JP4013463B2 - Shift reaction catalyst - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a shift reaction catalyst, and more particularly to a shift reaction catalyst that promotes a shift reaction that generates hydrogen and carbon dioxide from carbon monoxide and water vapor.
[0002]
[Prior art]
Conventionally, a shift unit including such a shift reaction catalyst has been provided in a fuel reformer that generates a hydrogen rich gas by a reforming reaction and supplies the hydrogen rich gas as a fuel gas to a fuel cell, for example. The fuel reformer is a device that reforms a hydrocarbon-based fuel to generate a hydrogen-rich gas, and the hydrogen-rich gas generated by the reforming reaction contains a predetermined amount of carbon monoxide. If carbon monoxide is contained in the gas supplied to the fuel cell, the catalyst provided in the fuel cell may be poisoned and the cell performance may be reduced. Therefore, the fuel reformer further includes a shift unit, Prior to supplying the fuel cell as a gas, the concentration of carbon monoxide in the hydrogen-rich gas is reduced.
[0003]
The shift reaction catalyst includes a high temperature shift catalyst in which the temperature at which the activity for promoting the shift reaction is sufficiently high is higher, and a low temperature shift catalyst in which the temperature at which the activity for promoting the shift reaction is sufficiently high is lower. Are known. As the high temperature shift catalyst, a catalyst containing iron and chromium is known, and as the low temperature shift catalyst, a catalyst containing copper, zinc and alumina is known (for example, JP-A-2-174936). ). Thus, while selecting the kind of catalyst suitably and combining the several shift part provided with a different catalyst, shift reaction progressed more fully and the further reduction of the carbon monoxide density | concentration has been aimed at.
[0004]
[Problems to be solved by the invention]
However, as described above, when the hydrogen rich gas whose carbon monoxide concentration is reduced by the shift reaction is supplied to the fuel cell as the fuel gas, as the load connected to the fuel cell varies, The amount of hydrogen-rich gas supplied to the shift reaction that proceeds in the shift section also varies, but when the amount of hydrogen-rich gas varies, the activity of the shift reaction cannot be maintained sufficiently high, and the carbon monoxide concentration is reduced. May become insufficient. That is, when the amount of hydrogen-rich gas supplied to the shift reaction increases rapidly, the water vapor required for the shift reaction cannot be supplied sufficiently following the amount of increase of the hydrogen-rich gas, resulting in insufficient water vapor. In some cases, the shift reaction could not proceed sufficiently.
[0005]
In order to make up for the shortage of water vapor in the shift unit, a water vapor generator that vaporizes water to generate water vapor is added to the shift unit, and when the shift unit is short of water vapor, the water vapor generated by the water vapor generator is shifted. The structure which supplements the water vapor | steam which a part requires is considered. However, since it takes a predetermined time to vaporize water by a method such as heating, when the load of the fuel cell fluctuates and water vapor shortage occurs in the shift section, this load fluctuation can be handled with sufficient response. However, it is difficult to supply a desired amount of water vapor immediately to the shift section to ensure sufficient shift reaction activity.
[0006]
The shift reaction catalyst of the present invention has been made for the purpose of solving these problems and preventing the shift reaction from being reduced due to lack of water vapor used for the shift reaction, and has the following configuration.
[0007]
[Means for solving the problems and their functions and effects]
The shift reaction catalyst of the present invention is a shift reaction catalyst that promotes a shift reaction that generates hydrogen and carbon dioxide from carbon monoxide and water vapor,
A catalytic metal having an activity of promoting the shift reaction;
A water vapor adsorbing substance capable of adsorbing water vapor,
The water vapor adsorbing substance is in an equilibrium state in which water vapor is not exchanged with the surroundings under a predetermined condition, and when the ambient water vapor partial pressure is higher than the ambient water vapor partial pressure in the equilibrium state. The main point is to take an adsorption state in which water vapor is adsorbed on and a discharge state in which water vapor is released when the surrounding water vapor partial pressure is lower than the surrounding water vapor partial pressure in the equilibrium state.
[0008]
The shift reaction catalyst of the present invention configured as described above comprises a catalytic metal having an activity for promoting the shift reaction, and a water vapor adsorbing substance capable of adsorbing water vapor, and hydrogen and dioxide from carbon monoxide and water vapor. Promotes the shift reaction to produce carbon. Here, the water vapor adsorbing substance included in the shift reaction catalyst includes an equilibrium state in which water vapor is not substantially exchanged with the surroundings under a predetermined condition, and a surrounding water vapor partial pressure in the equilibrium state. An adsorption state where water vapor is adsorbed when higher than the water vapor partial pressure and a discharge state where water vapor is released when the surrounding water vapor partial pressure is lower than the surrounding water vapor partial pressure in the equilibrium state are taken.
[0009]
According to such a shift reaction catalyst, the water vapor partial pressure in the gas subjected to the shift reaction is lower than the surrounding water vapor partial pressure when the water vapor adsorbing substance is in an equilibrium state under the same predetermined conditions. In some cases, the water vapor-adsorbing substance releases water vapor, and the shift reaction can proceed using this water vapor. Therefore, when the amount of water vapor used for the shift reaction is insufficient, it is possible to prevent the shift reaction from being reduced due to the lack of water vapor. This makes it possible to maintain the activity of the shift reaction sufficiently high.
[0012]
In the shift reaction catalyst of the present invention,
A catalyst layer comprising the catalyst metal;
A water vapor adsorbing portion provided in at least a part of the catalyst layer, the water vapor adsorbing portion including the water vapor adsorbing substance;
It is good also as providing.
[0013]
With such a configuration, since the water vapor adsorbing portion is provided on the catalyst layer, the water vapor adsorbing substance reacts with a high response to a decrease in the water vapor partial pressure in the gas subjected to the shift reaction. It is possible to release water vapor from the water and supplement water vapor required for the shift reaction.
[0014]
In the shift reaction catalyst, the water vapor adsorption part may exist in a dispersed state on the catalyst layer. With such a configuration, the carbon monoxide and water vapor in the gas subjected to the shift reaction can easily reach the catalyst metal without being hindered by the water vapor adsorption part.
[0015]
In the shift reaction catalyst, the water vapor adsorption part may be formed to be porous. With such a configuration, carbon monoxide and water vapor in the gas subjected to the shift reaction can easily diffuse in the water-vapor adsorbing portion formed in a porous manner. This can prevent the supply of carbon monoxide and water vapor to the catalyst metal from being hindered.
