JPH06111838A - Reformer, reforming system, and fuel cell system - Google Patents

Abstract

PURPOSE:To miniaturize a reformer, by forming reforming catalysts on the grooves of one side plate and combustion catalysts on the grooves of the other side plate respectively, and supplying heat required for reforming reaction with these plates alternately laminated to be adopted as a fluid passage. CONSTITUTION:Reforming catalysts 6 are formed on the surfaces of grooves formed in a plate 1, and combustion catalysts 5 are formed on the surfaces of the grooves of a plate 2. The plates 1 and 2 are alternately laminated to supply fuel, composed of a mixture of a compound, including a hydrocarbon group, and water, to a fluid passage 3, formed by a surface having the grooves of the plate 1 and a surface having no groove of the plate 2; and hydrogen is generated by catalysts 6. Fuel and oxygen-containing fluid are supplied to a fluid passage 4 to cause catalyst combustion reaction by the catalyst 5. That is, exothermic reaction and endothermic reaction are concurrently caused at positions adjoined vertically to supply heat, required for reforming reaction, by combustion reaction. Consequently, reforming reaction is made without a burner, and moreover an auxiliary facility such as a reaction tank, heat insulating material, and a reaction pipe is eliminated for miniaturization.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fuel cell system, a reformer and a reforming system for converting a fuel composed of a compound having a hydrocarbon group into hydrogen for supplying hydrogen to the fuel cell, and particularly to a small size TECHNICAL FIELD The present invention relates to a fuel cell system, a reformer, and a reforming system having a structure suitable for conversion.

[0002]

2. Description of the Related Art In recent years, office automation equipment such as word processors and personal computers and household electric appliances have been miniaturized with the development of semiconductor technology and are required to be portable.
Conventionally, in order to satisfy such requirements, a handy primary battery or secondary battery has been used as a power source for these devices. However, the primary battery and the secondary battery are functionally limited in usage time, and the device using such a battery is naturally limited in usage time. When these batteries are used, the battery can be replaced and the device can be moved after the battery is discharged, but the conventional primary battery has a short usage time due to its weight and is not suitable for portable devices. Is.
In addition, the secondary battery can be charged when it is discharged, but on the other hand, it requires an external power source for charging, which limits the place of use and also requires a charging time, which interrupts the operation of the device. is there. In this way, in order to operate various small devices for a long time, conventional primary batteries and secondary batteries are
It is difficult to deal with, and there is a demand for a power supply suitable for longer operation.

One solution to the above problems is to use a fuel cell system instead of the conventional primary battery or secondary battery. Fuel cell systems are currently in practical use as large-scale power plants. In a fuel cell system, power is generated by supplying a fuel and an oxidant to the fuel cell main body, and air is used as the oxidant, and by supplying only the fuel from the outside, continuous power generation is possible. Have Therefore, if the fuel cell system can be miniaturized, it is extremely effective for the operation of various small devices.

Now, in the above fuel cell system,
Usually, a fuel composed of a compound containing a hydrocarbon group and water is reformed into hydrogen gas by a reforming mechanism provided separately from the fuel cell body, and the hydrogen gas is sent to the fuel cell body for power generation. In order to reduce the size of the fuel cell system as described above and provide a power generation system for mounting on equipment, it is necessary to reduce the size and efficiency of the reforming mechanism as well as the fuel cell body.

