JP2002201004A - Hydrogen extraction device - Google Patents

Abstract

(57) [Summary] [PROBLEMS] To make the whole device more compact while ensuring sufficient sealing performance in a gas flow path. SOLUTION: The hydrogen extraction device 10 includes a plurality of hydrogen separation membranes 20 stacked in an outer shell side wall 14. An inner spacer 2 is provided between the stacked hydrogen separation membranes 20.
4 and an outer spacer 26, and the space inside the hydrogen extraction device 10 is divided into two by the hydrogen separation membrane 20 and the spacer. One space has a reformed gas passage 3 through which a reformed gas containing hydrogen passes.
The other space serves as a purge gas passage 30 through which the purge gas passes. The connection between the hydrogen separation membrane 20 and each spacer has a sufficient sealing property, and only hydrogen in the reformed gas can move toward the purge gas flow path by permeating the hydrogen separation membrane 20. Thus, hydrogen is extracted.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a hydrogen extraction apparatus for extracting hydrogen from a gas containing hydrogen.

[0002]

2. Description of the Related Art Conventionally, as an apparatus for extracting hydrogen from a hydrogen-containing gas, an apparatus using a hydrogen separation membrane provided with a metal having a property of selectively permeating hydrogen (for example, palladium or a palladium alloy) is used. It has been known. Such a hydrogen extraction device is used, for example, in a fuel cell device including a fuel cell. Fuel cells are
This is a device that is supplied with a fuel gas containing hydrogen and obtains an electromotive force by an electrochemical reaction. As a method of supplying a fuel gas to a fuel cell, a method of 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 extracted from reformed gas using the hydrogen extraction device and supplied to a fuel cell. That is, if a flow path through which the reformed gas passes is provided on one surface side of the hydrogen separation membrane, only hydrogen in the reformed gas passes through the hydrogen separation membrane, so that the other surface side of the hydrogen separation membrane Hydrogen can be extracted into the provided channel.

An apparatus for supplying hydrogen to an apparatus that consumes hydrogen, such as a fuel cell, includes a hydrogen extraction device including the hydrogen separation membrane. , A hydrogen separation membrane, and a plurality of layers constituting a flow path through which hydrogen extracted by the hydrogen separation membrane flows (for example, JP-A-6-345408). Such). As described above, by laminating the structure including the two flow paths (the flow path through which the hydrogen-containing gas flows and the flow path through which the extracted hydrogen passes) sandwiching the hydrogen separation membrane, the entire apparatus is compact. In addition, the surface area of the hydrogen separation membrane can be secured more widely in the entire apparatus, and the efficiency of hydrogen extraction can be improved. In the configuration disclosed in the above publication, a reforming catalyst is provided in a layer constituting a flow path through which the reformed gas flows, and a reforming reaction for generating hydrogen from a hydrocarbon-based fuel proceeds in the flow path. By doing so, hydrogen generated in the reforming reaction can be immediately extracted, and the efficiency of the reforming reaction and hydrogen extraction is improved.

[0004]

However, as described above, when a structure composed of two flow paths sandwiching a hydrogen separation membrane is laminated to constitute a hydrogen extraction device, each flow path, particularly At the end, there is a problem that it is difficult to ensure sufficient sealing performance. In addition, a large manifold is required to distribute the gas to each of the laminated flow paths or to sequentially route the gas to each of the laminated flow paths, and the manifold structure becomes complicated. There is a problem that it causes an increase in size. Further, it has been difficult to sufficiently secure the sealing property (airtightness at the connection portion) between such a manifold and each flow path. Therefore, in the hydrogen extraction device in which the hydrogen separation membrane and the flow path are stacked as described above, the entire structure including the manifold structure can be formed more compactly, and the sealing performance at the end of the flow path and the connection portion can be improved. A configuration that can be easily secured has been desired.

[0005] The hydrogen extraction apparatus of the present invention has been made to solve the above-mentioned problems, and to make the entire apparatus more compact while ensuring sufficient sealing performance in the flow path, and has the following configuration.

[0006]

A first hydrogen extraction device of the present invention is a hydrogen extraction device for extracting hydrogen from a hydrogen-containing gas containing hydrogen, and has a predetermined space therein. It is possible to extract hydrogen from the hydrogen-containing gas by the property of selectively permeating hydrogen with the outer shell that forms, and the outer shell is stacked at a predetermined interval in the outer shell. A plurality of hydrogen separation membranes, disposed in the outer shell portion, between the stacked hydrogen separation membranes, to secure the predetermined spacing between the hydrogen separation membranes, A spacer forming a boundary that divides the predetermined space together with the membrane surface of the separation membrane, and a film surface of each of the stacked hydrogen separation membranes and the spacer are formed in the outer shell by dividing the predetermined space. , Through which the hydrogen-containing gas passes The first flow path, the membrane surface of each of the stacked hydrogen separation membranes, and the spacer separate the predetermined space, so that the first flow path faces the first flow path with the hydrogen separation membrane interposed in the outer shell. Formed on the side where
And a second flow path through which hydrogen extracted by the hydrogen separation membrane from the hydrogen-containing gas passing through the flow path passes.

[0007] The first hydrogen extraction apparatus of the present invention configured as described above can extract hydrogen from the hydrogen-containing gas by virtue of the property of selectively permeating hydrogen. The plurality of hydrogen separation membranes stacked at a predetermined interval in the unit and the stacked hydrogen separation membranes are disposed between the hydrogen separation membranes to secure the predetermined interval between the hydrogen separation membranes. By forming a boundary with the spacer
A predetermined space formed in the outer shell portion is formed between the first flow path and the second flow path.
And the flow path. When a hydrogen-containing gas containing hydrogen passes through the first flow path, and hydrogen is extracted from the hydrogen-containing gas by the hydrogen separation membrane, the extracted hydrogen passes through the second flow path.

According to the first hydrogen extraction apparatus of the present invention, by stacking a plurality of hydrogen separation membranes, the area of the hydrogen separation membrane involved in hydrogen extraction can be reduced while the whole apparatus is made compact. Can be sufficiently secured.
Further, the inner space of the outer shell is separated by the membrane surface of the hydrogen separation membrane and the spacer, whereby the first passage through which the hydrogen-containing gas passes and the second passage through which the extracted hydrogen passes. Because there is no need to provide a large manifold to supply and exhaust gas to and from the gas flow path formed on each hydrogen separation membrane, gas is supplied to the gas flow path on the hydrogen separation membrane. The structure of the supply / discharge manifold can be simplified. By simplifying the structure of the manifold, it is possible to simplify the structure of the connecting portion that connects the flow paths, and the sealing (airtightness) at the connecting portion
Is easy to secure.

Furthermore, since the outer shell is separated by arranging a spacer between the hydrogen separation membranes to form the two flow paths, the first flow path formed on each hydrogen separation membrane or In the second flow path, the flow paths formed on each hydrogen separation membrane are connected in series with each other. Therefore, the hydrogen-containing gas supplied to the hydrogen extraction device is supplied to the first flow path formed on each hydrogen separation membrane without being divided, and the first flow path and the second flow path are supplied to the first flow path. A sufficient hydrogen concentration difference can be secured with the road, and the efficiency of hydrogen extraction can be improved.

In the first hydrogen extraction apparatus of the present invention, one of the first flow path and the second flow path is formed in the inside using the hydrogen separation membrane and the spacer. Forming a hydrogen separation part, and forming the other of the first flow path and the second flow path between the hydrogen separation part and the outer shell part, The hydrogen separator may be housed in an outer shell.

In the first hydrogen extraction apparatus of the present invention, each of the plurality of hydrogen separation membranes is formed in substantially the same shape, and is arranged so as to overlap each other when viewed from the lamination direction. The end may be connected to the spacer.

With such a configuration, the entire hydrogen extraction apparatus can be made more compact. Further, the entire membrane surface of the hydrogen separation membrane can contribute to the operation of hydrogen extraction, and the efficiency of hydrogen extraction can be sufficiently ensured in the entire apparatus.

Here, the hydrogen separation membrane is formed in a donut shape having a circular arc at the outer periphery and a circular hole at the center, and the outer shell has a cylindrical shape. The hole of each of the stacked hydrogen separation membranes forms a part of one of the first flow path and the second flow path and has a cylindrical outer shell. A part of the other of the first flow path and the second flow path may be formed between the inner surface of the unit and the outer periphery of each of the stacked hydrogen separation membranes. Good.

With this configuration, the flow (flow rate) of gas in each flow path formed on each hydrogen separation membrane can be made more uniform throughout the hydrogen extraction apparatus.

In the first hydrogen extraction device of the present invention, the hydrogen separation membrane and the spacer are connected between a membrane surface of the hydrogen separation membrane and a surface of the spacer substantially parallel to the membrane surface. In addition, it may be sealed so as to secure airtightness between the hydrogen separation membrane and the spacer.

With such a configuration, the hydrogen separation membrane and the spacer are connected between the membrane surface of the hydrogen separation membrane and the surface of the spacer substantially parallel to the membrane surface. It becomes easy to secure airtightness at the connecting portion to be connected, and the configuration for sealing can be simplified.

In the first hydrogen extraction apparatus of the present invention, the hydrogen separation membrane is formed by forming a palladium or palladium alloy film on both surfaces of a base material formed of a group 5 metal or a group 5 metal alloy. Is also good.

[0018] In such a hydrogen extraction apparatus, the hydrogen separation membrane and the spacer are formed by a gasket, brazing,
It may be sealed by any of glass bonding. Adhesion between the surfaces parallel to the hydrogen separation membrane can easily ensure airtightness by the means described above,
The operation for realizing sufficient airtightness can be prevented from becoming complicated.

In such a hydrogen extraction device, the hydrogen separation membrane is formed by supporting a hydrogen separation metal on a porous substrate, and the porous substrate is connected to the hydrogen separation membrane and the spacer. A gas-impermeable coat layer capable of ensuring airtightness at the connection portion, and the hydrogen separation membrane and the spacer may be sealed between the coat layer and the spacer.

By forming the hydrogen separation membrane by supporting a hydrogen separation metal on a porous substrate, the strength of the hydrogen separation membrane can be improved. Further, by providing the coat layer, it is possible to prevent the airtightness from being impaired at the connection portion due to the gas permeability of the porous base material.

In the hydrogen extraction device of the present invention, the hydrogen extraction device is provided between the adjacent hydrogen separation membranes, and is provided between the first flow passage and the second flow passage formed between the adjacent hydrogen separation membranes. The apparatus may further include a gas rectifying plate that partitions at least one of the flow paths and guides a gas passing through the partitioned flow path along the hydrogen separation membrane.

With such a configuration, since the gas passing through the flow path flows along the hydrogen separation membrane, the operation of extracting hydrogen in the hydrogen separation membrane is effectively performed, and the efficiency of hydrogen extraction is improved. Can be done.

In such a hydrogen extraction device, the gas flow regulating plate may be formed integrally with at least one of the spacer and the outer shell.