[0018]
In the shift reaction catalyst of the present invention, the water vapor adsorbing substance may be zeolite. Zeolite can adsorb water vapor (water molecules) in the pores of a three-dimensional network structure formed by aluminum, silicon and oxygen atoms, and can hold it as crystal water. Water vapor is adsorbed or released according to the water vapor partial pressure or temperature. The adsorption power of zeolite to adsorb water vapor is stronger than general physical adsorption, can hold water vapor effectively, and responds with a decrease in water vapor partial pressure at a predetermined high temperature where the shift reaction proceeds. Water vapor can be released with good performance.
[0019]
  The carbon monoxide concentration reducing method of the present invention is a carbon monoxide concentration reducing method for reducing the carbon monoxide concentration in a gas containing carbon monoxide,
  (A) Using a shift reaction catalyst that promotes a shift reaction that generates hydrogen and carbon dioxide from carbon monoxide and water vapor, the water vapor supplied onto the shift reaction catalyst, and the above-mentioned water supplied onto the shift reaction catalyst A step of reducing the carbon monoxide concentration by causing the shift reaction to proceed with carbon monoxide in the gas,
  The shift reaction catalyst is a catalytic metal having an activity of promoting the shift reaction.And a catalyst layer provided at least in a region on the catalyst layer.WithwaterWater vapor adsorbing substance capable of adsorbing vaporWhen,With
  In the step (a), the water vapor adsorbing substance is used in an equilibrium state in which water vapor is not substantially exchanged with the surroundings, an adsorption state in which the water vapor is adsorbed, and a reduction in the water vapor partial pressure. Accordingly, the gist is to take one of the states of releasing the water vapor to be used for the shift reaction.
[0020]
  According to such a carbon monoxide concentration reduction method of the present invention, the water vapor adsorbing substance releases water vapor as the ambient water vapor partial pressure decreases, and it is possible to supplement the water vapor required for the shift reaction. Therefore, it can suppress that the activity of shift reaction falls due to water vapor | steam shortage. Here, the water vapor supplied onto the shift reaction catalyst may be included in advance in the gas containing carbon monoxide, and is supplied onto the shift reaction catalyst separately from the gas. It may be a thing.In addition, since the water vapor adsorbing part is provided on the catalyst layer, it reacts with high responsiveness to the reduction of the water vapor partial pressure in the gas subjected to the shift reaction and releases water vapor from the water vapor adsorbing substance. And water vapor required for the shift reaction can be supplemented.
[0021]
In such a carbon monoxide concentration reducing method of the present invention, the water vapor adsorbing substance may be zeolite.
[0022]
  The carbon monoxide concentration reducing device of the present invention is a carbon monoxide concentration reducing device for reducing the carbon monoxide concentration in a gas containing carbon monoxide,
  A shift unit including a shift reaction catalyst that promotes a shift reaction that generates hydrogen and carbon dioxide from carbon monoxide and water vapor;
  A supply means for supplying a gas containing carbon monoxide and water vapor to the shift unit so as to be used for the shift reaction that proceeds on the shift reaction catalyst;
  The shift reaction catalyst may be any one of claims 1 to 3.4The gist of the present invention is any one of the shift reaction catalysts.
[0023]
In the carbon monoxide concentration reducing device of the present invention configured as described above, when a gas containing carbon monoxide and water vapor are supplied to the shift unit, hydrogen and carbon dioxide are generated from the carbon monoxide and water vapor in the shift unit. The shift reaction that produces carbon proceeds. Here, the shift reaction catalyst provided in the shift unit is the shift reaction catalyst of the present invention, and the water vapor partial pressure around the water vapor adsorbing substance provided in the shift reaction catalyst is higher than the water vapor partial pressure corresponding to the equilibrium state. When low, the water vapor adsorbing substance releases the adsorbed water vapor.
[0024]
According to such a carbon monoxide concentration reducing device of the present invention, when the water vapor partial pressure in the gas supplied to the shift unit becomes lower than the water vapor partial pressure corresponding to the equilibrium state, the water vapor adsorbing substance It is possible to proceed with the shift reaction using the water vapor released from. Therefore, when the amount of water vapor supplied from the supply means to the shift unit is insufficient, it is possible to suppress the activity of the shift reaction from being reduced due to the lack of water vapor. Thereby, it is possible to keep the activity of the shift reaction sufficiently high and to prevent the performance of reducing the carbon monoxide concentration in the gas from deteriorating. Here, the water vapor provided for the shift reaction by the supply means may be included in the gas containing carbon monoxide in advance, or may be provided for the shift reaction separately from the gas. .
[0025]
  A fuel cell device according to the present invention is a fuel cell device comprising a fuel cell that receives supply of a fuel gas containing hydrogen and an oxidizing gas containing oxygen to obtain an electromotive force by an electrochemical reaction,
  A reformer that reforms hydrocarbon fuel to produce hydrogen-rich gas;
  A shift reaction catalyst that promotes a shift reaction that generates hydrogen and carbon dioxide from carbon monoxide and water vapor; the supply of the hydrogen-rich gas from the reformer; and the carbon monoxide contained in the hydrogen-rich gas; A shift unit for reducing the carbon monoxide concentration in the hydrogen-rich gas by causing the shift reaction to proceed with water vapor supplied onto the shift reaction catalyst;
  Supply means for supplying the hydrogen-rich gas having a reduced carbon monoxide concentration in the shift unit as the fuel gas to the fuel cell;
  The shift reaction catalyst may be any one of claims 1 to 3.4The gist of the present invention is any one of the shift reaction catalysts.
[0026]
The fuel cell device of the present invention configured as described above includes a fuel cell that receives an supply of a fuel gas containing hydrogen and an oxidizing gas containing oxygen and obtains an electromotive force by an electrochemical reaction. Further, in a shift unit including a shift reaction catalyst that reforms a hydrocarbon-based fuel in a reformer to generate a hydrogen-rich gas and promotes a shift reaction that generates hydrogen and carbon dioxide from carbon monoxide and steam, Upon receiving the supply of the hydrogen rich gas, the shift reaction is allowed to proceed between the carbon monoxide contained in the hydrogen rich gas and the water vapor supplied onto the shift reaction catalyst, so that the carbon monoxide in the hydrogen rich gas is obtained. Reduce concentration. The fuel cell is supplied with the hydrogen-rich gas having a reduced carbon monoxide concentration as the fuel gas. Here, the shift reaction catalyst provided in the shift unit is the shift reaction catalyst of the present invention, and the water vapor partial pressure around the water vapor adsorbing substance provided in the shift reaction catalyst is higher than the water vapor partial pressure corresponding to the equilibrium state. When low, the water vapor adsorbing substance releases the adsorbed water vapor.
