particles.

  However, the reaction on the surface of the carrier varies depending on the loading conditions such as temperature and concentration, and when the above impregnation method is performed, the supported noble metal may be partially supported in the form of oxide or salt. . In addition, when water is volatilized and changed to a fine particle state from an aqueous solution state, the particles aggregate to increase in size, and the surface area per unit metal amount may decrease. As a result, the catalytic activity of the active metal (ruthenium, rhodium) may be reduced.

  In this regard, after impregnating the ruthenium salt and rhodium salt into the inorganic oxide carrier, liquid phase reduction treatment with hydrazine converts the ruthenium salt and rhodium salt into metal ruthenium and rhodium by liquid phase reduction, so that the aggregation Needless to say, it is rapidly made into fine particles and dispersed and supported on the inorganic oxide carrier. Therefore, finer ruthenium salts and rhodium salts are supported on the inorganic oxide carrier in a highly dispersed state, and are capable of supporting ruthenium and rhodium in a highly active state, and are highly active hydrocarbon compounds. It can be used as a steam reforming catalyst.

Also, characteristic feature of the fuel cell system of the present invention is that with the steam reforming reactor.

Ie, when provided with the steam reforming reactor, it is possible to start quickly, high responsive to changes in operating conditions, it can be an excellent fuel cell convenience. In addition, since the activity of the catalyst layer can be maintained high over a long period of time, the steam reforming reactor can be used with high reliability over a long period of time.

  Accordingly, it is to provide a steam reforming reactor having high start-up responsiveness and high long-term durability, thereby providing a steam reforming reaction apparatus and a fuel cell power generation apparatus with enhanced usability. did it.

Schematic diagram of the fuel cell of the present invention Schematic showing start / stop test pattern

  Below, the hydrogen production apparatus of this invention is demonstrated. In addition, although suitable examples are described below, these examples are described in order to more specifically illustrate the present invention, and various modifications can be made without departing from the spirit of the present invention. The present invention is not limited to the following description.

[Production of catalyst]
As the steam reforming catalyst 11a, a steam reforming catalyst 11a of a hydrocarbon compound in which ruthenium and rhodium are supported on a carrier was produced.
The steam reforming catalyst 11a can be obtained by supporting ruthenium and rhodium having a ruthenium content of 0.01 mass times or more and less than 0.1 mass times on a carrier mainly composed of alumina.
Here, ruthenium and rhodium can be supported on ruthenium and rhodium by impregnating an alumina carrier with a ruthenium salt and rhodium salt and then reducing the hydrazine.

(Impregnation support)
Specific production examples are shown below.
A spherical α-alumina (carrier) having a diameter of 3 mm is impregnated with a predetermined concentration of ruthenium chloride aqueous solution and rhodium chloride aqueous solution and dried. Here, the amount of rhodium chloride and ruthenium chloride impregnated is such that the amount of rhodium supported is 0.01 mass times or more and less than 0.1 mass times ( less than 0.1 mass times the content of the supported ruthenium content. It can be determined and determined from the relationship between the aqueous solution concentration and the amount of impregnation. Thereby, ruthenium-rhodium supported alumina (hereinafter, the composition of the steam reforming catalyst 11a is abbreviated as X mass% ruthenium-Y mass% rhodium / alumina catalyst) can be obtained.

(Wet reduction)
The obtained ruthenium-rhodium-supported alumina is immersed in an aqueous sodium hydroxide solution to fix the ruthenium on the carrier, and then reduced (wet reduction method) with an aqueous hydrazine solution at room temperature for 1 hour, washed and dried for steam reforming. A ruthenium-rhodium / alumina catalyst was obtained as the catalyst 11a.

[Steam reforming reactor]
As shown in FIG. 1, the steam reforming reaction apparatus includes a steam reforming reactor 1 including a catalyst layer 11 containing the steam reforming catalyst 11 a as a main component, and the catalyst layer 11 includes a hydrocarbon compound. A hydrocarbon compound gas supply unit 12 for supplying methane as a gas, an oxygen-containing gas supply unit 13 for supplying air as an oxygen-containing gas, and a water vapor supply unit 14 for supplying water vapor are provided. Here, city gas mainly composed of methane can be used as a supply source of methane. Further, the steam reforming reaction apparatus includes a combustion unit 15 that heats the steam reforming reactor 1 by combusting at least a part of the combustible gas discharged from the catalyst layer 11. Air and methane supplied from the supply parts 12 and 13 are supplied to the catalyst layer 11 in a state preheated by the combustion part 15. In addition, an evaporator 17 that is attached to the catalyst layer 11 and vaporizes water supplied to the water vapor supply unit 14 by heat from the combustion unit is provided so that water vapor can be supplied to the catalyst layer 11. ing. The catalyst layer 11 includes a control device 16 that controls the amount of each gas supplied from the hydrocarbon compound gas supply unit 12, the oxygen-containing gas supply unit 13, and the water vapor supply unit 14.