In such a hydrogen extraction device,
The gas rectifying plate may be further provided with a reinforcing member disposed between the hydrogen separation membranes adjacent to each other with the gas rectifying plate interposed therebetween, for connecting the hydrogen separation membranes and for supporting the gas rectification plate. By providing the reinforcing member, the strength of the entire hydrogen extraction device can be improved.

[0025] In such a hydrogen extraction apparatus, the first gas channel, the spacer, and the reinforcing member, wherein at least a part of the first flow path is formed between the gas flow plate and the hydrogen separation membrane. A laminated member, comprising: the gas flow regulating plate, the spacer, and the reinforcing member; and a second laminated member that forms at least a part of the second flow path between the hydrogen separation membrane, A first laminated member, the hydrogen separation membrane,
Each member is laminated in the order of the second laminated member and the hydrogen separation membrane, and the laminated adjacent members are connected to each other in a plane substantially parallel to a laminated surface when the respective members are laminated. In addition, the sealing member may be sealed so as to ensure airtightness between the adjacent members.

With such a configuration, the first and second
The simple operation of sequentially stacking the stacked members together with the hydrogen separation membrane makes it possible to easily manufacture a hydrogen extraction device having the above-described structure. At this time, since the members are sealed in a plane substantially parallel to the lamination surface, the configuration for ensuring airtightness is simplified, and sufficient airtightness can be easily ensured. Further, in at least one of the first laminated member and the second laminated member, a part of the outer shell portion is formed, and the outer shell portion is also formed when the respective members are stacked. Then, the process of manufacturing the hydrogen extraction device can be further simplified.

[0027] In the first hydrogen extraction apparatus of the present invention, the hydrogen extracted from the hydrogen-containing gas passes through the second flow path and guides the hydrogen to outside the second flow path. Derived gas supply means for supplying gas to the second flow path may be further provided.

With this configuration, the hydrogen extracted from the hydrogen-containing gas to the second flow path side by the hydrogen separation membrane is successively guided to the outside of the second flow path by the above-mentioned derived gas. It is possible to maintain a sufficient hydrogen concentration difference between the flow path and the second flow path. Thereby, the efficiency of hydrogen extraction in the hydrogen extraction device can be improved.

[0029] In such a hydrogen extraction device, the hydrogen-containing gas passing through the first flow path and the derived gas passing through the second flow path together with hydrogen extracted from the hydrogen-containing gas. Also, a configuration in which the gas flows in the directions facing each other is preferable.

With such a configuration, the hydrogen concentration difference between the first flow path and the second flow path can be sufficiently maintained in the entire hydrogen extraction apparatus, and the hydrogen extraction efficiency can be further improved. Can be improved.

[0031] In the first hydrogen extraction apparatus of the present invention, the first flow path includes a reforming catalyst for promoting a reforming reaction for generating a hydrogen-containing gas from a hydrocarbon-based fuel. The fuel may be supplied, and the hydrogen-containing gas generated by reforming the hydrocarbon-based fuel by the reforming catalyst may pass through.

With such a configuration, in the hydrogen extraction device, the reforming of the hydrocarbon fuel and the extraction of hydrogen can be performed simultaneously. Here, as the hydrocarbon-based fuel, various fuels that can generate hydrogen by a reforming reaction, such as liquid hydrocarbons such as gasoline, alcohols and aldehydes such as methanol, and natural gas, can be selected.

Here, the first flow path is provided with C for promoting a reaction for reducing the concentration of carbon monoxide in the hydrogen-containing gas.
An O reduction catalyst may be further provided. With such a configuration, the concentration of carbon monoxide in the hydrogen-containing gas is reduced prior to extracting hydrogen from the hydrogen-containing gas. The occurrence can be suppressed.

[0034] In the first hydrogen extraction apparatus of the present invention, the hydrogen-containing gas passing through the first flow path further contains carbon monoxide, and the first flow path includes a gas contained in the gas. A CO reduction catalyst that promotes a reaction for reducing the concentration of carbon monoxide may be provided. With such a configuration, it is possible to suppress the problem that the hydrogen separation membrane is poisoned by carbon monoxide contained in the hydrogen-containing gas used for hydrogen extraction.

The second hydrogen extraction device of the present invention is a hydrogen extraction device for discharging hydrogen to the outside, wherein a plurality of stacked hydrogen separation membranes having a property of selectively permeating hydrogen are provided;
A hydrogen-containing gas containing hydrogen passes therethrough, a first flow path in which a part of a wall surface is formed by the hydrogen separation membrane, and the first flow path is adjacent to the first flow path through the hydrogen separation membrane,
A second flow path into which hydrogen extracted from the hydrogen-containing gas passing through the first flow path by the hydrogen separation membrane flows, and a second flow path passing through the second flow path; And a derivation gas supply means for supplying a derivation gas for guiding the hydrogen flowing into the second flow path to the outside of the second flow path to the second flow path, and passing through the first flow path. The gist is that the hydrogen-containing gas and the derived gas passing through the second flow path together with the hydrogen extracted from the hydrogen-containing gas flow in directions opposite to each other.

The second hydrogen extraction apparatus of the present invention having the above-described structure is characterized in that a plurality of stacked hydrogen separation membranes having a property of selectively permeating hydrogen are partially separated by the hydrogen separation membrane. Is extracted from the hydrogen-containing gas passing through the first flow path in which is formed. The extracted hydrogen flows through the hydrogen separation membrane into a second flow path adjacent to the first flow path. To the second flow path, a derived gas that guides the hydrogen that has flowed into the second flow path to the outside of the second flow path by passing through the inside of the second flow path is used as the first gas. The gas is supplied so as to flow in a direction opposite to the hydrogen-containing gas passing through the flow path.

According to the second hydrogen extraction apparatus of the present invention, the hydrogen extracted from the hydrogen-containing gas to the second flow path by the hydrogen separation membrane is moved out of the second flow path by the above-mentioned derived gas. Since they are sequentially guided, it is possible to maintain a sufficient hydrogen concentration difference between the first flow path and the second flow path. Thereby, the efficiency of hydrogen extraction in the hydrogen extraction device can be improved. Further, the hydrogen-containing gas passing through the first flow path and the derived gas passing through the second flow path flow in directions opposite to each other. The difference in hydrogen concentration between the flow path and the flow path can be sufficiently maintained, and the efficiency of hydrogen extraction can be further improved.

The fuel cell device of the present invention is a fuel cell device provided with a fuel cell which receives a supply of a gas containing hydrogen and a gas containing oxygen and obtains an electromotive force by an electrochemical reaction utilizing the gas. A hydrogen extraction device according to any one of claims 1 to 17, wherein hydrogen extracted by the hydrogen extraction device is used for the electrochemical reaction.

With such a configuration, the hydrogen extraction device of the present invention having a simple manifold structure is provided.
An increase in the size of the entire fuel cell device can be suppressed. In addition, since the hydrogen extraction device of the present invention, which can easily ensure sufficient sealing performance, is provided, the reliability of a device for supplying a gas containing hydrogen to a fuel cell can be increased.

[0040]

DESCRIPTION OF THE PREFERRED EMBODIMENTS In order to further clarify the structure and operation of the present invention described above, embodiments of the present invention will be described based on examples in the following order. 1. 1. Configuration of hydrogen extraction device 10 of first embodiment 2. Configuration of hydrogen extraction device 110 of second embodiment Modified example 4. Application to fuel cell devices

(1) Configuration of hydrogen extraction apparatus 10 of first embodiment: FIG. 1 shows the configuration of a hydrogen extraction apparatus 10 according to a preferred embodiment of the present invention. FIG. 1 is a perspective view showing a state in which a part of the structure of the hydrogen extraction device 10 of the first embodiment is partially disassembled. The hydrogen extraction device 10 includes the hydrogen separation component 1
2. It comprises two side wall members 15 forming the outer shell side wall 14 and two outer shell lids 16 disposed at the upper end and the lower end as main components. FIG. 2 is an explanatory diagram schematically showing a cross section of the hydrogen extraction device 10 formed by assembling the above components. In FIG. 2, the state of the cross section of the hydrogen extraction device 10 is shown only on one side with respect to the center line (AA line shown in FIG. 1). The other side with respect to the center line is formed symmetrically with the side shown in FIG.

The hydrogen separation component 12 includes a circular (donut-shaped) hydrogen separation membrane 20 and a purge gas rectifying plate 2.
2 and an inner spacer 24 and an outer spacer 26 formed between adjacent hydrogen separation membranes 20 to form a cylindrical side surface (see FIG. 1). (The purge gas will be described later). Further, a purge gas inlet 31 and a purge gas outlet 32 are provided at the upper end and the lower end of the hydrogen separation component 12, and these are communicated with the internal purge gas flow path 30.

The side wall member 15 is provided with a reformed gas straightening plate 28 inside the side wall member 15.
Is stored inside, and combined with the outer shell lids 16 disposed at the upper end and the lower end, thereby forming a reformed gas flow path 33 between the hydrogen separation component 12 and the hydrogen separation component 12.
Note that the hydrogen separation component 12 is housed inside
When the hydrogen extraction device 10 is formed by combining the two side wall members 15, the reformed gas rectifying plate 28 provided on the side wall member 15 is connected to the corresponding reformed gas rectifying plate 28 provided on the other side wall member 15 to form a donut. In the hydrogen separation component, the hydrogen separation component is disposed in a space between two adjacent hydrogen separation membranes 20 with an inner spacer 24 interposed therebetween (see FIGS. 1 and 2). The two outer shell lids 16 are provided with a reformed gas inlet 34 and a reformed gas outlet 35, respectively, which are connected to a reformed gas passage 33 formed in the outer shell side wall 14. Communicating.

The hydrogen separation membrane 20 is a membrane including a metal having a property of selectively permeating hydrogen (hereinafter, referred to as a hydrogen separation metal). As the hydrogen separation metal, palladium or a palladium alloy (for example, Metal such as palladium-silver alloy). In this embodiment, the hydrogen separation membrane 20 is used.
In this method, the hydrogen separation metal is supported on a predetermined porous substrate. By supporting the hydrogen separation metal on the porous substrate, the strength of the hydrogen separation membrane can be improved. Here, as the hydrogen separation membrane 20, various configurations can be applied. The hydrogen separation membrane 20 can be formed, for example, by coating the porous substrate with a hydrogen separation metal by plating, chemical vapor deposition (CVD), physical vapor deposition (PVD), or the like. Alternatively, it may be formed by supporting the hydrogen separation metal on the pores of the porous substrate. Examples of such a method of supporting a hydrogen separation metal include, for example, an impregnation support method in which a porous substrate 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. A method in which the composition is applied to the surface and fired can be used. In addition,
The porous substrate is a gas-permeable member formed of a material having sufficient strength and heat resistance, and the material can be selected from, for example, ceramics and metal.