[0027]
According to such a fuel cell device of the present invention, when the water vapor partial pressure in the gas supplied to the shift unit is lower than the water vapor partial pressure corresponding to the equilibrium state, the water vapor adsorbing substance is released. The shift reaction can be advanced using water vapor. Therefore, when the amount of water vapor supplied to the shift unit is insufficient, it is possible to prevent the activity of the shift reaction from being reduced due to the lack of water vapor. In particular, in the fuel cell device, when the load connected to the fuel cell fluctuates, the amount of hydrogen-rich gas generated in the reformer and supplied to the shift unit and the shift reaction in the shift unit are used. However, the increase or decrease in the amount of water vapor cannot sufficiently follow the load fluctuation, and there is a possibility that the water vapor provided to the shift unit is insufficient in the shift unit. According to the fuel cell device of the present invention, when the water vapor is insufficient, the water vapor can be supplemented from the water vapor adsorbing substance provided in the shift catalyst, and the shift reaction is sufficiently activated even when the load of the fuel cell fluctuates. It is possible to ensure the performance of maintaining and reducing the carbon monoxide concentration in the hydrogen-rich gas.
[0028]
DETAILED DESCRIPTION OF THE INVENTION
  In order to further clarify the configuration and operation of the present invention described above, embodiments of the present invention will be described in the following order based on examples.
1. BurningOverall configuration of the battery unit 10
2. Shift catalyst provided in the shift unit 20
3. Shift catalystExamples about
[0029]
(1) FuelOverall configuration of the battery unit 10:
  FIG. 1 shows the present invention.is connected with1 is a block diagram showing an outline of the configuration of a fuel cell device 10. FIG. The fuel cell device 10 includes a gasoline tank 30 that stores gasoline, a water tank 32 that stores water, a desulfurizer 33 that removes sulfur in gasoline, an evaporator 34 that includes a heating unit 50, and hydrogen-rich gas by a reforming reaction. The reformer 36 to be generated, the shift unit 20 that reduces the carbon monoxide (CO) concentration in the hydrogen-rich gas by a shift reaction, the CO selective oxidation unit 38 that reduces the carbon monoxide concentration in the hydrogen-rich gas by an oxidation reaction, electrochemical The main components are a fuel cell 40 that obtains an electromotive force by reaction, a blower 42 that compresses air and supplies it to the fuel cell 40, and a control unit 60 that includes a computer.. BurningThe fuel cell device 10 is characterized by the configuration of the shift catalyst provided in the shift unit 20. First, the overall configuration of the fuel cell device 10 will be described with reference to FIG. 1.
[0030]
The gasoline stored in the gasoline tank 30 is supplied to the desulfurizer 33 and the heating unit 50. A pump 57 is provided in the fuel flow path 70 connecting the gasoline tank 30 and the desulfurizer 33, and a pump 56 is provided in the branch path 71 branched from the fuel flow path 70 and leading to the heating unit 50. Yes. The pumps 56 and 57 are connected to the control unit 60, are driven by a signal output from the control unit 60, and control the amount of gasoline supplied to the desulfurizer 33 and the heating unit 50.
[0031]
The desulfurizer 33 removes sulfur contained in the supplied gasoline by adsorption. Since the sulfur content lowers the activity of the reforming catalyst provided in the reformer 36 and inhibits the reforming reaction, the fuel cell device 10 is provided with a desulfurizer 33 prior to the reformer 36 to provide the sulfur content. Is removed. The gasoline from which the sulfur content has been removed by the desulfurizer 33 is supplied to the evaporator 34 via the fuel flow path 73.
[0032]
The fuel flow path 73 is connected to a water flow path 72 that is a flow path through which water supplied from the water tank 32 passes. The water passing through the water flow path 72 is mixed with the gasoline passing through the fuel flow path 73 at this connection, and supplied to the evaporator 34 together with the gasoline. A pump 58 is provided in the water flow path 72. The pump 58 is connected to the control unit 60, is driven by a signal output from the control unit 60, and adjusts the amount of water supplied to the evaporator 34 through the water flow path 72.
[0033]
The evaporator 34 is a device that vaporizes the gasoline from which sulfur has been removed and the water supplied from the water tank 32. As described above, the evaporator 34 receives a supply of gasoline and water, and is a mixed gas composed of water vapor and gasoline gas. The temperature is raised to a predetermined temperature and discharged. The mixed gas discharged from the evaporator 34 is supplied to the reformer 36 via the fuel gas channel 74. The evaporator 34 is provided with a heating unit 50 as a heat source for vaporizing water and gasoline. The heating unit 50 receives supply of gasoline supplied from the gasoline tank 30 and fuel exhaust gas discharged from a fuel cell described later. The heating unit 50 receives supply of compressed air from the blower 52. The heating unit 50 includes a combustion catalyst therein, performs a combustion reaction using the gasoline, fuel exhaust gas, and air, generates desired heat, and transfers the generated heat to the evaporator 34 by heat transfer. Supply. The amount of heat generated in the heating unit 50 is adjusted by controlling the amount of the gasoline and fuel exhaust gas supplied to the heating unit 50, whereby the evaporator 34 has a temperature corresponding to the reaction temperature in the reformer 36. The temperature of the mixed gas is raised to
[0034]
  The reformer 36 includes a reforming catalyst inside, and reforms the supplied mixed gas to generate a hydrogen-rich fuel gas. As the reforming catalyst, a noble metal such as platinum, palladium, rhodium, or an alloy thereof can be used. In addition, BreakIn the mass device 36, when the hydrogen rich gas is generated, in addition to the steam reforming reaction, the partial oxidation reaction accompanied by the generation of hydrogen proceeds simultaneously. Since the partial oxidation reaction is an exothermic reaction, when the steam reforming reaction proceeds, in addition to the heat brought from the evaporator 34 by the mixed gas, the heat generated by the partial oxidation reaction is also used. In order to supply oxygen necessary for this partial oxidation reaction, the reformer 36 is provided with a blower 53 for supplying air from the outside. The blower 53 is connected to the control unit 60, and the driving state is controlled by the control unit 60.
