JP2002128505A - Hydrogen extraction apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To maintain the capability of extracting hydrogen in a stable condition using a hydrogen separation membrane. SOLUTION: In a hydrogen extraction apparatus 10, hydrogen in a gas mixture is extracted to an extraction unit 23 using the selective permeation of a hydrogen separation membrane 12 when a gas mixture containing hydrogen is supplied to a gas mixture unit 20. In the apparatus, the hydrogen separation membrane 12 is formed on a porous material 14, which is heated with the current going through, thus heating the hydrogen separation membrane 12. Since the hydrogen separation membrane 12 is featured by a higher hydrogen permeability at a higher temperature, the hydrogen permeability of the hydrogen separation membrane 12 is ensured by heating the porous material 14 by electricity.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hydrogen extracting apparatus for extracting hydrogen from a mixed gas containing hydrogen.

[0002]

2. Description of the Related Art Conventionally, as an apparatus for extracting hydrogen from a mixed gas containing hydrogen, an apparatus equipped with a hydrogen separation membrane made of palladium or a palladium alloy is known (for example, Japanese Patent Application Laid-Open No. 5-123548, etc.). ). Here, hydrogen is extracted from a hydrogen-containing gas mixture by utilizing the property of the hydrogen separation membrane to selectively permeate hydrogen.

[0003] Such a hydrogen extraction device is used, for example, in a fuel cell device provided with a fuel cell. A fuel cell is a device that is supplied with a fuel gas containing hydrogen and obtains an electromotive force by an electrochemical reaction. As a method for supplying a fuel gas to a fuel cell, a method using a reformed gas (hydrogen-rich gas) obtained by reforming a hydrocarbon-based fuel is known. However, this reformed gas is used as a fuel gas. Prior to this, there has been proposed a configuration in which hydrogen is separated from reformed gas using the hydrogen extraction device and supplied to a fuel cell.

[0004]

However, the hydrogen separation membrane has a property that the hydrogen permeation amount gradually decreases as the temperature decreases. In such a hydrogen extraction device, it has been difficult to stably maintain the performance of extracting hydrogen from the mixed gas. Further, since the hydrogen separation membrane has a property of adsorbing carbon monoxide on its surface, when separating hydrogen from a gas containing carbon monoxide such as the reformed gas, hydrogen There is a problem that the hydrogen permeability gradually decreases due to the adsorption of carbon monoxide on the separation membrane.

[0005] The hydrogen extraction apparatus of the present invention has been made to solve the above-mentioned problems and has an object to maintain the hydrogen permeation performance of the hydrogen separation membrane in a stable state, and has the following configuration.

[0006]

The hydrogen extracting apparatus of the present invention is a hydrogen extracting apparatus for extracting hydrogen from a mixed gas containing hydrogen, and is composed of a porous body that generates heat when energized. A base material, a hydrogen separation membrane formed on the base material and having a property of selectively permeating hydrogen, and an energizing means for passing a current through the base material, and supplying the mixed gas to the hydrogen separation membrane. In addition, when hydrogen is extracted from the mixed gas by the hydrogen separation membrane, the gist is that the hydrogen separation membrane can be heated by energizing the base material by the energization means.

The hydrogen extraction apparatus of the present invention configured as described above supplies a mixed gas containing hydrogen to a hydrogen separation membrane formed on a base material made of a porous material, and the hydrogen separation membrane When hydrogen is extracted from the mixed gas, the hydrogen separation membrane can be heated by energizing the base material that generates heat by energization using the energizing unit.

According to such a hydrogen extraction apparatus, the hydrogen separation membrane can be heated. Therefore, when a hydrogen separation membrane having a property that the hydrogen permeation amount depends on the temperature is used, it is necessary to energize the base material. This makes it possible to sufficiently secure the hydrogen permeability of the hydrogen separation membrane. In addition, the hydrogen separation membrane is formed on a substrate that generates heat, and heat generated in the substrate is quickly transmitted to the hydrogen separation membrane. Can be suppressed. In addition, since the hydrogen separation membrane is heated by causing the base material formed thereon to generate heat, the hydrogen separation membrane is heated. By providing a configuration for heating the hydrogen separation membrane, the size of the hydrogen extraction device does not increase. .

Further, the heat generated in the base material is quickly transmitted to the hydrogen separation membrane. For example, even when the hydrogen extraction device is started, the hydrogen separation membrane can be sufficiently supplied immediately by energizing the base material. It is possible to raise the temperature of the hydrogen separation membrane to a temperature that shows a high hydrogen permeability, and it is possible to operate the hydrogen extraction device more quickly. In the above configuration, the operation of supplying the mixed gas to the hydrogen separation membrane may be such that the mixed gas is directly supplied to the hydrogen separation membrane formed on the base material or the mixed gas is supplied to the base material side. Then, the mixed gas may be supplied to the hydrogen separation membrane via the base material. That is, an operation may be performed in which hydrogen in the mixed gas reaching one surface of the hydrogen separation membrane is separated by the hydrogen separation membrane to the other surface.

[0010] In the hydrogen extraction apparatus of the present invention, a sensor for detecting the temperature of the hydrogen separation membrane, and the energizing means for flowing an electric current to the base material when the temperature detected by the sensor is lower than a predetermined temperature. May be further provided with control means for controlling

With such a configuration, when the temperature of the hydrogen separation membrane is equal to or lower than a predetermined temperature, an electric current is applied to the base material to generate heat, thereby heating the hydrogen separation membrane. By heating the hydrogen separation membrane in this way, the hydrogen permeability of the hydrogen separation membrane can be ensured regardless of other conditions such as the ambient temperature, and the performance of the hydrogen extraction device can be ensured. Here, the sensor does not necessarily need to directly detect the temperature of the hydrogen separation membrane, and may detect the temperature of another portion reflecting the temperature of the hydrogen separation membrane. It suffices if the state of energization to the base material can be controlled based on the above.

In the hydrogen extraction device of the present invention, the hydrogen separation membrane may be made of palladium or a metal containing palladium. The hydrogen separation membrane made of palladium or a metal containing palladium has a property that the higher the temperature, the higher the hydrogen permeability, and by applying the present invention, it is possible to sufficiently obtain the effects described above. it can.

[0013] In such a hydrogen extraction device, the predetermined temperature may be 300 ° C. With such a structure, hydrogen embrittlement of the hydrogen separation membrane (deterioration of hydrogen separation membrane due to retention or discharge of hydrogen in the molecular structure of the hydrogen separation membrane) is prevented. be able to.