The spacers, rectifying plates, side wall members and the like other than the hydrogen separation membrane 20 have sufficient strength and sufficient heat resistance (because the reforming reaction proceeds at a predetermined high temperature, the temperature of the supplied reformed gas is low). (Sufficient heat resistance). In the present embodiment, each of the above members is formed of stainless steel, but various materials such as ceramics can be selected in addition to such a metal material. These members are connected so as to ensure sufficient airtightness. Accordingly, the space inside the hydrogen extraction device 10 is divided into a purge gas passage 30 formed in the hydrogen separation component 12 and a reformed gas passage 33 formed between the hydrogen separation component 12 and the outer shell side wall 14. By passing through the hydrogen separation membrane 20, only hydrogen can move between the two flow paths. The part connecting the side wall member 15 and the outer shell lid 16 to each other is shown in FIG. 1 as a region with a “+” sign. The seal structure for connecting the members will be described later in detail.

When a metal containing palladium is used as the hydrogen separation metal as described above, the efficiency with which the hydrogen separation metal extracts hydrogen depends on the temperature of the hydrogen separation metal. Therefore, in order to ensure sufficient hydrogen extraction efficiency, the temperature at which hydrogen is extracted in the hydrogen separation membrane 20 is set to a predetermined temperature or higher (for example, 300 ° C. or higher, preferably 5 ° C. or higher).
(00 ° C. or higher). By using a high-temperature reformed gas as the reformed gas provided for the hydrogen extraction operation, a temperature at the time of performing the hydrogen extraction operation may be ensured. And the heating device may be used to heat the entire hydrogen extraction device 10 or the hydrogen separation membrane 20.

Next, the flow of gas in the hydrogen extraction device 10 and the operation of hydrogen extraction will be described with reference to FIG. A reformed gas, which is a hydrogen-containing gas, is supplied to the reformed gas flow path 33 in the hydrogen extraction device 10 from the outside via a reformed gas inlet 34 (in the present embodiment, the hydrogen extraction device 10 is It is assumed that the present invention is applied to a fuel cell device, and a description will be given based on an operation of extracting hydrogen from a reformed gas obtained by reforming a hydrocarbon-based fuel. The configuration related to the device will be described later). Reformed gas passage 3 formed in hydrogen extraction device 10
Reference numeral 3 denotes a manifold region 33a formed between the outer spacer 26 and the outer shell side wall 14 and guiding the reformed gas in the direction in which the members are stacked.
And a hydrogen extraction region 33b for guiding the reformed gas along the line 8. The operation of extracting hydrogen from the reformed gas is performed when the reformed gas passes through the hydrogen extraction region 33b. The manifold region 33a is used to supply and discharge the reformed gas to and from each hydrogen extraction region 33b. work.

The reformed gas supplied to the reformed gas passage 33 via the reformed gas inlet 34 passes through the manifold region 33a closest to the reformed gas inlet 34, and then passes through the reformed gas rectifying plate 28. The hydrogen extraction region 33b formed on the hydrogen separation membrane 20 (first hydrogen separation membrane 20) disposed closest to the reformed gas inlet 34
(First hydrogen extraction region 33b). The reformed gas that has passed through the first hydrogen extraction region 33b is guided to the inner spacer 24 connected to the end of the first hydrogen separation membrane 20, and changes the flow direction, and the first hydrogen The hydrogen extraction region 33b (second hydrogen separation region) formed on the hydrogen separation film 20 (second hydrogen separation film 20) disposed next to the separation film 20
To the hydrogen extraction region 33b).

The reformed gas that has passed through the second hydrogen extraction region 33b is supplied to the second region by the manifold region 33a formed between the outer spacer 26 and the outer shell side wall 14.
To the third hydrogen extraction region 33b formed on the third hydrogen separation membrane 20 provided next to the hydrogen separation membrane 20 of FIG. Such an operation is repeated according to the number of layers to reach the reformed gas discharge port 35 and discharged to the outside. In other words, the reformed gas flows from the reformed gas inlet 34 toward the reformed gas outlet 35 while being guided to the manifold region 33a and the inner spacer 24.
It flows sequentially in the hydrogen extraction region 33b formed on the zero. As described above, when the reformed gas flows in the hydrogen extraction region 33b, hydrogen in the reformed gas is extracted from the reformed gas by permeating the hydrogen separation membrane 20, and moves to the purge gas passage 30 side. .

In the hydrogen extraction apparatus 10 of this embodiment, in order to improve the efficiency of hydrogen extraction by the hydrogen separation membrane 20, the flow path in contact with the reformed gas flow path 33 with the hydrogen separation membrane 20 interposed therebetween is And the purge gas passage 30
, A purge gas is introduced to guide the extracted hydrogen to the outside. That is, by flowing a purge gas through the purge gas flow path 30 and carrying hydrogen extracted through the hydrogen separation membrane 20 and extracted from the reformed gas by the purge gas, the hydrogen concentration in the opposed flow path is always kept low. The aim is to ensure the efficiency of hydrogen extraction. As the purge gas, a gas that does not cause any 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.

The purge gas is supplied from the outside to the purge gas passage 30 through a purge gas inlet 31. Purge gas flow path 3 formed in hydrogen extraction device 10
Reference numeral 0 denotes a manifold region 30a formed by the inner spacer 24 and guiding the purge gas in the stacking direction of the members.
And a hydrogen extraction region 30b for guiding a purge gas along the hydrogen separation membrane 20 and the purge gas flow control plate 22. Hydrogen extracted from the reformed gas flows into the purge gas in the hydrogen extraction region 30b, and the manifold region 30a functions to supply and discharge the purge gas to and from the hydrogen extraction region 30b.

The purge gas supplied to the purge gas passage 30 through the purge gas inlet 31 is supplied to the hydrogen separation membrane 20 (first hydrogen separation membrane) disposed closest to the purge gas inlet 31 by the purge gas straightening plate 22. 20. However, the first hydrogen separation membrane 2 in the above description of the reformed gas side
It is located at the end opposite to 0. The same applies to the following) The hydrogen extraction region 30b (first hydrogen extraction region 30b) formed above
It is led to. The purge gas that has passed through the first hydrogen extraction region 30b is supplied by the manifold region 30a formed by the inner spacer 24 to the hydrogen separation film 20 (the second hydrogen separation film 20) disposed next to the first hydrogen separation film 20. It is led to the hydrogen extraction region 30b (second hydrogen extraction region 30b) formed on the hydrogen separation membrane 20).

The purge gas that has passed through the second hydrogen extraction region 30b is guided to the outer spacer 26 connected to the end of the second hydrogen separation membrane 20, and changes the flow direction. Hydrogen separation membrane 2 arranged next to 20
0 (third hydrogen separation membrane 20) is led to a hydrogen extraction area 30b (third hydrogen extraction area 30b) formed on the third hydrogen separation membrane 20. The reformed gas that has passed through the third hydrogen extraction region 30b is led to the manifold region 30a formed by the inner spacer 24, and the above operation is repeated according to the number of layers to reach the purge gas discharge port 32, and to the outside. Is discharged. That is, the purge gas is introduced into the purge gas inlet 3 while being guided to the manifold region 30a and the outer spacer 26.
From the first side toward the purge gas discharge port 32 side, the hydrogen gas sequentially flows in the hydrogen extraction region 30b formed on each hydrogen separation membrane 20. Thus, the purge gas is supplied to the hydrogen extraction region 30b.
When flowing through the inside, hydrogen extracted from the reformed gas through the hydrogen separation membrane 20 is mixed with the purge gas and guided to the outside.

The purge gas passage 30 and the reformed gas passage 3
The direction of the flow of the gas passing through the inside 3 is indicated by an arrow in FIG. The flow direction of the two gases may be the same in the reformed gas flow path 33 and the purge gas flow path 30 adjacent to each other with the hydrogen separation membrane 20 interposed therebetween. Then, it was decided to flow in the direction in which both face each other. Efficiency of hydrogen extraction by hydrogen separation membrane (speed)
Depends on the difference in hydrogen concentration between two adjacent flow paths via the hydrogen separation membrane. By adopting such a configuration, the efficiency of hydrogen extraction in the entire hydrogen extraction device 10 can be improved. Can be.

In the case where both are flowed in opposite directions as in this embodiment (see FIG. 3 (a)), the reformed gas on the upstream side, that is, the reformed gas having a high hydrogen concentration without much hydrogen extraction yet. Is in contact with a downstream purge gas, that is, a purge gas containing a large amount of extracted hydrogen and having a high hydrogen concentration, via the hydrogen separation membrane 20. Also,
The reformed gas on the downstream side, that is, the reformed gas whose hydrogen concentration has decreased due to the substantial progress of hydrogen extraction, is purge gas on the upstream side,
That is, the gas comes into contact with the purge gas containing almost no extracted hydrogen and having a very low hydrogen concentration via the hydrogen separation membrane 20. This state is shown in FIG. Note that FIG.
In (b), the length along the flow path shown on the horizontal axis is represented such that the upstream side of the reformed gas flow path is on the left side and the downstream side is on the right side. The movement of hydrogen from the reformed gas to the purge gas is performed in accordance with the difference in hydrogen concentration between the two as described above. However, as shown in FIG. Reformed gas passage 33 and purge gas passage 3
Since the hydrogen concentration difference between the gases flowing in the respective flow paths is maintained at a certain value or more over the entire flow path length of 0, hydrogen extraction by the hydrogen separation membrane 20 is effectively performed over the entire flow path.

On the other hand, in the case where the two types of gases are flowed in the same direction (see FIG. 4A), the reformed gas on the upstream side, that is, the reformed gas in which the hydrogen concentration is high and the hydrogen concentration is not high yet is high. The pure gas comes into contact with the purge gas on the upstream side, that is, the purge gas containing almost no extracted hydrogen and having a very low hydrogen concentration, through the hydrogen separation membrane 20.
Also, the downstream reformed gas, that is, the reformed gas whose hydrogen concentration has decreased due to the substantial progress of hydrogen extraction, is the same as the downstream purge gas, that is, the purge gas containing a large amount of extracted hydrogen and having a high hydrogen concentration. , Through the hydrogen separation membrane 20. This is shown in FIG. On the upstream side, the hydrogen concentration difference between the reformed gas and the purge gas is extremely large, and hydrogen extraction by the hydrogen separation membrane 20 is actively performed. On the downstream side where the hydrogen concentration difference between the two is small, hydrogen extraction is not sufficient. Will not be performed. Therefore, as in the present embodiment, it is desirable to flow the two types of gases in opposite directions in order to sufficiently secure the hydrogen extraction efficiency in the entire hydrogen extraction apparatus 10.

The purge gas passage 30 and the reformed gas passage 33 may be disposed adjacent to each other with the hydrogen separation membrane 20 interposed therebetween, and the arrangement of both may be reversed. That is, in the hydrogen extraction device 10, the flow path formed in the hydrogen separation component 12 is changed to the reformed gas flow path 33.
The flow path formed between the hydrogen separation component 12 and the outer shell side wall 14 may be the purge gas flow path 30.