[0035]
  As mentioned above, BurningIn the fuel cell device 10, air is supplied to the reformer 36 and the heat required for the steam reforming reaction is covered by the heat generated by the oxidation reaction. However, the reformer 36 does not perform the oxidation reaction and performs steam reforming. It is good also as producing | generating hydrogen only by reaction. Or it is good also as making steam reforming reaction with high efficiency which produces | generates hydrogen advance more compared with partial oxidation reaction. In the case of such a configuration, a heating device such as a heater may be provided in the reformer 36 in order to supply heat required for the steam reforming reaction.
[0036]
The hydrogen-rich fuel gas generated by the reformer 36 is supplied to the shift unit 20 via the gas flow path 75. The shift unit 20 is a device that reduces the concentration of carbon monoxide in the supplied hydrogen-rich gas. The hydrogen-rich gas produced by the reforming reaction from the mixed gas in the reformer 36 contains a predetermined amount (about 10%) of carbon monoxide. The carbon monoxide concentration in the hydrogen-rich gas in the shift unit 20 Is reduced.
[0037]
  The shift unit 20 is a device that reduces the carbon monoxide concentration in the hydrogen-rich gas by advancing a shift reaction in which carbon monoxide and water are reacted to generate hydrogen and carbon dioxide, and promotes the shift reaction. It has a catalyst. As a catalyst (catalyst metal) that promotes such a shift reaction, a low-temperature catalyst such as a copper-based catalyst, a high-temperature catalyst such as an iron-based catalyst, and the like are known. The shift unit 20 may include any shift catalyst, and may be configured to sufficiently reduce the carbon monoxide concentration by combining these low temperature catalyst and high temperature catalyst. The type of shift catalyst provided in the shift unit 20 is appropriately determined according to the carbon monoxide concentration in the hydrogen-rich gas discharged from the reformer, the limit of the carbon monoxide concentration in the fuel gas required by the fuel cell 40, or the like. Just select. ShiThe foot part 20 includes a Cu—Zn catalyst. Hereinafter, as the equation (1), an equation representing a shift reaction promoted by the shift catalyst is shown.
[0038]
CO + H₂O → CO₂+ H₂+40.5 (kJ / mol) (1)
[0039]
Although omitted from FIG. 1, a heat exchanger may be provided between the reformer 36 and the shift unit 20. The reformer 36 is normally controlled so that its internal temperature becomes 600 ° C. or higher and proceeds with the reforming reaction of gasoline. However, the shift reaction that proceeds in the shift unit 20 is performed under the catalyst described above. It proceeds well in a temperature range of 200 ° C to 400 ° C. Therefore, a heat exchanger is provided between the reformer 36 and the shift unit 20, and the temperature of the hydrogen-rich gas discharged from the reformer 36 is sufficiently lowered and then supplied to the shift unit 34. It is possible to prevent the high temperature gas from being supplied to the shift unit 20.
[0040]
In addition, since the shift reaction is an exothermic reaction as shown in the formula (1), a cooling unit may be provided inside the shift unit 20 to adjust the temperature in the shift unit 34 to a desired temperature range. . The hydrogen rich gas whose carbon monoxide concentration has been reduced by the shift unit 20 is supplied to the CO selective oxidation unit 38 via the flow path 76.
[0041]
The CO selective oxidation unit 38 is a device for further reducing the carbon monoxide concentration in the hydrogen-rich gas supplied from the shift unit 20. That is, in the shift unit 20, the carbon monoxide concentration in the hydrogen-rich gas is reduced to about several percent, but in the CO selective oxidation unit 38, the carbon monoxide concentration is reduced to about several ppm. The reaction that proceeds in the CO selective oxidation unit 38 is a carbon monoxide selective oxidation reaction that oxidizes carbon monoxide in preference to hydrogen abundantly contained in the hydrogen-rich gas. The CO selective oxidation unit 38 is filled with a carrier carrying a platinum catalyst, a ruthenium catalyst, a palladium catalyst, a gold catalyst, or an alloy catalyst using these as a first element, which is a selective oxidation catalyst for carbon monoxide. Under such a carbon monoxide selective oxidation catalyst, the carbon monoxide selective oxidation reaction proceeds well by maintaining the reaction temperature at 100 ° C. to 200 ° C.
[0042]
In order to supply oxygen required for the carbon monoxide selective oxidation reaction proceeding in the CO selective oxidation unit 38, the CO selective oxidation unit 38 is provided with a blower 54. The blower 54 takes in air from the outside, compresses it, and supplies it to the CO selective oxidation unit 38. The blower 58 is connected to the control unit 60, and the amount of air (oxygen) supplied to the CO selective oxidation unit 38 is adjusted by the control unit 60. The carbon monoxide selective oxidation reaction that proceeds in the CO selective oxidation unit 38 is an exothermic reaction. Therefore, the CO selective oxidation unit 38 is provided with a cooling means in order to keep the internal temperature (catalyst temperature) at the desired reaction temperature.
[0043]
The hydrogen-rich gas whose carbon monoxide concentration has been lowered in the CO selective oxidation unit 38 as described above is guided to the fuel cell 40 through the fuel gas flow path 78, and is supplied to the cell reaction on the anode side as fuel gas. The fuel exhaust gas after being subjected to the cell reaction in the fuel cell 40 is discharged to the fuel discharge path 79 and guided to the heating unit 50 as described above, and the hydrogen remaining in the fuel exhaust gas is used for combustion. Consumed as fuel. On the other hand, the oxidizing gas involved in the cell reaction on the cathode side of the fuel cell 40 is supplied as compressed air through the oxidizing gas flow path 43 by the blower 42 that outputs a drive signal from the control unit 60. The remaining oxidizing exhaust gas used for the battery reaction is discharged to the outside.
[0044]
The fuel cell 40 is a solid polymer electrolyte type fuel cell, and is configured by laminating a plurality of single cells each including an electrolyte membrane, an anode, a cathode, and a separator. The electrolyte membrane is a proton-conductive ion exchange membrane formed of a solid polymer material such as a fluorine-based resin. Both the anode and the cathode are made of carbon cloth woven from carbon fibers. Further, a catalyst layer including a catalyst that promotes an electrochemical reaction is provided between the electrolyte membrane and the anode or the cathode. As such a catalyst, platinum or an alloy made of platinum and another metal is used. The separator is formed of a conductive member having gas impermeability, such as dense carbon that has been made impermeable to gas by compressing carbon, or a metal having excellent corrosion resistance. In addition, the separator forms a flow path of fuel gas and oxidizing gas between the anode and the cathode. The fuel cell 40 is supplied with hydrogen rich gas as a fuel gas and compressed air as an oxidizing gas to the flow path, and generates an electromotive force by proceeding an electrochemical reaction. The electric power generated by the fuel cell 40 is supplied to a predetermined load connected to the fuel cell 40. The electrochemical reaction that proceeds in the fuel cell 40 is shown below. Formula (2) represents the reaction on the anode side, Formula (3) represents the reaction on the cathode side, and the reaction represented by Formula (4) proceeds in the entire battery.