[0014] In the hydrogen extraction device of the present invention, the porous body constituting the base material may include a conductive ceramic.

In such a hydrogen extraction apparatus,
The conductive ceramic may include silicon carbide.

In the hydrogen extraction apparatus according to the present invention, a recovery gas is supplied to the hydrogen separation membrane, instead of the mixed gas, a recovery gas acting to remove impurities adsorbed on the hydrogen separation membrane from the hydrogen separation membrane. Further comprising gas supply means,
When the recovery gas is supplied to the hydrogen separation membrane using the recovery gas supply unit, the hydrogen separation membrane may be heated by energizing the base using the current supply unit.

With this configuration, when the recovery gas is supplied to the hydrogen separation membrane, the temperature of the hydrogen separation membrane can be increased by supplying electricity to the base material. It is possible to raise the temperature of the hydrogen separation membrane to a temperature sufficient to perform an operation of removing impurities adsorbed thereon from the hydrogen separation membrane. Therefore, the impurities adsorbed on the hydrogen separation membrane are removed,
The operation of restoring the hydrogen permeability of the hydrogen separation membrane can be favorably performed. As an operation of removing the impurities adsorbed on the hydrogen separation membrane, for example, a method of causing a chemical reaction to proceed between the impurities and a substance contained in the recovery gas can be given. In such a case, by energizing the base material to raise the temperature of the hydrogen separation membrane, it is possible to sufficiently secure the activity of the chemical reaction.

Further, in the hydrogen extraction apparatus of this embodiment,
The hydrogen separation membrane, in place of the mixed gas, further comprises a stop-time gas supply means for supplying a gas substantially containing no hydrogen, when it is determined to perform the operation of stopping the hydrogen extraction device, By supplying the gas not containing hydrogen to the hydrogen separation membrane using a gas supply unit at the time of stoppage, and supplying electricity to the base material using the current supply unit, the hydrogen separation membrane may be heated. Good.

With such a configuration, when it is determined that the operation of stopping the hydrogen extraction device is performed, the temperature of the hydrogen separation membrane can be increased by energizing the base material. By supplying a gas substantially containing no hydrogen to the hydrogen separation membrane instead of the above-mentioned mixed gas, it is possible to prevent the hydrogen from remaining in the hydrogen separation membrane. This can prevent hydrogen embrittlement of the hydrogen separation membrane.

The hydrogen extraction method of the present invention is a hydrogen extraction method for extracting hydrogen from a mixed gas containing hydrogen, which is formed on a porous base material and has a property of selectively permeating hydrogen. When extracting hydrogen from the mixed gas using the hydrogen separation membrane having the above, the gist is to heat the hydrogen separation membrane by causing an electric current to flow through the base material to generate heat in the base material.

According to such a hydrogen extraction method, the hydrogen separation membrane can be heated. Therefore, when using a hydrogen separation membrane having a property that the hydrogen permeation amount depends on the temperature, it is necessary to energize the base material. This makes it possible to sufficiently secure the hydrogen permeability of the hydrogen separation membrane. In addition, the hydrogen separation membrane is formed on a substrate that generates heat, and heat generated in the substrate is quickly transmitted to the hydrogen separation membrane. Can be suppressed. In addition, since the hydrogen separation membrane is heated by causing the base material formed thereon to generate heat, the hydrogen separation membrane is heated. By providing a configuration for heating the hydrogen separation membrane, the size of the hydrogen extraction device does not increase. .

[0022] In the hydrogen extraction method of the present invention, the energization state to the substrate may be changed according to the temperature of the hydrogen separation membrane. With such a configuration, the hydrogen separation membrane can be heated to a desired temperature regardless of other conditions such as the ambient temperature, and the hydrogen permeability of the hydrogen separation membrane can be secured. Changing the state of energization to the base material may be in various forms, such as switching on / off of energization, changing the amount of current flowing to the base material, and the like.
The substrate may be heated by energization to control the temperature of the hydrogen separation membrane in a desired state.

The fuel cell device according to the present invention is a fuel cell device provided with a fuel cell which obtains an electromotive force by an electrochemical reaction using hydrogen, wherein the fuel cell device reforms a hydrocarbon-based fuel to generate a hydrogen-containing gas. A hydrogen extraction device according to any one of claims 1 to 8, wherein the hydrogen extraction device receives the supply of the hydrogen-containing gas from the reformer and extracts hydrogen from the hydrogen-containing gas. The gist of the invention is to provide a supply means for supplying hydrogen extracted by the hydrogen extraction device to the fuel cell.

According to such a fuel cell device, the hydrogen permeability of the hydrogen separation membrane can be ensured by heating the hydrogen separation membrane provided in the hydrogen extraction device, so that the supply of hydrogen to the fuel cell can be stabilized. Can be done.

[0025]

DESCRIPTION OF THE PREFERRED EMBODIMENTS 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) Configuration of hydrogen extraction device 10 (2) Properties of hydrogen separation membrane 12 (3) Configuration of fuel cell device 30 including hydrogen extraction device 10

(1) Configuration of hydrogen extraction device 10: FIG.
It is an explanatory view showing the outline of the composition of hydrogen extraction device 10 of this example. FIG. 1 schematically illustrates a cross section of the hydrogen extraction device 10. The hydrogen extraction device 10 includes a hydrogen separation membrane 1 made of a metal having a property of selectively permeating hydrogen.
2, a porous substrate 14 on which a hydrogen separation membrane 12 is formed
And a power supply 26 connected to the porous substrate 14 and supplying power when the porous substrate 14 is energized, and a porous substrate provided in a circuit connecting the porous substrate 14 and the power supply 26. Lumber 14
The main components are a switch 28 for turning on and off the power supply to the temperature, a temperature sensor 27 for detecting the surface temperature of the hydrogen separation membrane 12, and a control unit 29 for controlling the state of power supply to the porous substrate 14.