According to the hydrogen extraction apparatus 10 of the present embodiment configured as described above, the space inside the hydrogen extraction apparatus 10 is divided into a reformed gas flow path by a plurality of stacked hydrogen separation membranes and spacers. 33 and a purge gas channel 30. Therefore, by forming the hydrogen extraction device by stacking the hydrogen separation membranes, in addition to the effect of reducing the size of the entire device and securing the surface area of the hydrogen separation membrane to improve the efficiency of hydrogen extraction, The effect of suppressing the manifold structure from becoming complicated and large due to drawing the gas into the gas flow path formed as described above can be obtained. Furthermore, since the gas is led to the flow paths formed on the respective hydrogen separation membranes by the spacers disposed between the stacked hydrogen separation membranes, a manifold composed of a tubular flow path or the like is separately provided to supply the gas. The shape of the connection part of the flow path can be simplified as compared with the case where the wiring is performed. That is, in the present embodiment, the connection between the hydrogen separation membrane 20 and the inner spacer 24 or the connection between the hydrogen separation membrane 20 and the outer spacer 26 can be performed by bonding substantially parallel surfaces to each other. It becomes easy to secure the sealing performance of the part. In addition, by simplifying the shape of the connecting portion of the flow path, the connection between the above members, such as disposing a seal member between the members,
By using a general-purpose bonding method such as brazing or glass bonding, sufficient sealing performance can be easily ensured (an example of a specific structure of the connection portion will be described later).

Further, according to the hydrogen extraction apparatus 10 of the present embodiment, since the purge gas flows into the flow path through which the hydrogen extracted from the reformed gas by the hydrogen separation membrane 20 flows, the hydrogen permeating the hydrogen separation membrane 20 is It is immediately removed downstream and does not stay in the flow path. Therefore, the efficiency of hydrogen extraction can be sufficiently maintained. Further, in two flow paths provided with the hydrogen separation membrane 20 interposed therebetween,
Since the reformed gas and the purge gas flow in opposite directions, the efficiency of hydrogen extraction can be ensured sufficiently high in the entire hydrogen extraction device 10 as described above.

When the space inside the hydrogen extraction device 10 is divided into two flow paths by the hydrogen separation membrane 20 and the spacer, a spacer (an inner spacer 24 and an outer spacer 26) is formed at an end of the hydrogen separation membrane 20. A rectifying plate (purge gas rectifying plate 22 and reformed gas rectifying plate 2
8), the surface area of the hydrogen separation membrane 20 can be more effectively used for hydrogen extraction. That is, the reformed gas in the reformed gas flow path 33 can flow along the surface of the hydrogen separation membrane 20 until the flow direction is changed by the spacer at the end of the hydrogen separation membrane 20,
When performing the operation of extracting hydrogen, substantially all the membrane surfaces of the hydrogen separation membrane 20 can be effectively used for hydrogen extraction.

If a hydrogen extraction device is constructed by stacking hydrogen separation membranes, as described above, it is possible to secure a sufficient area of the hydrogen separation membrane while making the entire device compact. As in the hydrogen extraction apparatus 10 of the embodiment, the gas flow paths formed on the respective stacked hydrogen separation membranes 20 are connected in series, and the gas flow paths formed on the respective hydrogen separation membranes 20 are stacked in the stacking direction. In this configuration, the gas can flow more sequentially, so that the efficiency of hydrogen extraction can be more sufficiently secured than in the case where gas flow paths formed on each hydrogen separation membrane are connected in parallel. Play. Here, a hydrogen extraction device 310 is shown in FIG. 18 as an example of a configuration in which gas channels formed on each hydrogen separation membrane are connected in parallel. In FIG.
Only the stacked layers and the flow of gas are shown, and members common to the hydrogen extraction device 10 are given member numbers obtained by adding the value 300.

When the gas flow paths formed on the respective stacked hydrogen separation membranes 20 are connected in series as in the hydrogen extraction apparatus 10 of this embodiment, the flow directions of the reformed gas and the purge gas are It is possible to easily realize a configuration in which the components are opposed to each other, and thereby it is possible to increase the efficiency of hydrogen extraction as described above. In contrast, the hydrogen extraction device 3
When the gas flow paths formed on each hydrogen separation membrane 220 are connected in parallel as in 10, it is extremely difficult to make the flow directions of both gases opposite. In FIG. 18, in the flow path formed on the hydrogen separation membrane, the flow directions of the reformed gas and the purge gas are configured to be orthogonal to each other, but the flow directions of both gases may be opposed to each other. Then, the configuration related to the piping and connection of the gas flow path becomes extremely complicated, and it is practically difficult to adopt the configuration.

Further, in the hydrogen extraction device 10 of this embodiment,
Since the gas sequentially flows in the gas passage formed on each hydrogen separation membrane 20, a gas having a flow rate corresponding to the amount of gas supplied to the hydrogen extraction device 10 flows in each gas passage, In the extraction device 10, the operation of hydrogen extraction proceeds at a predetermined efficiency according to the supplied gas amount. On the other hand, when the gas flow paths are connected in parallel as in the hydrogen extraction device 310, the flow paths formed on the respective hydrogen separation membranes are always uniformly or constantly set. In addition, it is difficult to stably distribute the gas, and there is a possibility that the operation of extracting hydrogen may not be performed at the expected efficiency. Further, when the gas flow paths formed on the respective stacked hydrogen separation membranes 20 are connected in series as in this embodiment, the reformed gas flow path 33 and the purge gas flow path When a design change is made for the flow path length of 30, such a design change can be easily made by adjusting the number of members to be laminated.

Further, the configuration in which the gas flow paths formed on each hydrogen separation membrane 20 are connected in series has an effect that the structure of the manifold can be simplified more than the configuration in which the gas flow paths are connected in parallel. . That is, as shown in FIG. 18, when the above-mentioned respective flow paths are connected in parallel, a manifold for distributing the gas supplied to the hydrogen extraction device to the respective stacked flow paths, A manifold is required to collect the gas discharged from the road (Fig. 1
8), the hydrogen extraction device 10 of the present embodiment does not require such a configuration for distribution, and can further simplify the structure of the manifold and the structure for connection thereof.

In the hydrogen extraction apparatus 10 shown in FIG. 1 and FIG. However, a plurality may be provided. In consideration of the state of the gas flow at each inlet of the gas supplied from the outside and the state of the gas flow when the gas is discharged to the outside from each outlet, for example, the gas flow on the surface of the hydrogen separation membrane 20 is considered. The number and positions of the supply ports or discharge ports may be appropriately set so that the flow becomes more uniform.

Further, as described above, the gas flow in the purge gas passage 30 or the reformed gas passage 33 is
A member (a baffle plate or the like) for rectifying the flow of gas may be further provided near the above-described inlets or outlets so that the state becomes more uniform on the hydrogen separation membrane 20.

Here, the sealing method and the holding method of each member will be further described. FIG. 5 shows an example of a configuration related to the connection between the hydrogen separation membrane 20 and the spacer (the inner spacer 24 or the outer spacer 26). FIG. 5 shows only a main part related to the connection between the hydrogen separation membrane 20 and the spacer in a cross section similar to the cross section of the hydrogen extraction device 10 shown in FIG. As described above, the hydrogen separation membrane 2
Numeral 0 is a member formed by supporting a hydrogen separation metal on a porous substrate. In the present embodiment, at the connection portion between the hydrogen separation membrane 20 and the spacer, the end of the porous base material (the region related to the connection with the spacer) is used so that the sealing performance is not impaired by the porous base material having air permeability. ) To cover the
It was formed of a material that was gas impermeable and had sufficient heat resistance. The coating portion 21 can be formed of, for example, a metal material that does not transmit hydrogen, such as stainless steel, and according to the material, using a method such as glass coating, glass impregnation, silver mirror reaction, plating, and sputtering.
It may be formed by coating a predetermined region of the hydrogen separation membrane 20.

In order to secure a sufficient bonding area between the spacer and the hydrogen separation membrane 20, the bent portion 25 is formed on the spacer.
Is provided. Coating part 2 provided on hydrogen separation membrane 20
A seal portion 23 having a structure for preventing gas leakage between the purge gas flow channel 30 and the reformed gas flow channel 33 is provided between 1 and the bent portion 25 provided on the spacer. The seal part 23 can be constituted by a gasket, for example. Alternatively, the spacer and the coating portion 21 may be bonded by brazing or glass bonding, and the sealing portion 23 may be configured by the bonding portion. Depending on the spacer, the porous base material, or the material forming the coating portion 21, the sealing portion 2
The configuration of No. 3 may be appropriately selected. If the spacer is formed to be sufficiently thick and a sufficient area can be secured as a connection surface substantially parallel to the hydrogen separation membrane 20, the bent portion 2
5 may not be provided.

FIG. 6 is an explanatory view showing an example of a method of holding the purge gas flow regulating plate 22 disposed in the hydrogen separation component 12. Here, in the cross section of the hydrogen extraction device 10, only the main parts related to the holding of the purge gas straightening plate 22 are shown. In addition, in FIG. 11 to be described later from FIG. 6, a line corresponding to the center line of the hydrogen extraction device 10 is shown as an AA line in the drawings, similarly to FIGS. 1 and 2. The purge gas flow control plate 22 is disposed between two adjacent hydrogen separation membranes in the hydrogen separation component 12, and the purge gas flow path 3 formed between the two hydrogen separation membranes is formed.
0 is a member that guides the flow of purge gas along the hydrogen separation membrane. The purge gas straightening plate 22 shown in FIG.
The purge gas circulation section 27 (FIG. 6)
) Is formed as a disc-shaped structure having a hole or notch near its outer periphery. The purge gas straightening plate 22 formed as such a disk structure is
The outer peripheral portion is connected to the outer spacer 26. Purge gas straightening plate 22 formed as a disc-shaped structure
As shown in FIG. 6, the purge gas rectifying plate 22 can be accurately disposed at a desired position between the two hydrogen separation membranes 20 by supporting the outer periphery of the purge gas rectifying plate 22.

FIG. 7 is an explanatory view showing another example of the method of holding the purge gas straightening plate 22. Similar to FIG. 6, only the main parts related to holding the purge gas straightening plate 22 in the cross section of the hydrogen extraction device 10 are shown. Is shown. The purge gas straightening plate 22 shown in FIG. 7 is provided so as to be connected to a stay 40 connecting the inner peripheral portions of the adjacent hydrogen separation membranes 20 instead of being connected to the outer spacer 26 as shown in FIG. (Integrally formed). The stay 40 is provided between two adjacent hydrogen separation membranes 20 along a hole provided at the center of the hydrogen separation membrane 20 in the hydrogen separation component 12.
It is a member that connects between them. By providing such a connection with the stay 40, the purge gas rectifying plate 22 disposed substantially in parallel with the hydrogen separation membrane 20 is held in the hydrogen separation component 12. The strength (with respect to the force applied in the stacking direction) of the extraction device 10 can be improved. Stay 4
0 indicates a purge gas flow path 4 which is a path of the purge gas.
1 and a bent portion 46 for securing an adhesion area between the hydrogen separation membrane 20 and the hydrogen separation membrane 20 (see FIG. 7). The connection method between the bent portion 46 of the stay 40 and the hydrogen separation membrane 20 is based on the hydrogen separation membrane 20 described above.
What is necessary is just to follow the method of connection between the and the spacer.