[0045]
H₂  → 2H⁺+ 2e^-                         ... (2)
(1/2) O₂+ 2H⁺+ 2e^-  → H₂O ... (3)
H₂+ (1/2) O₂  → H₂O ... (4)
[0046]
The control unit 60 is configured as a logic circuit centered on a microcomputer, and more specifically, a CPU 64 that executes a predetermined calculation according to a preset control program, and a control that is necessary for the CPU 64 to execute various calculation processes. ROM 66 in which programs, control data, and the like are stored in advance, RAM 68 in which various data necessary for performing various arithmetic processes in CPU 64 are temporarily read and written, detection signals from various sensors provided in fuel cell device 10, The input / output port 62 and the like for inputting information related to the load connected to the fuel cell and outputting a drive signal to each of the blowers and pumps already described according to the calculation result in the CPU 64 are provided. The controller 60 controls the operation state of the entire fuel cell device 10 by inputting and outputting various signals in this way.
[0047]
(2) Shift catalyst provided in the shift unit 20:
  BurningThe fuel cell device 10 is characterized in that the shift catalyst provided in the shift unit 20 further includes zeolite, which is a substance capable of adsorbing water vapor, in addition to the catalyst metal described above. Zeolite has a structure in which alkali metal, alkaline earth metal, and water molecules are contained in pores of a three-dimensional network structure formed by aluminum, silicon, and oxygen atoms. The water (crystal water) contained in the zeolite is called zeolite water. Even if this water molecule is taken out (dehydrated) from the three-dimensional network structure by reducing the surrounding water vapor partial pressure, the three-dimensional network structure of the zeolite is The vacancies in which the water molecules exist are left as they are, and the water molecules can be strongly adsorbed (condensed) again in the vacancies.
[0048]
  FIG. 2 is an explanatory diagram showing a manufacturing process of the shift catalyst provided in the shift unit 20.. ShiThe shift catalyst included in the foot unit 20 is formed by supporting a catalyst metal and the zeolite on a honeycomb. When manufacturing a shift catalyst, first, a catalyst metal is prepared (step S100).. ShiAs described above, the rotary unit 20 includes the Cu—Zn catalyst as a shift catalyst. In Step S100, the Cu—Zn catalyst is prepared by a well-known coprecipitation method using copper and zinc oxide. .
[0049]
Next, the catalyst metal and the zeolite powder are mixed (step S110). That is, the Cu—Zn catalyst prepared in step S100 is pulverized to form a catalyst powder, and the catalyst powder and the zeolite powder are mixed. Thereafter, a binder such as alumina slurry is added to the mixed powder (step S120), and this is coated on the honeycomb to coat the honeycomb (step S130), and then dried and fired (step S140). Complete the catalyst. The honeycomb used for manufacturing the shift catalyst may be any material that can be used as a catalyst carrier, such as a metal honeycomb or a ceramic honeycomb.
[0050]
  Configured as aboveBurningAccording to the fuel cell device 10, since the shift catalyst includes zeolite, when the amount of water vapor in the hydrogen-rich gas supplied to the shift unit 20 is large, water vapor in the hydrogen-rich gas is adsorbed by the zeolite, When the amount of water vapor is small, the water molecules retained as zeolite crystal water are released. Therefore, even when the amount of water vapor in the hydrogen-rich gas supplied to the shift unit 20 is temporarily reduced and the amount of water vapor is insufficient for proceeding with the shift reaction, the water molecules retained by the zeolite as crystal water are reduced. It is possible to obtain the effect that the water vapor required for the shift reaction can be released and the shift reaction can proceed favorably.
[0051]
  BurningIn the fuel cell device 10, the water required for the shift reaction that proceeds in the shift unit 20 is supplied via the evaporator 34 together with the water that is required for the steam reforming reaction that proceeds in the reformer 36. At this time, the amount of water supplied via the evaporator 34 for the steam reforming reaction and the shift reaction is equal to the efficiency of the steam reforming reaction that proceeds in the reformer 36 (the steam reforming is performed when the steam amount is increased). The quality reaction is easy to proceed) and the energy efficiency of the entire apparatus is reduced by consuming energy to vaporize water in the evaporator 34 (the more the amount of water vaporized in the evaporator 34 is, the more fuel is consumed) The amount of hydrogen-rich gas to be generated increases as the load increases (for example, the energy efficiency of the battery device 10 decreases). The amount of gasoline and the amount of water vapor to increase should also be adjusted accordingly.
[0052]
  As described above, when the amount of water vapor supplied via the evaporator 34 is controlled in accordance with the load variation, when the desired amount of water vapor increases rapidly, the amount of water vapor supplied with sufficient responsiveness. Cannot be increased, and there is a risk that the amount of water vapor will temporarily be insufficient in the shift unit 20. Even in this case,In the ft part 20, the water required for the shift reaction can be supplemented from the zeolite included in the shift catalyst, and the shift reaction activity can be prevented from being reduced due to the lack of water. By sufficiently securing the activity of the shift reaction, it is possible to stably perform the operation of supplying the hydrogen-rich gas with a sufficiently reduced carbon monoxide concentration to the CO selective oxidation unit 38 side, and to further improve the performance of the fuel cell 40. Can be secured.
[0053]
Further, in the fuel cell device 10 shown in FIG. 1, as described above, the water required for the shift reaction is supplied through the evaporator 34 together with the water required for the steam reforming reaction. A steam generator similar to the above may be provided in the shift unit 20, and the steam may be supplied to the shift unit 20 by this steam generator. Even in such a configuration, the above-mentioned effect due to the fact that the shift catalyst includes zeolite can be sufficiently obtained.