The hydrogen separation membrane 12 is a membrane made of a metal having a property of selectively permeating hydrogen as described above (hereinafter, referred to as a hydrogen separation metal). The hydrogen separation metal may be palladium or palladium. It can be selected from metals containing palladium, such as alloys. The porous substrate 14 is formed as a porous body through which gas can pass, and is formed of a conductive material having a predetermined resistance value. As will be described later, the hydrogen extraction device 10 of the present embodiment generates heat by energizing the porous base material 14 and raises the temperature of the hydrogen separation membrane 12 to a temperature at which the hydrogen permeability of the hydrogen separation membrane 12 can be sufficiently ensured. Is heated, the material constituting the porous substrate 14 has sufficient resistance to heat the hydrogen separation membrane 12 in order to secure hydrogen permeability, It is selected from materials having. In this embodiment, the porous substrate 14
Is formed of silicon carbide which is a conductive ceramic. Various conductive ceramics are known as ceramic heating elements. Of these, any of these, when energized, generates heat that can sufficiently raise the temperature of the hydrogen separation membrane formed on the surface. The above porous substrate 1
4 can be used as a material. Further, instead of forming the entirety of the porous base material 14 with conductive ceramic, conductive ceramic may be provided at a predetermined ratio, so that desired heat generation may be obtained at the time of energization. For example, the porous substrate 14 may be formed by laminating a layer made of the conductive ceramic and a layer made of an insulating ceramic having no conductivity. Alternatively, in addition to such a conductive ceramic, the porous substrate 14 may be formed of a metal exhibiting a sufficient resistance value, for example, a nickel-chromium alloy or the like.

Here, as the hydrogen separation membrane 12 provided on the porous substrate 14, various configurations can be applied.
The hydrogen separation membrane 12 can be formed, for example, by coating the porous substrate 14 by plating, chemical vapor deposition (CVD), physical vapor deposition (PVD), or the like. Alternatively, it may be formed by supporting the hydrogen separation metal in the pores of the porous substrate 14. Examples of the method for supporting the hydrogen separation metal include, for example, an impregnation support method in which the porous substrate 14 is immersed in a solution containing the hydrogen separation metal, and a paste in which the hydrogen separation metal is mixed in an organic solvent. For example, a method of applying to the surface of No. 14 and firing it can be used.

The control section 29 controls the state of energization of the porous substrate 14 by driving the switch 28.
The control unit 29 is a one-chip microcomputer including a CPU, a RAM, a ROM, and the like, and the CPU performs control processing according to a program recorded in the ROM. The control unit 29 is connected to the temperature sensor 27 shown in FIG.
When it is determined that the temperature of the hydrogen separation membrane 12 has become equal to or lower than a predetermined temperature based on the detection signal input from the switch 28, the switch 28 is turned on and a predetermined amount of current flows through the porous Generate heat. The hydrogen separation membrane 12
When it is determined that the temperature of the
The switch 28 is turned off to stop energizing the porous substrate 14.

On the porous substrate 14 side with the hydrogen separation membrane 12 and the porous substrate 14 interposed therebetween, a mixed gas portion 20 as a gas flow path is formed. Is
A mixed gas containing hydrogen is supplied from the inlet 21.
On the side of the hydrogen separation membrane 12 with the hydrogen separation membrane 12 and the porous substrate 14 interposed therebetween, an extraction portion 23 as a gas flow path is formed. Hydrogen in the mixed gas permeates through the hydrogen separation membrane 12 and flows into the extraction unit 23 from the mixed gas unit 20 side (see FIG. 1). The hydrogen extracted from the mixed gas to the separation unit 23 side by the hydrogen separation membrane 12 is discharged to the outside of the hydrogen extraction device 10 through the discharge port 25. The residual gas after the extraction of hydrogen by the hydrogen separation membrane 12 is:
It is discharged out of the hydrogen extraction device 10 through the discharge port 22.
Of course, in the hydrogen extraction device 10 shown in FIG. 1, the mixed gas section 20 and the extraction section 23 may be provided in reverse.

As described above, in the hydrogen extraction apparatus 10 according to the present embodiment, hydrogen is extracted from the hydrogen-containing mixed gas by utilizing the property of the hydrogen separation membrane 12 to selectively permeate hydrogen, and the hydrogen is discharged to the outlet. 25. Here, the speed at which hydrogen permeates the hydrogen separation membrane 12 depends on the mixed gas section 20 and the extraction section 23 provided with the hydrogen separation membrane 12 interposed therebetween.
And the hydrogen concentration difference between That is, the extraction unit 23
The lower the hydrogen concentration in the inside, the higher the efficiency of hydrogen permeation to the extraction unit 23 side. Therefore, in order to maintain the hydrogen concentration on the extraction unit 23 side at a sufficiently low state, an appropriate gas (hereinafter, referred to as a purge gas) is supplied to the extraction unit 23 side through the inflow port 24 to remove the hydrogen separation membrane 12. The configuration may be such that the permeated hydrogen is discharged to the outside from the discharge port 25 by the purge gas. As the purge gas, a gas that does not cause inconvenience in the subsequent process using hydrogen extracted from the hydrogen extraction device 10 and that has a sufficiently low hydrogen concentration may be appropriately selected according to the purpose.

In the hydrogen extraction apparatus 10 shown in FIG. 1, the temperature sensor 27 is provided on the hydrogen separation membrane 12, but may have a different configuration. That is, if a value reflecting the temperature of the hydrogen separation membrane 12 can be detected, a configuration other than directly detecting the temperature of the hydrogen separation membrane 12 on the hydrogen separation membrane 12 may be adopted.

(2) Properties of Hydrogen Separation Membrane 12: In the hydrogen extraction apparatus 10 of the present embodiment, a current is applied to the porous substrate 14 to generate heat, and the hydrogen extraction membrane 10 is provided on the porous substrate 14. The structure of securing hydrogen permeability in the hydrogen separation membrane 12 by heating the hydrogen separation membrane 12 will be described below. The properties of the hydrogen separation membrane 12 will be described below. FIG.
FIG. 3 is a diagram showing a relationship between hydrogen permeability and temperature in a hydrogen separation membrane.

As shown in FIG. 2, the hydrogen separation membrane shows higher hydrogen permeability as the temperature increases. FIG. 2 shows the properties of a hydrogen separation membrane made of palladium, but other types of hydrogen separation membranes containing palladium, such as a hydrogen separation membrane made of a palladium-silver alloy, show similar properties. Therefore, in the hydrogen extraction apparatus 10 including such a hydrogen separation membrane, when it is determined that the temperature of the hydrogen separation membrane has decreased, the porous base material 14 is energized to generate heat, so that the hydrogen separation membrane 12 Can improve hydrogen permeability.