Further, the purge gas flow regulating plate 22 may be connected to the outer spacer 26 as shown in FIG. 6 and may be held integrally with the stay 40 as shown in FIG. FIG. 8 shows such a configuration.
Shown in As shown in FIG. 7, the adjacent hydrogen separation membrane 20
It is said that the strength of the hydrogen extraction device 10 can be further improved by further providing a member (stay 40) for connecting between them, and by connecting this member to the outer spacer 26 as shown in FIG. It works.

Next, a method for holding and connecting the reformed gas flow control plate 28 will be described with reference to examples. FIG. 1 shows a state in which the reformed gas straightening plate 28 is provided on the inner wall of the side wall member 15. FIG. 9 is a cross-sectional view of the same configuration as that of FIG. FIG. 10 shows that the reformed gas straightening plate 28 is
FIG. 10 is an explanatory view showing a state of a main part of a cross section similarly to FIG. 9, which illustrates a configuration molded integrally with an inner spacer 24 in place of FIG. As shown in FIG. 10, when the reformed gas straightening plate 28 is formed integrally with the inner spacer 24, the reformed gas straightening plate 28 is
A hole for forming a reformed gas flowing portion 42 which is a passage of the reformed gas is provided in the vicinity of a connection portion with the reformed gas 4. Further, the reformed gas flow control plate 28 and the inner wall surface of the outer shell side wall 14 are connected by providing a seal portion 43. In the seal portion 43, both can be connected by a simple method of disposing a seal material such as alumina mat, for example. Of course, the two parts are bonded together by brazing, glass bonding, etc.
3 may be formed to secure more sufficient sealing performance. Donut-shaped reformed gas straightening plate 28
As shown in FIG. 10, the outer peripheral portion is held at both the outer peripheral portion and the inner peripheral portion (the outer peripheral portion is connected to the outer shell side wall 14, and the inner peripheral portion is connected to the inner spacer 24), whereby more accurate In addition, it becomes possible to dispose the reformed gas straightening plate 28 at a desired position between the two hydrogen separation membranes 20.

FIG. 11 shows a state in which a stay 44 is provided between two adjacent hydrogen separation membranes 20 forming a reformed gas flow path 33 therebetween to connect the two. Provided in connection with 44 (for example, molded integrally)
Show the situation. In the configuration shown in FIG.
Is provided. Also, stay 44
The inner wall and the connecting portion of the outer shell side wall 14 are provided with the same sealing portion 43 as in FIG. By providing the stay 44, in the hydrogen extraction device 10 (with respect to the force applied in the stacking direction)
Strength can be further improved. Figure 1
11 and the configuration of FIG. 11, the reformed gas flow control plate 28 may be connected to all of the inner spacer 24, the stay 44, and the inner wall of the outer shell side wall 14. With such a configuration, both effects obtained by the configuration of FIG. 10 and the configuration of FIG. 11 can be obtained.

The reformed gas straightening plate 28 and the stay 44 or the purge gas straightening plate 22 and the stay 40
It is not necessary to integrally mold at the time of manufacture, and a member including a current plate and a stay may be formed by combining and bonding a plurality of members. Also, stay 40
Holes formed in the purge gas flow portion 41,
Various shapes can be selected for the hole provided in the waste 44 and forming the reformed gas flowing portion 45 as long as the gas can pass therethrough. For example, a region where the purge gas flow portion 41 is formed in the stay 40 and a region where the reformed gas flow portion 45 is formed in the stay 44 may be formed in a mesh shape. In addition, since the stays 40 and 44 described above connect between two adjacent hydrogen separation membranes 20, an effect of improving the strength of the hydrogen extraction device 10 can be obtained. Two adjacent
The gas rectifying plate can be supported even if it is configured to be connected to only one of the two hydrogen separation membranes 20.

In the hydrogen extraction apparatus 10 of the above embodiment,
As described above, the internal space is formed by the stacked hydrogen separation membranes 20 and the spacers connecting them.
Divided into the reformed gas channel 33 and the purge gas channel 30,
The size of the whole is reduced while securing the area of the hydrogen separation membrane involved in hydrogen extraction, and the manifold structure is simplified. Further, the space inside the hydrogen extraction device 10 is divided in this way to divide the reformed gas passage 33 and the purge gas passage 30.
Is formed, the flow direction of the reformed gas and the flow of the purge gas passing through the reformed gas flow path 33 and the purge gas flow path 30 adjacent to each other with the hydrogen separation membrane 20 interposed therebetween are set to the opposite directions. And the efficiency of hydrogen extraction can be improved. Here, in the above embodiment, each hydrogen separation membrane 20 to be laminated is formed in a donut shape so that the whole is formed in a cylindrical shape, and between the outer periphery of the hydrogen separation membrane 20 and the outer shell side wall 14, and the hydrogen separation membrane Since the central portion corresponding to the hole of the membrane 20 is configured like a manifold, the gas flow state (flow rate) is made uniform throughout each hydrogen separation membrane in performing hydrogen extraction, and the entire hydrogen separation membrane is Can be obtained more effectively. That is, the above-described configuration in which the hydrogen separation membrane has a donut shape is such that the flow of the gas flowing from the gas flow path configured in the central portion into a flow path formed on each hydrogen separation membrane 20 from the gas flow path configured like a manifold, and It is desirable that the flow of gas flowing from the gas flow path formed like a manifold along the inside of the shell side wall into the flow path formed on each hydrogen separation membrane 20 becomes highly uniform. Furthermore, the configuration in which the doughnut-shaped or disk-shaped members are stacked to form the entire hydrogen extraction device 10 into a cylindrical shape is different from the case where the hydrogen extraction device is formed by stacking polygonal members. When the internal temperature rises during operation and each member thermally expands, there is an effect that strength is advantageous.

As described above, it is desirable to make the hydrogen extraction device 10 cylindrical so that each hydrogen separation membrane 20 can be easily operated without waste.
May have different shapes. If the uniformity of the flow of the gas passing over the hydrogen separation membrane 20 can be ensured to a desired degree, for example, a laminated member such as a hydrogen separation membrane or a rectifying plate is formed as a square plate-like member, and the entire hydrogen extraction apparatus is formed. May be formed in the shape of a quadrangular prism. Such a configuration,
FIG. 12 schematically shows a modification of the first embodiment.
FIG. 12 shows the inside of a hydrogen extraction device 10A in which a hydrogen separation membrane and a flow straightening plate formed as a rectangular plate-like member are stacked with spacers interposed therebetween, with one side surface cut off. FIG. In the hydrogen extraction device 10A of FIG. 12, members corresponding to the configuration of the hydrogen extraction device 10 are indicated by adding "A" to the member numbers.

In the hydrogen extraction device 10A, the hydrogen extraction device 1
As shown in FIG. 2, a hydrogen separation component forming a flow path therein is not configured, but the flow of gas in the hydrogen extraction device 10A is similar to that of the hydrogen extraction device 10 shown in FIG. Similarly, that is, the hydrogen extraction device 10
Is the same as the cross section of the region on one side from the center line. In such a case as well, the area of the hydrogen separation membrane is sufficiently ensured and the manifold structure is simplified, whereby the sealability of the connection portion can be easily ensured, and the reformed gas flowing through the reformed gas flow path It is possible to improve the efficiency of hydrogen extraction by causing the gas flow direction to oppose the purge gas flowing through the purge gas flow path. Also in the hydrogen extraction device 10A shown in FIG. 12, various configurations described in the first embodiment (for securing the sealing performance at the connection between the members and improving the strength of the hydrogen extraction device) are also used. 5 to 11) can be applied.

(2) Structure of the hydrogen extraction device 110 of the second embodiment: The hydrogen extraction device 10 of the first embodiment shown in FIG. 12 and further, the outer shell side wall 1 is provided outside the hydrogen separation component 12.
4 is assembled. Here, a hydrogen extraction device that realizes the same operation as the hydrogen extraction device 10 is
It can be formed by stacking members having a shape that facilitates assembly. Such a configuration,
A second embodiment will be described below.

FIG. 13 shows a hydrogen extraction apparatus 11 according to the second embodiment.
FIG. 2 is an explanatory diagram showing an outline of a configuration of No. 0. FIG. 13 is a schematic cross-sectional view illustrating the configuration of the hydrogen extraction device 110, and also illustrates the flow of gas inside. In the hydrogen extraction device 110, the outer wall-integrated reformed gas flow path member 50 and the purge gas flow path member 52, each of which is a member having a circular cross section, are provided with a hydrogen separation membrane, which is a donut-shaped thin plate member, between them. It is constituted by laminating. FIGS. 14A, 14B, and 14C are perspective views showing appearances of the purge gas flow path member 52, the hydrogen separation membrane 120, and the outer wall-integrated reformed gas flow path member 50, respectively. Note that, in the cross-sectional view of FIG. 13, these stacked members are shown separated from each other, but the actual hydrogen extraction device 110 is
Each member is laminated in a predetermined order while securing a sufficient sealing property while sandwiching a sealing member such as a gasket between the members,
The entire structure is maintained by applying a predetermined pressing force in the laminating direction.

In FIGS. 13 and 14, the members corresponding to the above-described members provided in the hydrogen extraction device 10 of the first embodiment have the member numbers obtained by adding the value 100 to the member numbers assigned by the hydrogen extraction device 10. Is attached. 13 and FIG. 14, similarly to FIG. 1 and FIG.
The center line of 0 was designated as line AA. Hydrogen extraction device 11
In FIG. 0, the outer wall-integrated reformed gas flow path member 50 has a side wall portion 115 that constitutes a structure corresponding to the outer shell side wall 14 in the hydrogen extraction device 10 when the members are stacked to form the hydrogen extraction device 110. , A reformed gas flow regulating plate 128, an inner spacer 124, and a stay 144. Here, the inner spacer 124 is provided as a convex structure formed on the inner peripheral portion of the reformed gas straightening plate 128 formed in a donut-shaped flat plate shape, and inside the inner spacer 124, a purge gas flow path is formed. Hole 170 is provided. Also, the stay 144 is provided with the reformed gas straightening plate 1.
A protrusion 172 is formed between the stay 144 and the side wall 115. The recess 172 forms a flow path for the reformed gas. In such an outer wall-integrated reformed gas flow path member 50, in a region where the reformed gas straightening plate 128 is formed, a hole 160 that forms a passage for the reformed gas is provided near a connection portion with the inner spacer 124. The stay 144 is provided with a hole 162 that forms a passage for the reformed gas.