[Fuel cell power generator]
As shown in FIG. 1, a fuel cell power generator according to the present invention includes a steam reforming reactor 1 that reforms raw fuel to generate a fuel gas mainly composed of hydrogen gas, and a steam reforming reactor 1. The fuel cell 3 having the anode 31 to which the fuel gas generated in step 1 is supplied, the cathode 32 to which the oxygen gas is supplied, and the fuel component in the exhaust fuel gas discharged from the anode 31 after being used in the power generation reaction And a combustion section 15 that burns exhaust gas discharged from the cathode 32 after being used in the power generation reaction in a mixed state and heats the steam reforming reactor 1 with the combustion heat. In the present embodiment, the steam reforming reaction device, the fuel cell 3, and the combustion unit 15 are accommodated inside the device housing 30.

[Steam reforming reaction]
In the catalyst layer 11, a POX process in which a partial oxidation reaction is caused by a hydrocarbon compound gas and an oxygen-containing gas and the catalyst layer 11 is heated by the reaction heat; In addition to the similar gas and the oxygen-containing gas, water vapor is introduced to cause an autothermal reforming reaction, and the ATR step of raising the temperature of the catalyst layer 11 by the reaction heat is sequentially performed, followed by hydrocarbons. The control device 16 supplies from the hydrocarbon compound gas supply unit 12, the oxygen-containing gas supply unit 13, and the water vapor supply unit 14 so as to perform a steam reforming process in which a steam reforming reaction is performed using a compound gas and steam. Control the amount of each gas.
Hydrogen consumed in the fuel cell 3 is generated by the steam reforming process, and the catalyst layer is quickly heated by the POX process and the ATR process performed prior to the steam reforming process. The steam reforming process can be started in a very short time.

[Catalyst durability test]
Using the microreactor simulating the steam reforming reaction apparatus of FIG. 1, with the catalyst layer 11 filled with steam reforming catalysts 11a having various ruthenium rhodium ratios, reduction treatment and oxidation treatment at high temperatures are performed under the conditions shown in Table 1. Repeated tests were conducted. That is, nitrogen, hydrogen, nitrogen, and air were sequentially supplied to the catalyst layer 11 of the microreactor preheated to 700 ° C., and the degree of decrease in the activity of the steam reforming catalyst 11a was measured. The degree of decrease in activity was determined as the amount of carbon monoxide (CO) adsorbed on the catalyst layer 11 before and after the test (it is known that the amount of adsorption decreases as the activity decreases).

  Hereinafter, the method for producing the steam reforming catalyst 11a used in the durability test will be described more specifically.

(Catalyst A: 2% by mass ruthenium / α alumina catalyst)
98 g of α-alumina as an inorganic oxide carrier having a diameter of 3 mm was impregnated with 30 ml of an aqueous ruthenium chloride solution (ruthenium content: 2 g), dried at 80 ° C. for 3 hours, and immersed in an aqueous 0.375 N-NaOH solution for 20 hours. A liquid phase reduction treatment with an aqueous solution of% hydrazine, a washing treatment with pure water, followed by drying at 80 ° C. for 3 hours to obtain a catalyst in which 2% by mass of ruthenium was supported on α-alumina.

(Catalyst B: 1.99 mass% ruthenium-0.01 mass% rhodium / α alumina catalyst)
A total of 30 ml of a mixed aqueous solution of ruthenium chloride and rhodium chloride (ruthenium content 1.99 g, rhodium content 0.01 g) was impregnated into 98 g of α-alumina as a 3 mm diameter inorganic oxide carrier, and dried at 80 ° C. for 3 hours. After immersion treatment with 0.375N-NaOH aqueous solution for 20 hours, liquid phase reduction treatment with 1% hydrazine aqueous solution, washing treatment with pure water, drying at 80 ° C. for 3 hours, and 1.99 mass% in α-alumina. A catalyst in which ruthenium and 0.01% by mass of rhodium were supported was obtained.