In FIG. 2, the relationship between the temperature and the amount of permeated hydrogen is shown over a temperature range of 300 to 500 ° C.
The tendency that the amount of hydrogen permeation increases with an increase in temperature is also observed at temperatures below this temperature range or above this temperature range. When controlling the power supply to the porous substrate 14 in order to secure the hydrogen permeation amount of the hydrogen separation membrane, the temperature at which the power supply is performed is controlled by the lower limit of the hydrogen permeation amount required for the hydrogen separation membrane 12, It is set in consideration of the accuracy in controlling the current supply and the energy efficiency of the entire apparatus in order to secure the hydrogen permeation amount based on the temperature. When the temperature of the hydrogen separation membrane 12 is 300 ° C. or lower, hydrogen In the separation membrane 12, the problem of hydrogen embrittlement further arises.

Hydrogen embrittlement means that the hydrogen separation membrane gradually deteriorates when the temperature of the hydrogen separation membrane is not maintained sufficiently high. That is, when the temperature of the hydrogen separation membrane is not high enough, instead of permeating the hydrogen through the hydrogen separation membrane, the hydrogen may remain in the molecular structure constituting the hydrogen separation membrane, or may be discharged once again. In this manner, the entry and exit of hydrogen in the molecular structure of the hydrogen separation membrane means that the molecular structure gradually collapses.
Therefore, in order to maintain the temperature of the hydrogen separation membrane 12 sufficiently high, and to prevent hydrogen embrittlement in the hydrogen separation membrane 12, the reference temperature for starting the energization of the porous substrate 14 is as follows: It is desirable to set the temperature to 300 ° C. or higher.

The lower the temperature, the more strongly the hydrogen separation membrane is poisoned by carbon monoxide. Therefore, the temperature at which the energization of the porous substrate 14 is started depends on the influence of the carbon monoxide poisoning. It is desirable to set in consideration of. FIG.
It is a figure showing the relationship between carbon monoxide poisoning and temperature in a hydrogen separation membrane. Here, in a device similar to the hydrogen extraction device 10, nitrogen gas is used as a purge gas and hydrogen gas is used as a mixed gas, and 5% is used as a mixed gas.
2 shows a state in which the hydrogen permeation amount is compared with the case where a hydrogen gas containing carbon monoxide is used. The “reduction rate of the amount of hydrogen permeation due to carbon monoxide poisoning” shown on the vertical axis is “the amount of hydrogen permeation when a gas containing no carbon monoxide is used as a mixed gas” and “ The ratio of the amount of hydrogen permeation when the contained gas is used as a mixed gas. " As shown in FIG. 3, the higher the temperature, the smaller the effect of the decrease in the amount of permeated hydrogen caused by carbon monoxide. Therefore, in order to suppress a decrease in the amount of hydrogen permeation due to carbon monoxide, it is only necessary to set a higher temperature as a reference for starting energization of the porous base material 14, In the hydrogen extraction device 10 of the present embodiment, the reference temperature is set to 500 ° C.

Excessive heating of the hydrogen separation membrane 12 by causing the porous substrate 14 to generate heat may cause inconvenience such as deterioration of the members constituting the hydrogen extraction device 10. In addition, there is a possibility that the energy efficiency of the entire apparatus may be reduced. Therefore, in consideration of such inconveniences, the temperature at which hydrogen is permeated with sufficient efficiency is set as a temperature at which hydrogen is passed through the porous substrate 14 when energizing the porous substrate 14. What is necessary is just to set the upper limit of the film temperature.

The hydrogen extraction apparatus 10 constructed as described above
According to this, the porous substrate 14 on which the hydrogen separation membrane 12 is formed is formed of a conductive material having a predetermined resistance value, and the porous substrate 14 is configured to be able to conduct electricity. The porous substrate 14 is energized to generate heat,
The hydrogen separation membrane 12 can be heated.
Can be sufficiently ensured regardless of the ambient temperature. Further, since the hydrogen separation membrane 12 is formed on the porous base material 14, heat generated by energizing the porous base material 14 can be transmitted to the hydrogen separation membrane 12 without waste, and hydrogen The separation membrane 12 can be heated, and the provision of the means for heating the hydrogen separation membrane 12 does not cause an increase in the size of the hydrogen extraction device 10. Further, as described above, the hydrogen separation membrane 1
2 to maintain the temperature of the hydrogen separation membrane 12 sufficiently high, the hydrogen separation membrane 12 is poisoned with carbon monoxide even if the mixed gas contains carbon monoxide. It is possible to suppress a decrease in transmittance.

Although the structure of the hydrogen extraction device 10 is schematically shown in FIG. 1, the shape of the hydrogen extraction device to which the present invention can be applied is not limited to such a shape, and the structure shown in FIG. Different shapes may be used, such as laminating them as a unit. A similar effect can be obtained if the porous substrate 14 formed of a material having a predetermined resistance can be energized to generate heat and heat the hydrogen separation membrane. In addition, if a hydrogen separation membrane having a property capable of sufficiently securing hydrogen permeability by increasing the temperature is used, even when another type of hydrogen separation membrane is used, the present embodiment is not limited to this. Configuration can be applied.

(2-1) Operation for Restoring Hydrogen Permeability: When operating the hydrogen extraction device 10 for a longer period of time, if carbon monoxide is contained in the mixed gas, the operation is performed as described above. Even if the hydrogen separation membrane 12 is heated in advance, the carbon monoxide poisoning may gradually progress. If the mixed gas supplied to the hydrogen extraction device 10 contains impurities such as carbon and carbon compounds in addition to carbon monoxide, these impurities are also adsorbed on the hydrogen separation membrane 12 and There is a possibility that hydrogen permeability may be reduced.
As in the hydrogen extraction device 10 of the present embodiment, the hydrogen separation membrane 12
In the case of having a configuration for heating the hydrogen, it is possible to perform an operation of restoring the hydrogen permeability (hydrogen separation performance) lowered by the adsorption of these impurities. Hereinafter, such an operation will be described.

To remove the above-mentioned impurities such as carbon monoxide adsorbed on the hydrogen separation membrane 12, the hydrogen extraction device 1
0, the operation of extracting hydrogen is temporarily stopped, the temperature of the hydrogen separation membrane 12 is maintained at a predetermined temperature (for example, a temperature of about 300 to 400 ° C.) by controlling the energization state of the porous base material 14, and the mixed gas is removed. A recovery gas such as an oxygen-containing gas or water vapor may be supplied to the unit 20 instead of the mixed gas. With such a configuration, the hydrogen separation membrane 12
The operation of removing the carbon monoxide and the impurities adsorbed thereon from the hydrogen separation membrane is promoted, and the hydrogen permeability of the hydrogen separation membrane can be restored. For example, when an oxygen-containing gas (air) is supplied as a recovery gas while carbon monoxide is being adsorbed on the hydrogen separation membrane 12, the carbon monoxide adsorbed on the hydrogen separation membrane 12 is oxidized to carbon dioxide. , Together with the recovery gas.