[0054]
  In this way, if the shift unit 20 is provided with a steam generator, the amount of steam required for the shift reaction can be adjusted independently of the amount of steam required for the steam reforming reaction. When the amount of water vapor is insufficient when the reaction proceeds, the necessary water vapor can be supplied to the shift unit 20 by the water vapor generator. However, a steam generator that vaporizes water by heating does not necessarily have sufficient response to generate a desired amount of steam. For example, when the load connected to the fuel cell 40 suddenly increases and the amount of hydrogen-rich gas generated by the reformer 36 increases suddenly, the amount of water vapor to be supplied to the shift unit 20 increases. Also in this case, it takes a predetermined time until the amount of water vaporized is increased and the amount of water vapor actually supplied to the shift unit 20 is sufficiently increased, and the amount of water vapor is temporarily insufficient in the shift unit 20. There are cases. Even in this case,the aboveBy applying the shift catalyst, it is possible to supplement the water required for the shift reaction from the zeolite provided in the shift catalyst, and it is possible to prevent the shift reaction from being reduced due to the lack of water.
[0055]
In addition, the operation | movement in which a zeolite takes in and discharge | releases crystal water depends on ambient gas pressure, water vapor partial pressure, and temperature. Further, heat is generated when the zeolite takes in the crystal water, and heat is absorbed when the crystal water is released. As described above, the inside of the shift unit 20 is maintained at a predetermined temperature suitable for the shift reaction, and since the shift reaction is an exothermic reaction, the partial pressure of water vapor in the hydrogen-rich gas supplied to the shift unit is low. When it decreases, that is, when the water vapor partial pressure around the zeolite included in the shift catalyst decreases, crystal water is easily released from the zeolite.
[0056]
Since the shift catalyst provided in the shift unit 20 is formed by mixing powdered catalyst metal and zeolite, the catalyst metal and zeolite are located close to each other microscopically. Therefore, the water released from the zeolite is quickly supplied onto the catalyst metal, the water vapor partial pressure around the catalyst metal can always be kept sufficiently high, and the shift reaction can proceed efficiently. As described above, since the partial pressure of water vapor around the catalyst metal can always be maintained sufficiently and the activity of the shift reaction can be maintained high, the shift unit 20 can be further downsized.
[0057]
  In addition,Shift unit 20Then, although it was decided to use a Cu-Zn catalyst as a catalyst metal with which a shift catalyst is provided, as mentioned above, it is good also as using another kind of catalyst metal. Use any catalytic metalTheAlso when promoting the shift reaction, TouchBy making the medium metal and zeolite coexist, it is possible to prevent the lack of water vapor when the shift reaction proceeds.ConstitutionThe same effect can be obtained.
[0058]
  Also, aboveShift unit 20In this example, the honeycomb is used as the carrier for supporting the catalyst metal, but a carrier having a different shape may be used. It is only necessary to hold both the catalyst metal and the zeolite so that they are sufficiently close to each other so that the crystal water released from the zeolite, which is a water vapor-adsorbing substance, is quickly supplied onto the catalyst metal.
[0059]
(3) Shift catalystExamples about:
  the aboveShift unit 20Then, the catalyst metal powder and the zeolite powder are mixed to form the shift catalyst, but different configurations may be used. Examples relating to the shift catalyst in which the catalyst metal layer and the zeolite layer are separately formed are shown below.
[0060]
  Figure 3, RealFIG. 4 is an explanatory diagram showing the state of the shift catalyst of the example., RealIt is process drawing showing the manufacturing process of the shift catalyst of an Example.. FruitThe example shift catalyst is, Configuration already describedIs provided in a shift unit 20 provided in the fuel cell device 10, and includes a catalyst metal layer formed on a predetermined carrier and a zeolite layer formed thereon. Here, as the carrier supporting the shift catalyst,Configuration already describedAlthough the honeycomb is used in the same manner as described above, a carrier having a different shape may be used. Also, RealExample shift catalyst,As already mentionedSimilar to the shift catalyst, the Cu—Zn catalyst is provided as the catalyst metal, but various catalyst metals can be selected. When a hydrogen rich gas containing water vapor is supplied from the reformer 36 to the shift unit 20 having such a shift catalyst, the hydrogen rich gas passes through the zeolite layer which is the surface of the shift catalyst while passing through the zeolite layer. It diffuses in and reaches the catalytic metal layer provided under the zeolite layer and is subjected to the shift reaction.
[0061]
  like thisFruitThe manufacturing method of the shift catalyst of an Example is demonstrated based on FIG. First, a Cu—Zn catalyst that is a catalytic metal is prepared (step S200). This process is shown in FIG.TThis is the same process as step S100 in the manufacturing process of the catalyst. Next, the pulverized Cu—Zn catalyst prepared in step S200 is mixed with a binder such as alumina slurry (step S210), and this is applied to the surface of the carrier to form a catalyst metal layer (step S220).
[0062]
Next, the zeolite powder, the urethane powder, and the binder are mixed (step S230), and applied to the catalyst metal layer formed in step S220 to form a zeolite layer (step S240). When the catalytic metal layer and the zeolite layer are formed on the support, they are dried and calcined (step S250) to complete the shift catalyst.
[0063]
Here, drying was performed at 150 ° C. for 1 hour, and baking was performed at 500 ° C. for 1 hour. In this example, the urethane powder was mixed with the zeolite powder when forming the zeolite layer, but this urethane powder is removed from the zeolite layer by being melted by heat in the firing step. Therefore, the zeolite layer provided in the completed shift catalyst becomes a porous body in which voids are formed at the place where the urethane powder was present before firing.
[0064]
  Configured as aboveFruitAccording to the shift catalyst of the example, since the zeolite is provided with the catalyst metal,Configuration already describedSimilarly, when the partial pressure of water vapor in the gas supplied to the shift unit 20 is low, the shift reaction can proceed using crystallization water released from the zeolite, and the amount of water vapor is insufficient. As a result, the activity of the shift reaction can be prevented from decreasing. In addition, since the zeolite layer is formed in contact with the catalyst metal layer, the crystal water released from the zeolite is immediately supplied to the catalyst metal, and the effect of maintaining the activity of the shift reaction can be sufficiently obtained.
[0065]
Furthermore, since the shift catalyst of the present embodiment forms a zeolite layer on the surface in contact with the gas passing through the honeycomb surface provided in the shift portion 20, according to the water vapor partial pressure in the gas passing through the shift portion 20, Zeolite quickly adsorbs or releases water vapor. Therefore, when the partial pressure of water vapor in the gas passing through the shift unit 20 decreases, the crystal water can be released with high responsiveness to make up for the water required for the shift reaction. Moreover, since the zeolite layer provided on the surface of the shift catalyst of this example is formed as a porous body (high porosity), the gas can easily diffuse in the zeolite layer. Accordingly, a sufficient amount of gas can be provided for the shift reaction that proceeds on the catalyst metal, and hydrogen and carbon dioxide generated by the shift reaction can be quickly removed from the catalyst surface, so that the activity of the shift reaction can be sufficiently increased. Can be kept high.