(Catalyst C: 1.9% by mass ruthenium-0.1% by mass rhodium / α alumina catalyst)
A total of 30 ml of a mixed aqueous solution of ruthenium chloride and rhodium chloride (ruthenium content 1.9 g, rhodium content 0.1 g) was impregnated into 98 g of α-alumina as a 3 mm diameter inorganic oxide carrier, dried at 80 ° C. for 3 hours, After immersion treatment with 0.375N-NaOH aqueous solution for 20 hours, liquid phase reduction treatment with 1% hydrazine aqueous solution, washing treatment with pure water, drying at 80 ° C. for 3 hours, 1.9% by mass in α-alumina A catalyst in which ruthenium and 0.1% by mass of rhodium were supported was obtained.

(Catalyst D: 0.7 mass% ruthenium / α alumina catalyst)
99.3 g of α-alumina as a 3 mm diameter inorganic oxide carrier was impregnated with 30 ml of an aqueous ruthenium chloride solution (0.7 g ruthenium content), dried at 80 ° C. for 3 hours, and immersed in an aqueous 0.375 N-NaOH solution for 20 hours. Treatment, liquid phase reduction treatment with 1% hydrazine aqueous solution, washing treatment with pure water, and drying at 80 ° C. for 3 hours to obtain a catalyst in which 0.7 mass% of ruthenium is supported on α-alumina. .

(Catalyst E: 0.69 mass% ruthenium-0.01 mass% rhodium / α alumina catalyst)
99.3 g of α-alumina as a 3 mm diameter inorganic oxide carrier was impregnated with 30 ml of a mixed aqueous solution of ruthenium chloride and rhodium chloride (ruthenium content 0.69 g, rhodium content 0.01 g) and dried at 80 ° C. for 3 hours. And then immersed in a 0.375N-NaOH aqueous solution for 20 hours, subjected to a liquid phase reduction treatment with a 1% hydrazine aqueous solution, washed with pure water, dried at 80 ° C. for 3 hours, and 0.69 mass in α-alumina. % Of ruthenium and 0.01% by mass of rhodium were obtained.

(Catalyst F: 0.6 mass% ruthenium-0.1 mass% rhodium / α alumina catalyst)
99.3 g of α-alumina as a 3 mm diameter inorganic oxide carrier was impregnated with 30 ml of a mixed aqueous solution of ruthenium chloride and rhodium chloride (ruthenium content 0.6 g, rhodium content 0.1 g) and dried at 80 ° C. for 3 hours. And then immersed in a 0.375N-NaOH aqueous solution for 20 hours, subjected to a liquid phase reduction treatment with a 1% hydrazine aqueous solution, washed with pure water, dried at 80 ° C. for 3 hours, and 0.6 mass in α-alumina. % Of ruthenium and 0.1% by mass of rhodium were obtained.

As a result, it became as shown in Table 2. Ruthenium, rhodium and formed by loading a catalyst of 0.01 mass times less than 0.1 mass times the content of ruthenium (including less than 0.1 times by weight) is also decreased activity is low after test I understood.

[Operation test of steam reforming reactor]
Using the microreactor simulating the steam reforming reaction apparatus of FIG. 1, the catalyst layer 11 is filled with steam reforming catalysts 11a having various ruthenium rhodium ratios, and the start / stop test pattern of FIG. Then, a start / stop test was conducted. That is, at the start of start-up, only air is circulated, followed by a POX process for supplying air and methane, followed by a preheating process for preparing a temperature increase of the catalyst layer 11 to achieve a primary temperature increase of the catalyst layer 11. Subsequently, the ATR process is performed in the catalyst layer 11 by supplying water vapor, and further the secondary temperature rise of the catalyst layer 11 is achieved. At this time, it became clear that the catalyst layer 11 was heated to a temperature suitable for the steam reforming process in a very short time. When the inlet temperature of the catalyst layer 11 reaches the target temperature (500 ° C.), the supply of air is stopped, the steam supply amount is increased, and the steam reforming process is performed while maintaining the inlet temperature. In the steam reforming step, the catalyst outlet temperature gradually increases, and when the catalyst outlet temperature reaches 800 ° C., the amount of steam supplied is decreased to bring the steam reforming step toward convergence. When the catalyst outlet temperature is lowered to some extent, the methane supply amount is reduced to further lower the temperature of the catalyst layer 11. When the catalyst layer 11 reaches 300 ° C., the supply of steam and methane is stopped, the steam reforming process is terminated, and a purge process for supplying only air to the catalyst layer 11 is performed. Then, when the temperature of the catalyst layer 11 is sufficiently lowered, one cycle (4 hours) of the start / stop repetition test is set. This start / stop repetition was repeated 200 cycles.