When the hydrogen permeability of the hydrogen separation membrane is reduced, a configuration in which the hydrogen separation membrane is maintained at a predetermined high temperature and an oxygen-containing gas or water vapor is supplied to restore the hydrogen permeability is disclosed in, for example, Japanese Patent Laid-Open Publication JP-A-8-257376 and JP-A-2000-
As disclosed in Japanese Patent Publication No. 140584, the hydrogen extraction apparatus 10 of the present embodiment employs the hydrogen separation membrane 1 by heating the porous substrate 14 which is in direct contact with the hydrogen separation membrane 12.
2 is heated, the decrease in energy efficiency due to the heating can be kept extremely low. Furthermore, by heating the hydrogen separation membrane 12 efficiently as described above, the temperature of the hydrogen separation membrane 12 can be immediately raised to a desired temperature if necessary, and after the operation of restoring the hydrogen permeability is performed. Since the temperature of the hydrogen separation membrane 12 is sufficiently raised, the hydrogen extraction operation can be performed immediately. Further, since the hydrogen separation membrane 12 is heated by generating heat from the porous substrate 14 on which the hydrogen separation membrane 12 is formed, it is not necessary to raise the temperature of the recovery gas in advance, and the recovery gas is heated. Therefore, there is no need to consume energy.

(2-2) Operation for Stopping the Hydrogen Extraction Device 10: As described above, when the temperature of the hydrogen separation membrane 12 is not sufficiently high, hydrogen embrittlement may occur in the hydrogen separation membrane 12. Hereinafter, an operation performed to prevent the hydrogen separation membrane 12 from causing hydrogen embrittlement when the hydrogen extraction device 10 is stopped will be described.

When the supply of the mixed gas to the hydrogen extraction apparatus 10 is stopped when the hydrogen extraction apparatus 10 is stopped, a part of the hydrogen contained in the mixed gas supplied immediately before the stop is turned off.
2 may be retained in the molecular structure constituting hydrogen and cause hydrogen embrittlement. Therefore, when the hydrogen extraction device 10 is stopped, while maintaining the hydrogen separation membrane 12 at a sufficiently high temperature, a gas containing substantially no hydrogen (a gas having a sufficiently low hydrogen concentration) is supplied to the mixed gas portion 20. And replace the inside of the mixed gas section 20 with the above-mentioned gas containing no hydrogen,
It is desirable that hydrogen does not stay in the hydrogen separation membrane 12.

According to the hydrogen extraction apparatus 10 of the present embodiment, when supplying the gas containing no hydrogen to the mixed gas section 20, the hydrogen separation membrane 12 is heated by energizing the porous substrate 14. Therefore, when the inside of the mixed gas section 20 is replaced with a gas containing no hydrogen,
Hydrogen flowing into the hydrogen separation membrane 12 from the mixed gas section 20 side quickly permeates through the hydrogen separation membrane 12 and is discharged to the extraction section 23 side. Therefore, when the inside of the mixed gas portion 20 is replaced with a gas containing no hydrogen, the hydrogen separation membrane 12 is in a state where hydrogen does not stay inside, and the hydrogen separation membrane 12 is stopped when the hydrogen extraction device 10 is stopped. Hydrogen embrittlement can be prevented from being caused. The heating of the hydrogen separation membrane 12 is performed by the hydrogen separation membrane 1.
Since the heating is performed by heating the porous base material 14 that is in direct contact with the fuel cell 2, the hydrogen separation membrane 12 can be heated with high efficiency, and the apparatus is increased in size by providing a configuration for heating the hydrogen separation membrane 12. I won't.

(3) Configuration of the fuel cell device 30 including the hydrogen extraction device 10: The hydrogen extraction device 10 of the above embodiment can be used to supply hydrogen to various devices that consume hydrogen. However, the following describes the hydrogen extraction device 10
The configuration applied to the fuel cell device will be described, and the effect of the hydrogen extraction device 10 will be described according to the configuration applied to the fuel cell device. FIG. 4 is an explanatory diagram schematically showing the configuration of a fuel cell device 30 which is an example of a fuel cell device provided with the hydrogen extraction device 10 of the above embodiment. The fuel cell device 30 includes a fuel tank 32 for storing reformed fuel, a water tank 34 for storing water, an evaporator / mixer 36 for raising and mixing the temperature of reformed fuel and water, and a reformer for accelerating a reforming reaction. Reformer 38 with catalyst, hydrogen extraction device 1
0, a fuel cell 40, and a blower 42 as main components.

The reformed fuel stored in the fuel tank 32 is used for a reforming reaction that proceeds in a reformer 38. Examples of the reformed fuel include liquid hydrocarbons such as gasoline and the like.
Various hydrocarbon fuels that can generate hydrogen by a reforming reaction, such as alcohols such as methanol, aldehydes, and natural gas, can be selected. The evaporating / mixing unit 36 has a structure for evaporating and raising the temperature of the reformed fuel supplied from the fuel tank 32 and the water supplied from the water tank 34 and mixing the two.

The mixed gas of the reformed fuel and water discharged from the evaporator / mixer 36 is subjected to a reforming reaction in a reformer 38 to generate a hydrogen-rich gas. Here, the reformer 38
Is provided with a reforming catalyst corresponding to the reformed fuel to be used, and the internal temperature of the reformer 38 is controlled so as to be a temperature suitable for a reaction for reforming the reformed fuel. The reforming reaction that proceeds in the reformer 38 can be selected from various modes such as a steam reforming reaction, a partial oxidation reaction, or a combination of both. What is necessary is just to select the thing according to the reforming reaction advanced in the vessel 38.

The hydrogen-rich gas generated by the reformer 38 is supplied to the mixed gas section 20 of the hydrogen extraction device 10 described above, and hydrogen is extracted from the hydrogen-rich gas. The extracted hydrogen is supplied as fuel gas to the anode side of the fuel cell 40. Further, compressed air is supplied as an oxidizing gas from the blower 42 to the cathode side of the fuel cell 40. By using the fuel gas and the oxidizing gas, an electromotive force is generated in the fuel cell 40 by an electrochemical reaction.