[0066]
In this embodiment, in order to make the zeolite layer porous, the urethane resin is used as the material to be mixed with the zeolite powder when forming the zeolite layer. However, a different material may be used. Other types of resins such as phenol resins may be used. If a substance that can be removed from the zeolite layer by melting at a predetermined high temperature, such as a urethane resin, is used, the porous zeolite layer It can be formed easily.
[0067]
  UpRealIn the examples, the zeolite layer is formed so as to cover the catalyst metal layer, but it is not always necessary to cover the entire catalyst metal layer. If a sufficient amount of zeolite is present on the catalyst metal layer, the same thing is necessary. An effect can be obtained. FIG., RealIt is explanatory drawing showing the structure of the shift catalyst as a modification of an Example.
[0068]
  In the shift catalyst shown in FIG., RealThe catalyst metal layer is formed on the support as in the examples. However, the zeolite included in the shift catalyst is not layered to cover the catalyst metal layer but is dispersed in islands on the catalyst metal layer. Exists. To manufacture such a shift catalyst, first, as shown in FIG.FruitA catalytic metal layer is formed on the support by the same processes as steps S200 to S220 of the manufacturing process of the shift catalyst of the example. Next, instead of step S230, a process of mixing zeolite powder and a binder such as alumina slurry is performed. At this time, the slurry is sufficiently diluted and mixed using a liquid such as water or an organic liquid. The concentration of zeolite powder and binder in the slurry is made sufficiently low. When the slurry thus obtained is applied onto the catalyst metal layer formed on the support and dried, as shown in FIG. 5, the zeolite is present in the form of islands dispersed on the catalyst metal layer. A shift catalyst can be produced. Here, when the surface of the catalyst metal layer formed by applying the catalyst metal mixed with the binder on the support has irregularities, the zeolite is mainly held in the recesses as shown in FIG. The The density at which the zeolite is dispersed on the catalytic metal layer can be adjusted to a desired state by the concentration of the slurry obtained by mixing the binder and the zeolite and the amount of the slurry applied on the catalytic metal layer.
[0069]
  Such as shown in FIG.FruitAccording to the shift catalyst as a modified example of the example, since the zeolite which is a water vapor adsorbing substance is present adjacent to the catalyst metal as in the above-described examples, the activity of the shift reaction is caused by the lack of water vapor. The effect which prevents that falls may be acquired. Further, since the zeolite is dispersed on the catalytic metal layer, carbon monoxide and water vapor used for the shift reaction can more easily reach the catalytic metal and are generated by the shift reaction. Hydrogen and carbon dioxide can also more easily diffuse from the catalytic metal into the hydrogen rich gas.
[0070]
  FIG.As a reference exampleIt is explanatory drawing showing the structure of this shift catalyst.Reference exampleThe shift catalyst is, RealContrary to the shift catalyst of the example, a catalytic metal layer is provided on the zeolite layer formed on the support. In order to produce such a shift catalyst, first, a mixture of zeolite powder and binder is applied on a support to form a zeolite layer, and then the catalyst metal prepared in the same manner as in the above-described examples is used. A mixture of powder and binder may be applied onto the zeolite layer to form a catalytic metal layer.
[0071]
  like thisReference exampleSimilarly to the shift catalyst of the above-described embodiment, the shift catalyst has a zeolite which is a water vapor adsorbing substance adjacent to the catalyst metal, so that the activity of the shift reaction is reduced due to the lack of water vapor. The effect which prevents that can be acquired. Also,Reference exampleIn this shift catalyst, since the catalytic metal layer is formed on the surface side of the shift catalyst, the carbon monoxide and water vapor used for the shift reaction are not prevented from reaching the catalytic metal.
[0072]
In addition, although the shift catalyst of each Example mentioned above was equipped with zeolite as a substance which can adsorb | suck water vapor | steam and can discharge | release the adsorbed water vapor | steam, this zeolite is not only natural zeolite but coal. Synthetic zeolite artificially synthesized from ash or the like may be used. Moreover, in the shift catalyst of the Example mentioned above, although the zeolite layer was formed on the support | carrier, it is good also as a support | carrier comprising a zeolite. Any structure may be used as long as the zeolite exists sufficiently close to the catalyst metal and the crystal water released from the zeolite can be used in a shift reaction that proceeds on the catalyst metal.
[0073]
Further, a substance other than zeolite may be used as the water vapor adsorbing substance provided in the shift catalyst. The same effect can be obtained as long as it is a substance that can adsorb and release water vapor according to the amount of water vapor in the gas supplied in the environment within the shift section. In particular, zeolite retains water molecules as crystal water in the pores of a three-dimensional network structure, so that it can adsorb water vapor much more strongly than simple physical adsorption, and can easily crystallize at a predetermined high temperature. Since water is released, it is excellent as a water vapor adsorbing substance provided in the shift catalyst of the present invention.
[0074]
In the fuel cell device 10 of the above-described embodiment, gasoline is used as the fuel for the reforming reaction, but different hydrocarbon fuels may be used. In addition to hydrocarbons such as gasoline and natural gas, alcohols such as methanol, ethers, or aldehydes that can generate a hydrogen-rich gas containing carbon monoxide by proceeding with a reforming reaction at a predetermined high temperature If it is good. Such various hydrocarbon compounds can be used as fuel in the fuel cell device similar to the fuel cell device 10, and in the hydrogen rich gas obtained by reforming the fuel by the shift unit including the shift catalyst of the present invention. The operation of reducing the carbon monoxide concentration can be performed stably.
[0075]
Further, in the fuel cell device 10 of the present invention, the hydrogen rich gas whose carbon monoxide concentration is reduced using the shift catalyst of the present invention is supplied to the fuel cell 40 which is a solid polymer fuel cell. It is good also as supplying to the fuel cell of a kind. In the case of a fuel cell that is poisoned with carbon monoxide, hydrogen rich gas with a reduced carbon monoxide concentration is supplied as a fuel gas using the shift catalyst of the present invention, thereby suppressing catalyst poisoning. The effect of ensuring performance can be obtained.