  Hereinafter, the method for producing the steam reforming catalyst 11a used in the operation test will be described more specifically.

(Catalyst G: 1.8% by mass ruthenium-0.2% by mass rhodium / α alumina catalyst)
A total of 30 ml of a mixed aqueous solution of ruthenium chloride and rhodium chloride (ruthenium content 1.8 g, rhodium content 0.2 g) was impregnated into 98 g of α-alumina as a 3 mm diameter inorganic oxide carrier, and dried at 80 ° C. for 3 hours. After immersion treatment with 0.375N-NaOH aqueous solution for 20 hours, liquid phase reduction treatment with 1% hydrazine aqueous solution, washing treatment with pure water, drying at 80 ° C. for 3 hours, and 1.8% by mass in α-alumina. A catalyst in which ruthenium and 0.2% by mass of rhodium were supported was obtained.

(Catalyst H: 1.5 mass% ruthenium-0.5 mass% rhodium / α alumina catalyst)
A total of 30 ml of a mixed aqueous solution of ruthenium chloride and rhodium chloride (ruthenium content 1.5 g, rhodium content 0.5 g) was impregnated into 98 g of α-alumina as a 3 mm diameter inorganic oxide carrier, and dried at 80 ° C. for 3 hours. After immersion treatment with 0.375 N-NaOH aqueous solution for 20 hours, liquid phase reduction treatment with 1% hydrazine aqueous solution, washing treatment with pure water, drying at 80 ° C. for 3 hours, and 1.5 mass% in α-alumina. A catalyst in which ruthenium and 0.5% by mass of rhodium were supported was obtained.

As a result, it became as shown in Table 4. Ruthenium, rhodium and formed by loading a catalyst of 0.1 times the mass of less than 0.01 mass times or more of the content of ruthenium (including less than 0.1 times by weight), as compared to not adding the catalyst, deactivation It was found that the decrease in methane conversion due to repetition was small, and that the long-term durability was excellent.

  The steam reforming reaction apparatus of the present invention has excellent start-up response and long-term durability by performing the operation method of the steam reforming reactor of the present invention, so that it can be used as an extremely high-performance fuel cell. Can do.

1: Steam reforming reactor 11: Catalyst layer 11a: Steam reforming catalyst 12: Hydrocarbon compound gas supply unit 13: Oxygen-containing gas supply unit 14: Steam supply unit 15: Combustion unit 16: Controller 17: Evaporation Device 3: Fuel cell 30: Device casing 31: Anode 32: Cathode

Claims (3)

A steam reforming reactor including a catalyst layer mainly composed of a steam reforming catalyst is provided, and a hydrocarbon compound gas supply unit for supplying a hydrocarbon compound gas to the catalyst layer and an oxygen-containing gas are supplied. Combustion that provides an oxygen-containing gas supply unit and a water vapor supply unit that supplies water vapor, and burns at least part of the combustible gas discharged from the steam reforming reactor to heat the steam reforming reactor A steam reforming reaction apparatus comprising a section,
The steam reforming catalyst is formed by supporting ruthenium and rhodium having a ruthenium content of 0.01 mass times or more and less than 0.1 mass times on a carrier mainly composed of alumina ,
A POX step of causing a partial oxidation reaction between the hydrocarbon compound gas and the oxygen-containing gas in the catalyst layer and raising the temperature of the catalyst layer by the reaction heat;
In the catalyst layer, in addition to the hydrocarbon compound gas and the oxygen-containing gas, an ATR step of introducing water vapor to cause an autothermal reforming reaction and raising the temperature of the catalyst layer by the reaction heat; After going in order,
The catalyst layer is supplied from a hydrocarbon compound gas supply unit, an oxygen-containing gas supply unit, and a steam supply unit so as to perform a steam reforming process in which a steam reforming reaction is performed using a hydrocarbon compound gas and steam. A steam reforming reaction apparatus provided with a control device for controlling the amount of each gas. The steam reforming reaction apparatus according to claim 1 , wherein the steam reforming catalyst is a catalyst in which ruthenium and rhodium are supported in a metal state . A fuel cell power generator comprising the steam reforming reaction apparatus according to claim 1 .

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