Although FIG. 4 shows the main constituent elements of the fuel cell device, as described above, various types of reformed fuel can be selected, and the fuel cell can be selected depending on the reformed fuel used. The configuration of the device 30 may be appropriately changed. For example, when a reformed fuel containing a sulfur content such as gasoline is used, a desulfurizer may be provided prior to the evaporation / mixing section 36 to desulfurize the reformed fuel. Further, a device for reducing the concentration of carbon monoxide in the reformed gas may be provided between the reformer 38 and the hydrogen extraction device 10. As a device for reducing the concentration of carbon monoxide in the reformed gas, for example, a shift unit provided with a shift catalyst for promoting a shift reaction to generate carbon dioxide and water from carbon monoxide and water vapor, A CO selective oxidation unit having a CO selective oxidation catalyst for promoting a selective oxidation reaction of carbon monoxide that preferentially oxidizes carbon oxide can be used.

According to the fuel cell device 30 of the present embodiment configured as described above, the hydrogen permeability of the hydrogen separation membrane 12 is ensured by heating the hydrogen separation membrane 12,
The above-described effect of suppressing the occurrence of carbon monoxide poisoning by the hydrogen separation membrane 12 can be obtained. Therefore,
The hydrogen permeation amount in the hydrogen extraction device 10 can be kept stable, and the supply of the fuel gas to the fuel cell 40 can be stabilized.

The fuel cell device 30 receives a detection signal (such as a reaction temperature of each component or a signal relating to the magnitude of a load connected to the fuel cell 40) relating to the operating state of each component of the fuel cell device 30. Together with the fuel cell device 3
Drive signals for controlling the operating state of each part constituting the unit 0 (a valve for adjusting the flow rate of the fluid supplied to each part, a blower 4).
2 which outputs a drive signal for the second device (not shown). Such a control unit includes the hydrogen extraction device 10
May be provided as a member in common with the above-described control unit 29 provided in the first embodiment. Alternatively, both may be provided separately and communication may be performed between the two.

The fuel cell device 30 is not shown in order to cover the power required by each component of the fuel cell device 30 at least when sufficient power cannot be obtained from the fuel cell 40 at the time of start-up. It has a secondary battery.
The above-described power supply 26 included in the hydrogen extraction device 10 may be configured by such a secondary battery, or may be configured by the fuel cell 40 when sufficient power is obtained from the fuel cell 40.

Furthermore, in the above-described embodiment, a configuration has been described in which a predetermined purge gas is flown to the extraction section 23 side of the hydrogen extraction apparatus 10 to improve the efficiency of hydrogen extraction. However, when such a purge gas is used, In this case, a gas that does not cause a problem in the electrochemical reaction when supplied to the fuel cell 40 may be selected as the purge gas. For example, water may be vaporized using a predetermined evaporator to generate steam, and this may be supplied to the extraction unit 23 as a purge gas.
Alternatively, a configuration is also possible in which gas discharged from various members constituting the fuel cell device 30 is used as a purge gas. For example, after being subjected to an electrochemical reaction, the fuel cell 4
It is possible to use the anode off-gas discharged from the anode side of 0 as a purge gas. Alternatively, after hydrogen is extracted by the hydrogen separation membrane 12, the outlet 2
A gas obtained by further reducing the concentration of carbon monoxide in the residual gas discharged from Step 2 may be used as a purge gas.

In FIG. 1, the mixed gas section 20 and the extraction section 23 provided in the hydrogen extraction device 10 are represented as spaces surrounded by predetermined outer walls. Can pass through, a porous member may be provided inside. When such a hydrogen extraction device is applied to a fuel cell device, a predetermined catalyst can be supported on the porous member. For example, if a porous member is provided in the mixed gas section 20 and the above-described reforming catalyst is supported on the porous member, the hydrogen extraction device 10 and the reformer 38 can be integrally formed. It becomes possible. Further, it is assumed that a catalyst relating to the reduction of the concentration of carbon monoxide such as the shift catalyst or the CO selective oxidation catalyst described above is supported, and the hydrogen extraction device 10
The shift portion and the CO selective oxidation portion may be formed integrally. Alternatively, a plurality of the above-described catalysts may be provided, and the hydrogen extraction device 10 may be formed integrally with a plurality of members of the reformer, the shift unit, and the CO selective oxidation unit.

In the case where the reforming catalyst is provided in the mixed gas section 20 as described above, the hydrogen separation membrane 12 is maintained at a desired temperature during the steady operation, so that the hydrogen separation membrane 12 also serves as the reforming catalyst. The temperature is maintained at a temperature corresponding to the reaction temperature. Here, for example, when the amount of the reforming fuel supplied to the reforming reaction fluctuates, the temperature of the reforming catalyst may temporarily and partially decrease, but even in such a case, the hydrogen separation The film 12 is independently affected by temperature fluctuations, and is separately temperature-controlled by supplying electricity to the porous substrate 14.
Sufficient hydrogen permeability can be maintained. Of course,
When the temperature at which the performance of the hydrogen separation membrane 12 can be sufficiently ensured is higher than the temperature of the reforming reaction, the hydrogen permeability can be sufficiently maintained by energizing the porous substrate 14.

(3-1) Start-up operation of the fuel cell device 30: The fuel cell device 30 including the hydrogen extraction device 10 can take various operation states.
The operation at the time of starting will be described. When the fuel cell device 30 is started, the components of the fuel cell device 30 are warmed up. For example, the evaporator / mixer 36 includes the reformer 3
Although a heat source for evaporating and raising the temperature of the mixed gas supplied to the side 8 is provided, in the warm-up operation, the inside of the mixed gas is heated by the heat source so that the temperature of the mixed gas can be sufficiently raised.

In the warm-up operation, the inside of the reformer 38 is heated until the temperature reaches a temperature at which the reforming reaction proceeds favorably. When the reformer 38 is provided with a heating device for supplying heat required for the reforming reaction, the temperature of the inside of the reformer 38 may be raised by the heating device. The evaporating / mixing unit 36
Gradually rises, and a high-temperature mixed gas is supplied from the evaporating / mixing section 36 side, so that the reformer 38 is also heated by the high-temperature mixed gas.

In the fuel cell 40, a temperature range in which the electrochemical reaction proceeds with sufficient activity is determined (for example, about 60 to 100 ° C. in the case of a polymer electrolyte fuel cell). Driving is performed. Fuel cell 40
Is not provided with a special heating device, the warm-up of the fuel cell 40 is started by the heat introduced by the gas supplied to the fuel cell 40. When the temperature of the gas supplied to the fuel cell 40 rises and the internal temperature of the fuel cell 40 starts to rise, and the electrochemical reaction in the fuel cell 40 gradually progresses, heat is generated due to the electrochemical reaction. This heat further warms up the fuel cell 40.