FIG. 19 is a schematic view of a conventional reforming mechanism including peripheral devices. A heat insulating material 1 is provided on the tank wall of the reforming tank body 101.
02 is provided. The reaction tube installed in the reforming tank main body 101 is composed of an outer tube 103 and an inner tube 104, and the inside of the reaction tube is filled with a reforming catalyst 105 that performs a fuel reforming reaction. . As the material of the reforming catalyst,
Nickel or the like supported on ceramics is used. The burner 106 is installed to heat the reforming catalyst to a temperature that maintains sufficient reforming activity. A mixture of hydrocarbon and water as fuel is supplied from the fuel tank 108 to the heat exchanger 107 by the pump 109. In the heat exchanger 107, the fuel contained in the hydrocarbon group-containing compound and water is heated and vaporized by using the heat of the combustion exhaust gas of the burner 106. The vaporized fuel is the reforming tank body 101.
After being sent to the inner reaction tube and reformed to hydrogen in the reaction tube,
It is supplied to the fuel cell body. On the other hand, the reaction for reforming a mixture of a compound containing a hydrocarbon group and water to obtain hydrogen gas is
For example, when methane is used, CH ₄ + 2H ₂ O → 4H ₂ + CO ₂ −39 kcal / mol (25 ° C.) (1), and when methanol is used, CH ₃ OH + H ₂ O → 3H ₂ + CO ₂ −31 kcal. / mol (25 ° C.) (2), and both are endothermic reactions, as exemplified in (1) and (2) above. In order to cause the above reaction efficiently, it is usually at least 150 ° C in the case of methane, and at least 150 even in the case of using methanol which is reacted at a relatively low temperature
It is necessary to heat the fuel to temperatures above ° C. In order to perform this heating, in the above-described conventional reforming mechanism, the flame of the burner 106 is used for heating. However, considering that the fuel cell system is incorporated in a device or carried, the heating using the flame of the burner causes a risk of disaster such as flame and burn.

Further, in consideration of the influence on peripheral equipment and safety, it is necessary to provide a heat insulating material or the like to prevent the heat in the reaction tank body 101 from leaking to the outside. However, the use of a thick heat insulating material is not suitable for downsizing the reforming mechanism.

Further, although tubes made of stainless steel or the like are used for the reaction tubes and the like in the conventional reforming mechanism, not only the volume of the tube itself is required, but also distortion due to thermal expansion in the length direction is caused. It is necessary to devise such as providing a space to absorb the Further, when a granular catalyst is packed in a reaction tube for use, the tube diameter must be increased to some extent, which also hinders miniaturization.

[0008]

As described above, in consideration of the miniaturization of the reforming mechanism, the conventional reforming mechanism has a burner, a reaction tank, It requires equipment such as a reaction tube, requires a volume per se, and is difficult to miniaturize from the viewpoint of safety.

The present invention has been made in order to solve the above-mentioned problems, and the heat necessary for the reforming reaction can be converted into heat necessary for the reforming reaction without using the above-mentioned auxiliary equipment such as a burner, a reaction tank and a reaction tube. It is an object of the present invention to obtain a reforming mechanism suitable for miniaturization and a fuel cell system using the same, by efficiently supplying a reforming reaction of fuel by supplying the reforming mechanism to the reforming mechanism.

[0010]

According to the present invention, a plurality of flat plates having grooves are laminated to form a fluid passage, and the reforming catalyst is formed on the surface of the groove on one of the adjacent flat plates.
The reformer is characterized in that the combustion catalyst is formed on the surface of the groove of the other flat plate.

The basic structure of the reformer of the present invention will be shown below with reference to FIGS. 1 and 2. In the reformer of the present invention, by stacking at least two flat plates (shown as flat plate 1 and flat plate 2 in FIG. 1) having grooves, the grooved surface of the flat plate 1 and the groove of the flat plate 2 are formed. The fluid flow path 3 by the surface that does not have
Further, the fluid passage 4 is formed by the grooved surface of the flat plate 2 and the grooveless surface of the flat plate 1.

FIG. 2 shows a partial sectional view of the reformer of the present invention. The flat plate 1 and the flat plate 2 shown in FIG. 2 correspond to the flat plate 1 and the flat plate 2 shown in FIG. 1, respectively. The reforming catalyst 6 is formed on the surface of the groove formed on one of the adjacent flat plates 1. A combustion catalyst 5 is formed on the surface of the groove formed on the flat plate 2 adjacent to the flat plate 1. A flat plate 1 on which the reforming catalyst 6 is formed and a flat plate 2 on which the combustion catalyst 5 is formed are alternately laminated.