In the hydrogen extraction device 110, the concave portion 1 provided on one surface side of the outer wall-integrated reformed gas flow path member 50 is provided.
The reformed gas that has reached the flow path formed by
Hole 1 formed in stay 144 forming the inner wall surface of 72
It flows into the flow path formed on one surface side of the reformed gas straightening plate 128 via 62, and flows toward the inner peripheral portion along one surface of the reformed gas straightening plate 128. Such a reformed gas flows into a flow path formed on the other surface side of the reformed gas rectification plate 128 through a hole 160 provided on an inner peripheral portion of the reformed gas rectification plate 128, This reformed gas straightening plate 12
8 flows toward the outer peripheral portion along the other surface. Such a reformed gas is supplied to the stay 1 formed on the other surface side.
When the stay 144 is reached, the holes 16 of the stay 144 are provided.
2, flows out to the flow path formed by the concave portion 172 provided on the other surface side, and further flows through the flow path formed by the concave portion 172 provided in the adjacent outer wall integrated reformed gas flow path member 50. Are successively guided to a similar flow path formed by the adjacent outer wall-integrated reformed gas flow path member 50.

The purge gas flow path member 52 integrally includes a purge gas flow regulating plate 122, an outer spacer 126, and a stay 140. Here, stay 140
Is provided as a convex structure formed on the inner peripheral portion of the doughnut-shaped flat plate-shaped purge gas rectifying plate 122, and the purge gas Recess 1 that forms a flow path
74 are provided. Also, the outer spacer 126
Is provided as a convex structure formed on the outer peripheral portion of the purge gas straightening plate 122. In such a purge gas flow path member 52, in a region where the purge gas straightening plate 122 is formed, a hole 164 that forms a passage for the purge gas is provided near a connection portion with the outer spacer 126. A hole 166 that forms a passage for the purge gas is provided.

In the hydrogen extraction device 110, the purge gas reaching the flow path formed by the concave portion 174 provided on one surface side of the purge gas flow path member 52 is removed by the concave portion 174.
Hole 16 provided in a stay 140 formed around
6, flows into a flow path formed on one surface side of the purge gas straightening plate 122, and flows toward the outer peripheral portion along one surface of the purge gas straightening plate 122. Such a purge gas flows into a flow path formed on the other surface side of the purge gas straightening plate 122 through a hole 164 provided on an outer peripheral portion of the purge gas straightening plate 122, and the other side of the purge gas straightening plate 122. Flows toward the inner periphery along the surface of. When the purge gas reaches the stay 140 formed on the other surface side, the purge gas passes through the hole 166 provided in the stay 140 and the recess 17 formed on the other surface side.
4 flows through the flow path formed by the hole 170 provided in the adjacent outer wall-integrated reformed gas flow path member 50 (and the flow path formed by the hole provided in the hydrogen separation membrane 120). , A purge gas flow path member 5 disposed next to the
2 are successively guided to the same flow path formed by them.

As described above, the hydrogen separation membrane 120 is a donut-shaped thin plate-shaped member.
The inner wall of the inner spacer 124 in the outer wall-integrated reformed gas flow path member 50 and the inner circumference of the stay 140 in the purge gas flow path member 52 have substantially the same diameter. The outer circumference of the hydrogen separation membrane 120 is formed to have substantially the same diameter as the outer circumference of the stay 144 in the outer wall-integrated reformed gas flow path member 50 and the outer circumference of the outer spacer 126 in the purge gas flow path member 52. ing. These members are connected to an outer wall-integrated reformed gas flow path member 50, a hydrogen separation membrane 120, a purge gas flow path member 52,
A predetermined number of the hydrogen separation membranes 120 and the outer wall-integrated reformed gas flow path member 50 are stacked in this order, and the outer cover 116 is provided at the upper and lower ends to complete the hydrogen extraction device 110. The flow of the reformed gas and the purge gas in the hydrogen extraction device 110 is shown in FIG.
Can realize the same operation as the hydrogen extraction device 10 of the first embodiment.

In the hydrogen extraction device 110, the side wall portion 11 of the adjacent outer wall integrated reformed gas flow path member 50 is provided.
In FIG. 14, the part connecting the five elements 5 is indicated as an area with a “+” sign. Such a connection site,
For example, by arranging a sealing member such as a gasket between the members, the sealing property can be easily ensured.
Further, a connection portion between the hydrogen separation membrane 120 and an adjacent member (a connection portion between the inner spacer 124 provided in the outer wall-integrated reformed gas flow path member 50 and the inner peripheral portion of the hydrogen separation membrane 120,
A connection between the stay 140 provided in the purge gas flow path member 52 and the inner periphery of the hydrogen separation membrane 120, a connection between the stay 144 provided in the outer wall integrated reformed gas flow path member 50 and the outer periphery of the hydrogen separation membrane 120, the purge gas The connection between the outer spacer 126 provided in the flow path member 52 and the outer peripheral portion of the hydrogen separation membrane 120) can be bonded in the same manner as in the first embodiment. That is, a structure similar to that of the coating portion 21 is provided on the inner peripheral portion or the outer peripheral portion of the hydrogen separation membrane 120, and a structure similar to that of the seal portion 23 is provided between the adjacent member and the coating portion 21, so that a sufficient seal What is necessary is just to ensure the property (see FIG. 5). In addition, in order to secure the sealing property between the members to be stacked, if the gasket is used as described above and the pressing force is applied and held in the stacking direction in the hydrogen extraction device 110, the assembling operation is simplified. can do. Further, when the members are bonded by a method such as brazing or glass bonding, it is not necessary to hold the hydrogen extraction device 110 by applying the above pressing force.

According to the hydrogen extracting apparatus 110 of the second embodiment configured as described above, all of the parts involved in the adhesion between the members to be laminated are substantially parallel to each other. As compared with the hydrogen extraction device 10 described above, it is possible to more easily ensure the sealing performance between the members. For example, in the hydrogen extraction device 10 of the first embodiment, when connecting the two side wall members 15 and the two outer shell lids 16, it is necessary to simultaneously connect non-parallel surfaces (see FIG. 1). . In order to ensure sufficient sealing performance at these connection surfaces in such a configuration, when manufacturing each member,
Each member must be formed with strict accuracy. On the other hand, in the present embodiment, when each member is sequentially stacked, it is only necessary to secure the sealing property in a plane substantially parallel to the stacking surface. Does not require strictness in Therefore, the manufacturing process (the process of forming the member) can be simplified, and the manufacturing cost can be reduced.
Furthermore, when the hydrogen extraction device 110 is manufactured, the respective members may be stacked in a predetermined order, so that the assembling operation can be further facilitated.

As described above, in the hydrogen extraction apparatus, it is desirable that the reformed gas and the purge gas be configured to flow in opposite directions. It is also possible to make it flow in the direction. Of course, the hydrogen extraction device 110
In the above, the configuration may be such that the side of the reformed gas channel and the side of the purge gas channel are interchanged.

(3) Modification: In the first and second embodiments, the hydrogen separation membrane 20 or the hydrogen separation membrane 120 is formed by supporting a hydrogen separation metal on a porous substrate. On the other hand, a configuration in which a hydrogen extraction device is manufactured using a hydrogen separation membrane formed of only a metal material by combining a plurality of types of metals is also preferable. For example, in the hydrogen extraction device of the above embodiment, the hydrogen separation membranes 20, 120
Alternatively, a metal film having a sandwich structure provided with a palladium or palladium alloy film may be used on both surfaces of a substrate made of a Group 5 metal or a Group 5 metal alloy. FIG. 15 shows a modified example of such a structure of the hydrogen separation membrane 220.

FIG. 15 shows a hydrogen separation membrane 22 as a modification.
It is explanatory drawing showing the mode of the cross section of 0. Hydrogen separation membrane 22
0 denotes a substrate portion 60 and coating portions 62 formed on both surfaces thereof.
And As described above, the substrate section 60 is formed of a Group 5 metal or an alloy of a Group 5 metal. 5
The group metals include vanadium, niobium, and tantalum. The covering portion 62 is formed of palladium or a palladium alloy as described above.

Here, the mechanism by which hydrogen is extracted by the hydrogen separation membrane will be described. The operation of extracting hydrogen from the hydrogen-containing gas using the hydrogen separation membrane is considered to proceed as follows. That is, first, on the surface of the hydrogen separation membrane, a step in which each hydrogen molecule is separated into two hydrogen atoms proceeds, and then, a step in which hydrogen atoms pass through the hydrogen separation membrane 20 proceeds. The process in which the hydrogen atoms that have permeated into the hydrogen bond to form hydrogen molecules proceeds. Therefore,
The hydrogen separation membrane is required to have the activity of promoting the above-described reaction of separating hydrogen molecules and bonding of hydrogen atoms, and the activity of allowing hydrogen atoms to pass through the inside.

Palladium and palladium alloys are metals having both the activity of promoting the separation of hydrogen molecules and the reaction of bonding of hydrogen atoms, and the permeability of hydrogen (atoms). Group 5 metals or Group 5 metal alloys have hydrogen (atomic) permeability, and the hydrogen permeability is better than palladium or palladium alloys. In the hydrogen separation membrane 220 made of such a material, the separation of hydrogen molecules and the reaction of bonding of hydrogen atoms are promoted by palladium or a palladium alloy constituting the covering portion 62 formed on the surface. . The hydrogen atoms generated in the covering portion 62 move inside the substrate portion 60 toward the other surface.

According to such a hydrogen separation membrane 220, the thickness of the hydrogen separation membrane can be increased without impairing the hydrogen permeability of the hydrogen separation membrane. That is, as the hydrogen separation membrane is formed thinner, the hydrogen permeability thereof can be improved, but the Group 5 metal or the Group 5 metal alloy constituting the substrate portion 60 is more palladium or a palladium alloy. Has excellent hydrogen permeability. Therefore, by forming the substrate portion 60 using a Group 5 metal or a Group 5 metal alloy, the substrate portion 60 can be formed to be thicker while ensuring sufficient hydrogen permeability. Therefore, compared to the case where the hydrogen extraction function is realized only by palladium or a palladium alloy,
The thickness of the hydrogen separation membrane can be increased while ensuring sufficient hydrogen separation ability. For example, even if the thickness of the hydrogen separation membrane 220 is about several tens of μm, it is possible to sufficiently secure the hydrogen permeability of the entire hydrogen separation membrane 220. Therefore,
The hydrogen separation membrane 220 composed of only a metal material without using a porous substrate has sufficient strength for handling when assembling the hydrogen extraction device and sufficient strength for functioning in the hydrogen extraction device. And a self-supporting film having a sufficient thickness.

In the hydrogen separation membrane 220, palladium or a palladium alloy in an amount sufficient to promote the separation of hydrogen molecules and the reaction of bonding of hydrogen atoms may be secured on the surface. Therefore, the thickness of the covering portion 62 can be made extremely thin (for example, 1 μm or less), and the production cost can be reduced by reducing the amount of expensive palladium.