Here, if the hydrogen extraction device provided downstream of the reformer 38 is not provided with a structure for heating the hydrogen separation membrane, the reformed gas sufficiently heated from the upstream side is supplied. It is difficult to start the operation of hydrogen extraction until the hydrogen extraction device 1
In the case where a configuration for heating the hydrogen separation membrane 12 such as 0 is provided, when the supply of the gas containing hydrogen is started from the upstream side, the hydrogen separation membrane 12 is immediately heated to start the operation of hydrogen extraction. Then, hydrogen can be supplied to the fuel cell 40. In particular, in the hydrogen extraction device 10 of the present embodiment, since the hydrogen separation membrane 12 is formed on the porous base material 14 acting as a heating device, the heat generated by energizing the porous base material 14 The fuel cell device 30 is efficiently used to raise the temperature of the fuel cell 12, and does not delay the warming-up of the entire fuel cell device 30 to warm up the hydrogen extraction device 10. In addition, since the heating of the hydrogen separation membrane 12 is performed efficiently and no time is required to raise the temperature of the hydrogen separation membrane 12, the operation of hydrogen extraction before the temperature of the hydrogen separation membrane 12 is sufficiently increased is performed. Does not cause hydrogen embrittlement in the hydrogen separation membrane 12.

When the hydrogen separation membrane 12 is heated to start extracting hydrogen, the heated hydrogen separation membrane 12 is heated.
When the supply of hydrogen to the fuel cell 40 is started, hydrogen at a higher temperature can be supplied to the fuel cell 40 because the hydrogen is also heated by the permeation of the hydrogen. Therefore, in the fuel cell 40, the electrochemical reaction can be activated more quickly, and the heat generated by such an electrochemical reaction further warms up the fuel cell 40, and the warm-up time of the entire fuel cell device 30 is increased. Can be further shortened. As described above, when the reforming catalyst is provided in the mixed gas section 20 and the hydrogen extraction device 10 is formed integrally with the reformer 38, the reforming is performed by supplying electricity to the porous base material 14 at the time of startup. Effectively heats the high-quality catalyst to form the reformer 3
8 can also promote warm-up. Such an effect that the warm-up of the fuel cell device 30 can be promptly performed is because the fuel cell device 30 including the hydrogen extraction device 10
This can be obtained particularly remarkably when it is used for repeated starting and stopping, such as when it is used as a power source for driving a moving body such as an electric vehicle.

(3-2) Application of Operation for Recovering Hydrogen Separation Performance to Fuel Cell Device 30: In the fuel cell device 30, the reformed gas supplied from the reformer 38 side to the hydrogen extraction device 10 is somewhere. Since a fixed amount of carbon monoxide is contained, carbon monoxide poisoning may proceed in the hydrogen separation membrane 12, and the above-described operation for restoring the hydrogen permeability of the hydrogen separation membrane 12 is performed. Is useful.

In order to execute the operation for restoring the hydrogen permeability of the hydrogen separation membrane 12, as described above, the hydrogen extraction device 1 is used.
At 0, the operation of extracting hydrogen is temporarily stopped,
While maintaining the hydrogen separation membrane 12 at a predetermined temperature, the mixed gas section 2
For 0, supply of a recovery gas such as an oxygen-containing gas or water vapor is performed instead of the reformed gas. For example, a blower may be provided in addition to the hydrogen extraction device 10, and air may be supplied to the mixed gas section 20 as the recovery gas by the blower. Alternatively, in the evaporation / mixing unit 36,
A branch path is provided in a flow path through which water vapor formed by evaporating water supplied from the water tank 34 passes, and through this branch path,
Steam may be supplied to the mixed gas section 20 as the recovery gas.

In the fuel cell device 30, such an operation of restoring the hydrogen permeability of the hydrogen separation membrane 12 may be performed, for example, every time a predetermined time elapses after the fuel cell device 30 is started. Alternatively, it may be performed every time a predetermined amount of power is generated in the fuel cell 40 or every time a predetermined amount of fuel stored in the fuel tank 32 is consumed. Thereby, the hydrogen permeability of the hydrogen separation membrane 12 can be maintained in a favorable state,
A desired amount of hydrogen can be supplied to the fuel cell device 30.

Since the operation of restoring the hydrogen permeability is an operation performed by interrupting the operation of hydrogen extraction,
In the fuel cell device 30, if it is determined that the power generation may be interrupted or stopped, the operation of restoring the hydrogen permeability may be performed.
There is no hindrance to the operation of obtaining a desired amount of power from zero. For example, when the fuel cell device 30 is used as a power source for driving a moving body such as an electric vehicle, an operation in which the fuel cell 40 does not generate power, such as when the moving body is started or idling or when the moving body is decelerated. It is sufficient to perform the operation of restoring the hydrogen permeability when the state is possible in the moving body. With such a configuration, the moving performance of the moving body is reduced with the operation of restoring the hydrogen permeability. There is no limit. If the above-described operation of restoring the hydrogen permeability is performed when warming up each part of the fuel cell device 30 at the time of start-up, the hydrogen separation membrane 12 can be hydrogenated before the fuel cell device 30 enters a steady state. Power generation by the fuel cell 40 can be started in a state where the permeability is recovered and the hydrogen separation membrane 12 having sufficient performance is provided. The operation of restoring the hydrogen permeability may be automatically executed when the control unit of the fuel cell device 30 determines that the operation of not generating power of the fuel cell 40 is possible in the moving body. Alternatively, the operation of restoring the hydrogen permeability may be performed by a user of the mobile object inputting instructions from outside.

Further, in the fuel cell device 30 of the present invention, the hydrogen separation membrane 12 is heated by heating the porous base material 14 which is in direct contact with the hydrogen separation membrane 12, so that the hydrogen separation membrane is restored to restore the hydrogen permeability. By providing a configuration for heating the film 12, the entire apparatus does not increase in size,
It is particularly advantageous when the fuel cell device 30 is used as a power source for driving a moving body as described above. In addition, since the energy efficiency is prevented from being reduced due to the heating of the hydrogen separation membrane 12, the fuel cell device 30
This is particularly advantageous when the is used as a power source for driving the moving body and the amount of fuel that can be mounted is limited. Further, during the operation of restoring the hydrogen permeability, the hydrogen separation membrane 12 is kept at a predetermined high temperature, so that after the operation of restoring the hydrogen permeability is completed, the operation of extracting hydrogen is started immediately. Power generation by the fuel cell 40 can be performed.