In the reformer having the above structure, as shown in FIG.
The fluid flow path 3 formed by the grooved surface of the flat plate 1 on which the reforming catalyst 6 is formed and the grooveless surface of the flat plate 2 shown in FIG.
Is supplied with a fuel composed of a mixture of a compound containing hydrocarbon gas and water, and hydrogen is generated by a reforming reaction. Further, in the fluid passage 4 formed by the grooved surface of the flat plate 2 on which the combustion catalyst 5 is formed and the grooveless surface of the flat plate 1,
A fuel and an oxygen-containing gas are supplied, and a catalytic combustion reaction is caused by the combustion catalyst 5 on the surface of the groove of the flat plate 2. The oxygen-containing gas may be replaced by air.

Here, the catalytic combustion reaction occurring in the fluid passage 4 must be an exothermic reaction. The heat generated by the catalytic combustion reaction is conducted to the grooved surface of the flat plate 1 through the flat plate 1 and the reforming catalyst 6 on the surface of the groove of the flat plate 1.
Is used for the reforming reaction that occurs in. That is,
According to the present invention, by stacking a flat plate 2 having a combustion catalyst and a flat plate 1 having a reforming catalyst, a catalytic combustion reaction, which is an exothermic reaction, and a reforming reaction, which is an endothermic reaction, occur simultaneously at adjacent positions. Then, the heat required for the reforming reaction is supplied by the catalytic combustion reaction.

As a result, the reforming reaction can be efficiently generated without using a flame from the burner, and since the structure is a laminated body of flat plates, the burner, reaction tank, heat insulating material, reaction tube, etc. Ancillary equipment is not required, and a small reformer can be provided.

As a method of laminating a layer which causes a reforming reaction and a layer which causes a catalytic reaction, in addition to the constitution of the present invention, one surface of one partition is coated with a reforming catalyst layer. , The other surface is coated with a combustion catalyst layer to form a flow path by alternately forming the flow path on the front and back sides, or by extruding a material to form a number of honeycomb-shaped flow paths and adjoining flow paths. Although a method of supporting different catalysts on the path is conceivable, when considering the production of the reformer with the above structure, as compared with the method of laminating flat plates having one kind of catalyst formed on one side as in the present invention. , It is difficult to change the conditions (calcination temperature, calcination time, calcination atmosphere, etc.) for forming each catalyst layer for each catalyst formation site,
Therefore, a substantially effective catalyst layer cannot be formed. In the reformer of the present invention, since one kind of catalyst is formed on one flat plate, it is practical because optimum forming conditions can be produced for each catalyst.

On the other hand, the material of the flat plate having the groove according to the present invention is not particularly limited, such as ceramics, metal, semiconductors such as silicon, polymer resin plate, etc., but a substance having a large thermal conductivity is preferable.

The flat plate having the groove may be manufactured by mechanically cutting the flat plate of the above material, processing the target groove into a convex shape, and press-molding it with a die. It is also possible to form the groove by chemical processing or the like. It is also possible to form a groove by applying a photosensitive resist on the surface of a flat plate material using a microfabrication technology such as an etching technology or a lithography technology, and exposing and etching using a mask of the desired groove. Known catalysts can be used as the reforming catalyst and the combustion catalyst.

The reforming catalyst is Pt, Ni, Cu, Zn, A
1, Pd, Au, etc. can be used alone or as an alloy. In addition, ZnO, FeO, Cr, Cr ₂ O ₃ ,
BeO, K ₂ O, WO _{3 and the} like can also be used. In addition, Fe ₂ O ₃ —Cr ₂ O _{3 —K 2} O and Cr ₂ O ₃ —Al
Examples include multi-component catalysts such as ₂ O ₃ and Fe ₂ O ₃ —MoO ₃ .