Further, the metal material is excellent in strength against vibration and heat resistance as compared with ceramics. for that reason,
By using the hydrogen separation membrane 220 composed of only a metal material, the durability of the hydrogen extraction device can be improved as compared with the case where a hydrogen separation membrane having a ceramic porous substrate is used. Further, when the entire hydrogen extraction device is made of a metal material using the hydrogen separation membrane 220, the thermal expansion coefficient of the entire device can be made uniform. Can be improved.

As the metal forming the covering portion 62, a metal having sufficiently high activity to promote the separation of hydrogen molecules and the reaction of bonding of hydrogen atoms may be used as described above.
As described above, palladium or a palladium alloy is preferable, but another noble metal may be used. In addition, the substrate section 60 may further contain another kind of metal such as nickel in addition to the group 5 metal or the group 5 metal alloy.

Various methods can be used for manufacturing the hydrogen separation membrane 220. Here, the substrate section 6
The case where 0 is formed of vanadium and the covering portion 62 is formed of palladium will be described.

For example, a vanadium foil serving as the substrate portion 60 having a desired thickness is formed by rolling, and a film is formed on both surfaces of the vanadium foil using palladium. As a film formation method using palladium, plating or chemical vapor deposition (C
VD) or a known film forming method such as physical vapor deposition (PVD). Alternatively, after joining a palladium sheet or forming a palladium layer on both surfaces of a vanadium sheet to form a sandwich-like sheet, this sheet is rolled to form a hydrogen separation membrane 2.
20 may be manufactured.

When manufacturing the hydrogen extraction device, the hydrogen separation membrane 220 may be joined to an adjacent member by using a sealing member such as a gasket, brazing, A method such as glass bonding can be used. Further, a hydrogen separation membrane 2 made of only a metal material
When using 20, it is also possible to join with an adjacent member by diffusion bonding. Diffusion bonding is a method in which metal members to be bonded are heated and pressurized at a temperature lower than the melting point, and bonded by utilizing the diffusion of atoms. At the contact surface, both metals to be joined diffuse into each other, and the two are integrated. Like diffusion bonding and brazing,
When a joining method that does not involve melting of the base material is used, the entire device can be made thinner.

Further, in the hydrogen separation membrane 220, a covering portion 62 made of palladium may not be formed in a region related to bonding with an adjacent member (a region not related to hydrogen permeation). FIG. 16 shows a hydrogen separation membrane 220A as an example of such a hydrogen separation membrane. Hydrogen separation membrane 2
20A is formed in the same donut shape as the hydrogen separation membrane 120, and is used in place of the hydrogen separation membrane 120 in a hydrogen extraction device similar to the hydrogen extraction device 110 of the second embodiment. Further, the hydrogen separation membrane 220A has a sandwich structure including the substrate section 60 and the covering section 62.

In FIG. 16, a region related to connection with an adjacent member when assembling the hydrogen extraction device is indicated by a joint 65.
As shown. The hydrogen separation membrane 220A is
In the region except for (the region involved in hydrogen permeation),
However, the joining portion 65 does not include the covering portion 62. That is, at the joint portion 65, the vanadium layer forming the substrate portion 60 is exposed. When such a hydrogen separation membrane 220A is used, the hydrogen separation membrane 2
It is also preferable that the members (purge gas flow channel member 52 and outer wall integrated reformed gas flow channel member 50) adjacent to 20A are formed of the same material (vanadium) as the substrate unit 60. By forming both with the same kind of metal, the hydrogen separation membrane 220A
Can be performed more favorably, and inconvenience caused by a difference in coefficient of thermal expansion can be prevented.

The joining portion 65 may be covered with a metal of a different type from the metal forming the covering portion 62. In such a case, in the member adjacent to the hydrogen separation membrane 220A, at least a region related to the bonding with the hydrogen separation membrane 220A and the bonding portion 6 of the hydrogen separation membrane 220A.
5 is coated with the same kind of metal. Here, as the metal that covers the adjacent member and the joint portion 65, for example, titanium, copper, aluminum, or the like can be used.

(4) Application to fuel cell device: In the first and second embodiments, a reformed gas flow path is provided in the hydrogen extraction device, and the reformed gas which is a hydrogen-containing gas from which hydrogen is to be extracted is supplied. Is supplied into the reformed gas channel. As an example of a device including the hydrogen extraction device that operates as described above, a configuration of a fuel cell device including the hydrogen extraction device of the present invention will be described below.

FIG. 17 shows the hydrogen extraction apparatus 10 of the above embodiment.
FIG. 1 is an explanatory diagram schematically showing a configuration of a fuel cell device 80 which is an example of a fuel cell device provided with a fuel cell. Fuel cell device 80
Includes a fuel tank 82 for storing reformed fuel, a water tank 84 for storing water, an evaporator / mixer 86 for heating and mixing the reformed fuel and water, and a reforming catalyst for promoting a reforming reaction. The main component is a purifier 88, a hydrogen extraction device 10, a fuel cell 90, and a blower 92. In the following description based on FIG. 17, the fuel cell device 80 includes the hydrogen extraction device 10 described in the first embodiment, but may include the hydrogen extraction device 110 according to the second embodiment.

The reformed fuel stored in the fuel tank 82 is used for a reforming reaction that proceeds in the reformer 88. 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 section 86 has a structure for evaporating and raising the temperature of the reformed fuel supplied from the fuel tank 82 and the water supplied from the water tank 84 and mixing them.

The mixed gas of the reformed fuel and water discharged from the evaporating / mixing section 86 is subjected to a reforming reaction in a reformer 88 to generate a reformed gas (hydrogen-rich gas). Here, the reformer 88 is provided with a reforming catalyst corresponding to the reformed fuel to be used, and the inside of the reformer 88 is adjusted to a temperature suitable for a reaction for reforming the reformed fuel. Temperature is controlled. The reforming reaction that proceeds in the reformer 88 can be selected from various modes such as a steam reforming reaction, a partial oxidation reaction, or a combination of both.
Thus, what is necessary is just to select the thing according to the reforming reaction which advances in the reformer 88.

The reformed gas generated by the reformer 88 is supplied to the reformed gas passage 33 through the reformed gas inlet 34 of the hydrogen extraction device 10 described above, and the hydrogen is converted from the reformed gas to hydrogen. Are separated and extracted. The extracted hydrogen is supplied to the anode side of the fuel cell 90 as a fuel gas. Also,
Compressed air is supplied as an oxidizing gas from a blower 92 to the cathode side of the fuel cell 90. In the fuel cell 90, an electromotive force is generated by an electrochemical reaction using the fuel gas and the oxidizing gas.

Although FIG. 17 shows the main components of the fuel cell device, various types of reformed fuel can be selected as described above, and the fuel cell can be selected according to the reformed fuel used. The configuration of the device 80 may be changed as appropriate.
For example, when using a reformed fuel containing sulfur such as gasoline, a desulfurizer may be provided prior to the evaporating / mixing section 86 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 88 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 of generating 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 80 of the present embodiment configured as described above, in the hydrogen extraction device 10, hydrogen is extracted from the reformed gas generated in the reformer 88, and the hydrogen is extracted from the fuel cell 90. Since the fuel cell 90 is supplied as a fuel gas to the fuel cell 90, a fuel gas having an extremely low content of impurities such as carbon monoxide can be supplied to the fuel cell 90, and the power generation performance of the fuel cell 90 can be stably maintained. . Also,
As described above, the hydrogen extraction device 10 can be configured to be compact as a whole while sufficiently securing the area of the hydrogen separation membrane relating to the extraction of hydrogen from the reformed gas. The whole 80 can be made more compact.

In the above-described embodiment, a configuration has been described in which a predetermined purge gas is supplied to the purge gas passage 30 side of the hydrogen extraction device 10 to improve the efficiency of hydrogen extraction. In the extraction device 10, a gas that does not cause a problem in the electrochemical reaction when supplied to the fuel cell 90 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 purge gas passage 30 as a purge gas. Alternatively, the fuel cell device 80
It is also possible to employ a configuration in which gas discharged from various members constituting the above is used as a purge gas. For example, an anode off-gas discharged from the anode side of the fuel cell 90 after being subjected to an electrochemical reaction can be used as a purge gas. Alternatively, a gas obtained by further reducing the concentration of carbon monoxide in the residual gas discharged from the reformed gas discharge port 35 after hydrogen is extracted by the hydrogen separation membrane 20 may be used as a purge gas.

In FIG. 2, the reformed gas passage 33 and the purge gas passage 30 provided in the hydrogen extraction device 10 are represented as spaces surrounded by predetermined members. The channel 30 may have a configuration in which a porous member is provided inside as long as gas can pass therethrough. When such a hydrogen extraction device is applied to a fuel cell device, a predetermined catalyst can be supported on a porous member provided in the gas flow path. For example, if a porous member is provided in the reformed gas flow path 33 and the above-described reforming catalyst is supported on the porous member, the hydrogen extraction device 10 and the reformer 88 are integrally formed. It becomes possible. In addition, a catalyst relating to the reduction of the concentration of carbon monoxide, such as the above-described shift catalyst or CO selective oxidation catalyst, is supported.
The selective oxidation part 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.

As described above, in the hydrogen extraction device 10, the entire hydrogen extraction device 10 or the hydrogen separation membrane 20 is required to ensure that the hydrogen separation membrane 20 permeates hydrogen.
Although it is possible to provide a heating device for heating the gas, when the catalyst is provided in the gas flow path as described above, the heating device may be provided for the purpose of maintaining the activity of the reaction promoted by the catalyst. It may be. For example, when a reforming catalyst is provided in the reformed gas passage 33, the reformed gas passage 33
A layer provided with a combustion catalyst may be further provided in the vicinity of in order to advance the reaction that generates the heat required for the reaction.

In the above description, the hydrogen extraction device extracts hydrogen from the reformed gas. However, in order to extract hydrogen from a hydrogen-containing gas other than the reformed gas, the hydrogen extraction device of the present invention is used. It may be used. Further, the hydrogen extracted from the hydrogen-containing gas using the hydrogen separation membrane and discharged from the hydrogen extraction device may be supplied to a device consuming hydrogen other than the fuel cell. Alternatively, instead of supplying directly to such hydrogen-consuming devices,
It may be stored once.

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 a hydrogen extraction apparatus 1 according to a preferred embodiment of the present invention.
FIG. 2 is an explanatory diagram showing a configuration of a zero.

FIG. 2 is an explanatory diagram showing a state of a cross section of the hydrogen extraction device 10.

FIG. 3 is an explanatory diagram showing directions in which a reformed gas and a purge gas flow and a hydrogen concentration difference between the two.

FIG. 4 is an explanatory diagram showing directions in which a reformed gas and a purge gas flow and a hydrogen concentration difference between the two.