(3-3) Operation when the fuel cell device 30 is stopped: Next, the operation when the fuel cell device 30 is stopped will be described. When the fuel cell device 30 is stopped, by performing the above-described operation when the hydrogen extraction device 10 is stopped,
Hydrogen embrittlement of the hydrogen separation membrane 12 can be prevented.

When the fuel cell device 30 is stopped, the supply of the reformed fuel from the fuel tank 32 and the supply of water from the water tank 34 are stopped, and the operation is sequentially performed from the upstream side, that is, from the evaporation / mixing unit 36 side. Is completed, and finally the fuel cell 40
When the supply of fuel gas to the fuel cell is stopped, the fuel cell 4
At 0, no electromotive force is generated. At this time, the hydrogen extraction device 1
Although the temperature of the hydrogen extraction device 10 may decrease as the supply amount of the reformed gas to zero decreases, in the present embodiment, the above-described operation at the time of stop in the hydrogen extraction device 10 is performed. Even when the fuel cell device 30 is stopped, the temperature of the hydrogen separation membrane 12 is kept sufficiently high so that hydrogen permeates the hydrogen separation membrane 12 so that the hydrogen does not stay inside.
In this case, hydrogen embrittlement can be prevented. Note that when the fuel cell device 30 is stopped, that is, when the above-described operation at the time of stop is performed in the hydrogen extraction device 10, the hydrogen-free gas supplied to the mixed gas unit 20 instead of the mixed gas is described above. If a recovery gas (a gas containing oxygen or water vapor) is used, when the fuel cell device 30 is stopped,
The operation of restoring the hydrogen permeability of the hydrogen separation membrane 12 can be performed simultaneously.

The embodiments of the present invention have been described above.
The present invention is not limited to such embodiments at all, and it goes without saying that the present invention can be implemented in various modes without departing from the gist of the present invention.

[Brief description of the drawings]

FIG. 1 is an explanatory diagram showing a schematic configuration of a hydrogen extraction device 10 of the present embodiment.

FIG. 2 is a diagram showing a relationship between hydrogen permeability and temperature in a hydrogen separation membrane.

FIG. 3 is an explanatory diagram showing the relationship between the rate of decrease in the amount of hydrogen permeation caused by carbon monoxide poisoning and temperature.

FIG. 4 is an explanatory diagram showing a schematic configuration of a fuel cell device 30 including the hydrogen extraction device 10.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 10 ... Hydrogen extraction apparatus 12 ... Hydrogen separation membrane 14 ... Porous base material 15 ... Hydrogen separation membrane 20 ... Mixed gas part 21, 24 ... Inlet 22, 25 ... Outlet 23 ... Extraction part 23 ... Separation part 26 ... Power supply 27 ... Temperature sensor 28 ... Switch 29 ... Control unit 30 ... Fuel cell device 32 ... Fuel tank 34 ... Water tank 36 ... Evaporation / mixing unit 38 ... Reformer 40 ... Fuel cell 42 ... Blower

Continued on front page F term (reference) 4D006 GA41 KA31 KB30 KE16P KE25Q MA03 MA09 MB04 MC02X NA05 NA31 NA46 PB66 4G040 FA02 FB09 FC01 FE01 4G140 FA02 FB09 FC01 FE01 5H027 AA02 AA06 BA01 BA16 BA17 BA19 DD03

Claims (11)

[Claims] 1. A hydrogen extraction device for extracting hydrogen from a hydrogen-containing gas mixture, comprising: a base material made of a porous material that generates heat when energized; A hydrogen separation membrane having a property of allowing permeation; and an energizing means for flowing an electric current to the base material, wherein the mixed gas is supplied to the hydrogen separation membrane, and hydrogen is extracted from the mixed gas by the hydrogen separation membrane. A hydrogen extraction device capable of heating the hydrogen separation membrane by energizing the substrate by the energization means. 2. The hydrogen extraction device according to claim 1, wherein: a sensor for detecting a temperature of the hydrogen separation membrane; and a temperature detected by the sensor being equal to or lower than a predetermined temperature.
A hydrogen extraction device further comprising: control means for controlling the energization means so that an electric current flows through the base material. 3. The hydrogen extraction device according to claim 1, wherein the hydrogen separation membrane is made of palladium or a metal containing palladium. 4. The hydrogen extraction device according to claim 2, wherein the predetermined temperature is 300 ° C. 5. The hydrogen extraction device according to claim 1, wherein the porous body constituting the base material contains a conductive ceramic. 6. The hydrogen extraction device according to claim 5, wherein the conductive ceramic contains silicon carbide. 7. The hydrogen extraction device according to claim 1, wherein impurities adsorbed on the hydrogen separation membrane are removed from the hydrogen separation membrane instead of the mixed gas. Further comprising a recovery gas supply unit for supplying a recovery gas that works to perform the operation. When the recovery gas is supplied to the hydrogen separation membrane using the recovery gas supply unit, the base material is energized using the energization unit. A hydrogen extraction device for heating the hydrogen separation membrane. 8. The hydrogen extraction device according to claim 1, wherein a gas containing substantially no hydrogen is supplied to the hydrogen separation membrane in place of the mixed gas. When it is determined that the operation of stopping the hydrogen extraction device is performed, the non-hydrogen-containing gas is supplied to the hydrogen separation membrane using the stop-time gas supply unit, and the energizing unit is connected to the gas supply unit. A hydrogen extraction apparatus for heating the hydrogen separation membrane by applying electricity to the base material using the hydrogen extraction membrane. 9. A hydrogen extraction method for extracting hydrogen from a mixed gas containing hydrogen, comprising using a hydrogen separation membrane formed on a base material made of a porous material and having a property of selectively permeating hydrogen. A method of extracting hydrogen from the mixed gas, wherein a current is applied to the base material to generate heat in the base material, thereby heating the hydrogen separation membrane. 10. The method for extracting hydrogen according to claim 9, wherein an energization state of the substrate is changed according to a temperature of the hydrogen separation membrane. 11. A fuel cell device comprising a fuel cell that obtains an electromotive force by an electrochemical reaction using hydrogen, comprising: a reformer that reforms a hydrocarbon-based fuel to generate a hydrogen-containing gas; The hydrogen extraction apparatus according to any one of 1 to 8, wherein the hydrogen-containing gas is supplied from the reformer,
A fuel cell device comprising: a hydrogen extraction device that extracts hydrogen from the hydrogen-containing gas; and a supply unit that supplies the hydrogen extracted by the hydrogen extraction device to the fuel cell.