[0076]
Moreover, it is good also as supplying the hydrogen containing gas which reduced the carbon monoxide density | concentration in gas by advancing a shift reaction using the shift catalyst of this invention with respect to the apparatus which consumes hydrogen other than a fuel cell. . Even in such a case, when the amount of water vapor (water vapor partial pressure) in the gas subjected to the shift reaction fluctuates, the effect of preventing the activity of the shift reaction from being reduced due to the lack of water vapor is prevented. Obtainable. The shift catalyst of the present invention can be applied to various apparatuses for proceeding with the shift reaction. When the amount of water vapor used for the shift reaction is insufficient, a predetermined amount of water is compensated by supplementing water from the water vapor adsorbing substance. An effect can be obtained.
[0077]
Although the embodiments of the present invention have been described above, the present invention is not limited to these embodiments, and it is needless to say that the present invention can be implemented in various modes without departing from the gist of the present invention.
[Brief description of the drawings]
[Figure 1]Burning1 is an explanatory diagram schematically showing the overall configuration of a fuel cell device 10. FIG.
FIG. 2 is an explanatory diagram showing a manufacturing process of a shift catalyst provided in the shift unit 20;
[Fig. 3]FruitIt is explanatory drawing showing the mode of the shift catalyst of an Example.
[Fig. 4]FruitIt is process drawing showing the manufacturing process of the shift catalyst of an Example.
[Figure 5]FruitIt is explanatory drawing showing the mode of the shift catalyst as a modification of an Example.
[Fig. 6]Reference exampleIt is explanatory drawing showing the mode of this shift catalyst.
[Explanation of symbols]
    10 ... Fuel cell device
    20 ... Shift section
    30 ... gasoline tank
    32 ... Water tank
    33 ... desulfurizer
    34 ... Shift section
    34 ... Evaporator
    36 ... reformer
    38 ... CO selective oxidation part
    40 ... Fuel cell
    42 ... Blower
    43 ... Oxidizing gas flow path
    50 ... heating unit
    52, 53, 54, 58 ... Blower
    56, 57, 58 ... pump
    60 ... Control unit
    62 ... I / O port
    64 ... CPU
    66 ... ROM
    68 ... RAM
    70 ... Fuel flow path
    71 ... Branch
    72 ... Water flow path
    73 ... Fuel flow path
    74 ... Fuel gas flow path
    75 ... Gas flow path
    76 ... Flow path
    78 ... Fuel gas flow path
    79 ... Fuel discharge passage

Claims (8)

Prior to supplying a hydrogen rich gas as a fuel gas to a fuel cell by receiving a supply of a hydrogen rich gas containing carbon monoxide and promoting a shift reaction that generates hydrogen and carbon dioxide from carbon monoxide and water vapor. A shift reaction catalyst for a fuel cell that reduces the concentration of carbon monoxide in the hydrogen-rich gas ,
A catalyst layer comprising a catalyst metal having an activity of promoting the shift reaction;
A water vapor adsorbing portion provided with at least a part of the area on the catalyst layer, and comprising a water vapor adsorbing substance capable of adsorbing water vapor;
The water vapor adsorbing substance is in an equilibrium state in which water vapor is not exchanged with the surroundings under a predetermined condition, and when the ambient water vapor partial pressure is higher than the ambient water vapor partial pressure in the equilibrium state. An adsorption state in which water vapor is adsorbed and a discharge state in which water vapor is released when the surrounding water vapor partial pressure is lower than the surrounding water vapor partial pressure in the equilibrium state.
Shift reaction catalyst for fuel cells . The shift reaction catalyst for a fuel cell according to claim 1, wherein the water vapor adsorption part is present in a dispersed state on the catalyst layer. The shift reaction catalyst for a fuel cell according to claim 1, wherein the water vapor adsorption part is formed to be porous. The shift reaction catalyst for a fuel cell according to any one of claims 1 to 3, wherein the water vapor adsorbing substance is zeolite. To obtain a fuel gas supplied to the fuel cell, a carbon monoxide concentration reduction method for reducing the carbon monoxide concentration of the hydrogen-rich gas containing carbon monoxide,
(A) Using a shift reaction catalyst that promotes a shift reaction that generates hydrogen and carbon dioxide from carbon monoxide and water vapor, the water vapor supplied onto the shift reaction catalyst, and the above-mentioned water supplied onto the shift reaction catalyst by advancing the shift reaction between carbon monoxide hydrogen-rich gas, comprising the step of reducing the concentration of carbon monoxide,
The shift reaction catalyst includes a catalyst layer including a catalyst metal having an activity of promoting the shift reaction, and a water vapor adsorbing substance provided in at least a part of the catalyst layer and capable of adsorbing water vapor. And
In the step (a), the water vapor adsorbing substance is used in an equilibrium state in which water vapor is not substantially exchanged with the surroundings, an adsorption state in which the water vapor is adsorbed, and a reduction in the water vapor partial pressure. The carbon monoxide concentration reducing method is characterized in that it takes one of a release state in which water vapor is released and used for the shift reaction. The carbon monoxide concentration reducing method according to claim 5, wherein the water vapor adsorbing substance is zeolite. To obtain a fuel gas supplied to the fuel cell, a carbon monoxide concentration reduction apparatus for reducing the carbon monoxide concentration of the hydrogen-rich gas containing carbon monoxide,
A shift unit including a shift reaction catalyst that promotes a shift reaction that generates hydrogen and carbon dioxide from carbon monoxide and water vapor;
The hydrogen-rich gas and steam to carbon monoxide, the so subjected to shift the shift reaction proceeding on catalyst, and a supply means for supplying to said shift unit,
5. The carbon monoxide concentration reducing device according to claim 1, wherein the shift reaction catalyst is a shift reaction catalyst for a fuel cell according to claim 1. A fuel cell device comprising a fuel cell that receives a fuel gas containing hydrogen and an oxidizing gas containing oxygen and obtains an electromotive force by an electrochemical reaction,
A reformer that reforms hydrocarbon fuel to produce hydrogen-rich gas;
A shift reaction catalyst that promotes a shift reaction that generates hydrogen and carbon dioxide from carbon monoxide and water vapor; the supply of the hydrogen-rich gas from the reformer; and the carbon monoxide contained in the hydrogen-rich gas; A shift unit for reducing the carbon monoxide concentration in the hydrogen-rich gas by causing the shift reaction to proceed with water vapor supplied onto the shift reaction catalyst;
Supply means for supplying the hydrogen-rich gas having a reduced carbon monoxide concentration in the shift unit as the fuel gas to the fuel cell;
The fuel cell device according to claim 1, wherein the shift reaction catalyst is a shift reaction catalyst for a fuel cell according to claim 1.

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