FIG. 5 is an explanatory diagram illustrating a configuration related to a connection between a hydrogen separation membrane 20 and a spacer.

FIG. 6 is an explanatory view showing an example of a method of holding the purge gas flow regulating plate 22.

FIG. 7 is an explanatory diagram showing an example of a method of holding the purge gas flow regulating plate 22.

FIG. 8 is an explanatory view showing an example of a method of holding the purge gas flow regulating plate 22.

FIG. 9 is an explanatory view showing an example of a method of holding the reformed gas flow plate 28.

FIG. 10 is an explanatory view showing an example of a method of holding the reformed gas flow control plate 28.

FIG. 11 is an explanatory diagram showing an example of a method of holding the reformed gas flow regulating plate.

FIG. 12 is a hydrogen extraction apparatus 10 according to a modification of the first embodiment.
It is explanatory drawing showing the structure of A.

FIG. 13 is an explanatory diagram showing a schematic configuration of a hydrogen extraction device 110 according to a second embodiment.

FIG. 14 shows a purge gas flow path member 52 and a hydrogen separation membrane 12
FIG. 2 is a perspective view showing the appearance of a reformed gas passage member 50 with an outer wall.

FIG. 15 is an explanatory diagram illustrating a state of a cross section of the hydrogen separation membrane 220.

FIG. 16 is a diagram illustrating a hydrogen separation membrane 220A.

FIG. 17 is an explanatory diagram illustrating a schematic configuration of a fuel cell device 80.

FIG. 18 is an explanatory diagram schematically showing the configuration of a hydrogen extraction device 310 that connects stacked channels in parallel.

[Explanation of symbols]

 10, 10A, 110, 310 ... hydrogen extraction device 12 ... hydrogen separation component 14 ... outer shell side wall 15 ... side wall member 16, 116 ... outer shell lid 20, 120, 220, 220A ... hydrogen separation membrane 21 ... coating part 22, 122 ... Purge gas rectifying plate 23 ... Seal part 24,124 ... Inner spacer 25 ... Bent part 26,126 ... Outer spacer 27 ... Purge gas flow part 28,128 ... Reformed gas rectifying plate 30, ... Purge gas flow path 30a ... Manifold area 30b Hydrogen extraction area 31 ... Purge gas inlet 32 ... Purge gas outlet 33 ... Reformed gas flow path 33a ... Manifold area 33b ... Hydrogen extraction area 34 ... Reformed gas inlet 35 ... Reformed gas outlet 40, 140 ... Stay 41 ... Purge gas flow part 42 ... Reformed gas flow part 43 ... Seal part 44,144 ... Stay 45: reformed gas flow section 46: bent section 50: outer wall-integrated reformed gas flow path member 52: purge gas flow path member 80: fuel cell device 82: fuel tank 84: water tank 86: evaporation / mixing section 88: break Porcelain 90 ... Fuel cell 92 ... Blower 115 ... Side wall 160,162,164,166,170 ... Hole 172,174 ... Recess

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) H01M 8/06 H01M 8/06 R (72) Inventor Hiromichi Sato 1 Toyota Town, Toyota City, Aichi Prefecture Toyota Motor F term in reference (reference) 4D006 GA41 HA55 JA02A JA04A JA29A MA03 MA09 MA10 MB04 MB06 MC02 MC03 PA05 PB18 PB66 PC80 4G040 EA03 EB31 FA02 FC01 FD04 FE01 5H027 AA02 BA01 BA16

Claims (19)

[Claims] 1. A hydrogen extraction device for extracting hydrogen from a hydrogen-containing gas containing hydrogen, the hydrogen extraction device comprising: an outer shell forming a predetermined space therein; It is possible to extract hydrogen from the contained gas, and a plurality of hydrogen separation membranes stacked at predetermined intervals in the outer shell, and each of the stacked hydrogen separation membranes in the outer shell. A spacer disposed between the hydrogen separation membranes, securing the predetermined interval between the hydrogen separation membranes, and forming a boundary that separates the predetermined space with the film surface of each of the stacked hydrogen separation membranes; A first flow path through which the hydrogen-containing gas passes, formed in the outer shell by dividing the predetermined space by the membrane surface of each of the stacked hydrogen separation membranes and the spacer; Hydrogen separation membrane surface and spacer in front By dividing a predetermined space, the hydrogen-containing gas is formed on the side facing the first flow path with the hydrogen separation membrane interposed therebetween in the outer shell part, and the hydrogen-containing gas passes through the first flow path. And a second flow path through which hydrogen extracted by the separation membrane passes. 2. The hydrogen extraction device according to claim 1, wherein the first hydrogen is extracted using the hydrogen separation membrane and the spacer.
Forming a hydrogen separation part that forms one of the flow path and the second flow path inside, and the first flow path between the hydrogen separation part and the outer shell part A hydrogen extraction device including the hydrogen separation unit housed in the outer shell so as to form the other of the flow path and the second flow path. 3. Each of the plurality of hydrogen separation membranes is formed in substantially the same shape, is disposed so as to overlap each other when viewed in the laminating direction, and is connected to the spacer at an end thereof. 3. The method according to claim 1, wherein
The hydrogen extraction device according to claim 1. 4. The hydrogen extraction device according to claim 3, wherein the hydrogen separation membrane is formed in a donut shape having an outer periphery in an arc shape and a circular hole in a central portion, and the outer shell portion is a cylinder. In the outer shell portion, the hole of each of the stacked hydrogen separation membranes forms a part of one of the first flow path and the second flow path. The other of the first flow path and the second flow path is formed between the inner surface of the outer shell portion having a cylindrical shape and the outer periphery of each of the stacked hydrogen separation membranes. A hydrogen extraction device characterized by forming a part of a flow path. 5. The hydrogen extraction device according to claim 1, wherein the hydrogen separation membrane and the spacer are formed of a surface of the hydrogen separation membrane and a surface of the spacer substantially parallel to the surface of the hydrogen separation membrane. A hydrogen extraction device that is connected between the hydrogen extraction membrane and the spacer and is sealed so as to ensure airtightness between the hydrogen separation membrane and the spacer. 6. The hydrogen extraction device according to claim 5, wherein the hydrogen separation membrane and the spacer are sealed by any one of gasket, brazing, and glass bonding. 7. The hydrogen extraction device according to claim 5, wherein the hydrogen separation membrane is formed by supporting a hydrogen separation metal on a porous substrate, and the porous substrate is configured to perform the hydrogen separation. A gas-impermeable coat layer that enables airtightness to be secured at a connection portion where the membrane and the spacer are connected, wherein the hydrogen separation membrane and the spacer are sealed between the coat layer and the spacer. A hydrogen extraction device, comprising: 8. The hydrogen extraction device according to claim 1, wherein the hydrogen separation membrane is a film of palladium or a palladium alloy on both surfaces of a base material formed of a Group 5 metal or a Group 5 metal alloy. A hydrogen extraction device. 9. A method according to claim 1, further comprising the step of: disposing between the adjacent hydrogen separation membranes, at least one of the first flow path and the second flow path formed between the adjacent hydrogen separation membranes. The hydrogen extraction device according to any one of claims 1 to 8, further comprising: a gas rectifying plate for partitioning the gas and guiding a gas passing through the partitioned flow path along the hydrogen separation membrane. 10. The hydrogen extraction device according to claim 9, wherein the gas flow regulating plate is formed integrally with at least one of the spacer and the outer shell. 11. A reinforcing member provided between the hydrogen separation membranes adjacent to each other with the gas straightening plate interposed therebetween, and connecting the hydrogen separation membranes and supporting the gas straightening plate. Or the hydrogen extraction apparatus according to 10. 12. The hydrogen extraction device according to claim 11, further comprising the gas flow regulating plate, the spacer, and the reinforcing member, wherein at least a part of the first flow path is provided between the gas flow plate and the hydrogen separation membrane. A second laminated member comprising: a gas rectifying plate, the spacer, and the reinforcing member, wherein at least a portion of the second flow path is formed between the first flow member and the hydrogen separation membrane. The first laminated member, the hydrogen separation membrane, the second laminated member, the hydrogen separation membrane, the members are laminated in this order, between the laminated members adjacent to each other, A hydrogen extraction apparatus, wherein the hydrogen extraction device is connected on a surface substantially parallel to a stacking surface when the members are stacked, and is sealed so as to ensure airtightness between the adjacent members. 13. Passing through the second flow path together with hydrogen extracted from the hydrogen-containing gas, the hydrogen is supplied to the second flow path.
The hydrogen extraction device according to any one of claims 1 to 12, further comprising a derivation gas supply unit configured to supply a derivation gas guided outside the flow path to the second flow path. 14. The hydrogen-containing gas passing through the first flow path and the derived gas passing through the second flow path together with hydrogen extracted from the hydrogen-containing gas are opposed to each other. 14. The hydrogen extraction device according to claim 13, wherein the hydrogen flows in a direction. 15. The first flow path includes a reforming catalyst for accelerating a reforming reaction for generating a hydrogen-containing gas from a hydrocarbon-based fuel, and receives the supply of the hydrocarbon-based fuel to perform the reforming. The hydrogen extraction device according to any one of claims 1 to 14, wherein the hydrogen-containing gas generated by reforming the hydrocarbon-based fuel by a catalyst passes therethrough. 16. The hydrogen extraction device according to claim 15, wherein the first flow path further includes a CO reduction catalyst that promotes a reaction for reducing the concentration of carbon monoxide in the hydrogen-containing gas. 17. The hydrogen extraction device according to claim 1, wherein the hydrogen-containing gas passing through the first flow path further contains carbon monoxide, and the first flow path Is a hydrogen extraction device provided with a CO reduction catalyst that promotes a reaction for reducing the concentration of carbon monoxide in gas. 18. A hydrogen extraction device for discharging hydrogen to the outside, comprising: a plurality of stacked hydrogen separation membranes having a property of selectively permeating hydrogen; and a hydrogen-containing gas containing hydrogen passing therethrough. A first flow path in which a part of a wall surface is formed by the hydrogen separation membrane; and a first flow path adjacent to the first flow path via the hydrogen separation membrane, and the first flow path is formed by the hydrogen separation membrane. A second flow path into which hydrogen extracted from the passing hydrogen-containing gas flows, and a second flow path through which the hydrogen flowing into the second flow path is passed through the second flow path. A derivation gas supply means for supplying a derivation gas guided to the outside of the flow path to the second flow path, wherein the hydrogen-containing gas passing through the first flow path and extracted from the hydrogen-containing gas The derived gas passing through the second flow path together with the hydrogen , The hydrogen extraction apparatus characterized by flow in opposite directions to each other. 19. A fuel cell device comprising a fuel cell which receives a supply of a gas containing hydrogen and a gas containing oxygen, and obtains an electromotive force by an electrochemical reaction using the gas. A fuel cell device comprising the hydrogen extraction device according to any one of the preceding claims, wherein hydrogen extracted by the hydrogen extraction device is used for the electrochemical reaction.