Further, as the combustion catalyst, Pt, Au, A
A noble metal such as g can be used alone or as an alloy. Further Cu, CuO, Cul ₂ , Ag ₂ O, Z
n, Hg, Pd, PdCl ₂ , Co, OsO, Fe, F
eO, MoO ₃ , Cr, V, V ₂ O ₃ , TiO ₃ , Te
O, Se, SeO, P ₂ O ₅ , PbO, Pb, Sn, S
nO, Ba, BaO, Ca, etc. are mentioned. Also,
V ₂ O ₅ -K ₂ SO ₄ -diatomaceous earth, hobucarite (M
nO ₂ , CuO, Co ₂ O ₃ , AgO) and Ag ₂ O-A
l ₂ O ₃ and Cu ₂ O-SeO or _{V 2 O 5 -K 2 SO 4} -
Multi-component catalysts such as silica gel and Fe ₂ O ₃ —Cr ₂ O ₃ are also included.

When these catalysts are formed by forming a porous body on the surface of a groove formed on a flat plate and supporting the porous body by dispersing them in an island shape or in a granular form, the reaction area is increased and the utilization rate of the catalyst is improved. Therefore, it is preferable.

There are various methods for forming the porous body on the surfaces of the grooves of the flat plate. For example, when forming a porous body made of alumina on the surface of a flat plate groove, after coating the groove surface with metallic aluminum, the metallic aluminum is heated in an oxygen atmosphere for oxidation, or an oxidizing agent is used to oxidize it. Then, a porous body made of alumina can be formed. Further, the material of the flat plate itself may be oxidized. For example, when a groove is formed on a substrate made of silicon, the surface of the flat plate is oxidized by masking, a porous body made of SiO ₂ can be formed on the surface of the groove.

The material of the porous body is the above-mentioned Al.
₂ O _3, in addition to _{SiO 2, SiO 2 -Al 2 O} 3 formed by still another method, clay minerals, MgO, TiO
₂ , α-Al ₂ O ₃ , diatomaceous earth, silicone carbide, alundum and the like.

Further, the catalyst can be formed on the surface of the groove of the flat plate by various methods. For example, a method may be used in which a combustion catalyst or a reforming catalyst is used as a target and the catalyst is formed on a flat plate having grooves by sputtering. By forming the catalyst by sputtering, the catalyst can be uniformly formed on the surfaces of the flat plate grooves.

At this time, as a condition for sputtering, it is preferable to use oxygen or hydrogen as an atmosphere gas in which an inert gas such as argon is added in an amount of 0.3 vol% to 3 vol%. As a result, the activity of the catalyst can be increased as compared with the case of using the atmosphere gas containing only the inert gas.

In order to support the catalyst on the surface of the groove of the flat plate having the porous body, the porous layer is irradiated with the metal catalyst by sputtering, or the porous metal layer is impregnated with the catalytic metal salt aqueous solution or colloid. The method of drying and baking after that is mentioned. Alternatively, the raw material component of the porous material and the catalyst component may be coated on a flat plate as a mixed slurry and then dried and fired.

When the catalyst is supported on the porous material formed on the surface of the groove of the flat plate, the concentration of the catalyst particles may be distributed in a gradient as shown in FIG. FIG. 3 is a partial cross-sectional view of a porous body carrying a catalyst. In FIG. 3, the catalyst carrier 12 is a porous body formed on the surface of the flat groove, and 11 is a catalyst particle. It is preferable that the concentration of the catalyst particles is formed so as to be maximum on the fuel passage side.

The porous material in which the catalyst is distributed so as to have a gradient concentration has not only the reformer as in the present invention but also the reforming catalyst on one surface of the partition wall of one plate, It can also be used in a reformer of the type in which an element having a combustion catalyst on the other surface is alternately laminated on the front and back to form a flow path.

FIG. 4 is a partial sectional view showing the structure of the reformer. As shown in FIG. 4, the catalyst carrier 12 is a porous body, and the combustion catalyst particles 13 are supported on one surface in an inclined distribution so that the surface thereof has a higher concentration. On the other surface, the reforming catalyst particles 14 are similarly formed with a gradient distribution so that the surface has a higher concentration. As the structure of the reformer, the catalyst carriers as described above are laminated so that the catalyst surfaces of the same kind face each other and have spaces for forming the fluid flow paths 15 and 16. At the boundary between the portion having the distribution of the combustion catalyst particles 13 and the portion having the distribution of the reforming catalyst particles 14, the fuel and the products supplied to the respective flow paths are not mixed and the heat conduction is hindered. It is preferable to provide a non-heat-conducting separator 17. Further, the fuel and product flow paths 15 can be provided on the surface or inside of each catalyst carrier 12. (FIG. 5) Alternatively, the fuel and product passages 16 may be provided inside the carrier having a concentration gradient, and the carriers having different diameters may be laminated. (FIG. 6) The following method can be mentioned as a method for forming a catalyst carrier having a concentration gradient of the carried catalyst. Here, A or B is a catalyst or a supporting material. 1) Infiltration method

This is a method of melting and permeating another B into the voids of the porous body A to fill it. If B, which has a lower melting point than the porous body A, is used and wets well with the porous body, it permeates into the voids by a capillary phenomenon. It is also possible to combine the green compacts of A and B and infiltrate them while also serving as sinter bonding. In addition, heat treatment is necessary. By using a green compact by changing the void of A or changing the mixing ratio of A and B, a carrier having a concentration gradient of A or B can be obtained. 2) Powder rolling method

The powder A is directly and continuously formed into a compacted plate with a rolling roll, and subsequently sintered into a porous sintered plate, and further hot rolled into a true density rolled plate. In any of these steps, powder B is supplied, and the same step is repeated by changing the amount of powder B to obtain a carrier having a concentration gradient of A and B. 3) Injection molding method

By spraying hot water of A and B with nitrogen gas and spray depositing while rotating a round bar as a cooling collector, the spraying amount of A and B is repeatedly spray deposited. If it is peeled off, a carrier having a concentration gradient of A and B is formed. 4) Other methods Concentration of A and B is made by sintering forging method, hot isostatic pressing method, pseudo hot isostatic pressing method, etc. by making a layer of green compact with different mixing ratio of A and B. It becomes a supporting body that is inclined.

In the reformer using the porous material in which the catalyst is distributed so as to have a gradient concentration, the most active reaction occurs in the surface layer of the porous material with a large amount of fuel permeation, and the fuel The reaction occurs even inside the porous material with low permeation, and an incomplete reaction is unlikely to occur. Therefore, the supplied fuel can be used for reaction to the maximum extent, and it is possible to minimize the catalyst contamination due to the generation of carbon and carbon monoxide due to the incomplete reaction of the fuel or the generation of a substance that becomes a catalyst poison. It In addition, since the reaction occurs inside the porous body, in the reforming reaction and the heat exchange in the catalytic combustion part,
Heat loss is suppressed. Therefore, the efficiency of the reformer is improved.

On the other hand, in the reformer having a structure in which the flat plate on which the reforming catalyst is formed and the flat plate on which the combustion catalyst is formed as shown in FIG. 1 are laminated, the flat plate 1 on which the reforming catalyst 6 is formed. Of the flat plate 2 on which the combustion catalyst 5 is formed by supplying a mixture of hydrocarbon and water to the fluid passage 3 formed by the grooved surface of the flat plate 2 and the flat surface of the flat plate 2 It is necessary to supply a mixture of fuel and oxygen to the fluid flow path 4 formed by the surface having no groove. Also,
Hydrogen, carbon dioxide, and carbon monoxide that are products are generated downstream of the fluid flow path 3, and products such as carbon dioxide and water are generated in the fluid flow path 4, and these products are separately discharged. There is a need. It is preferable to use an internal manifold when supplying and discharging two or more different fluids between the layers of such a laminate. This simplifies the fluid supply pipe and the fluid discharge pipe. FIG. 7 is a perspective view showing a part of the reformer of the present invention. Flat plate 2 in FIG.
Reference numeral 0 has a groove that forms the fluid flow path 21, and a combustion catalyst (not shown) is formed on the surface of the groove.
Similarly, the flat plate 22 also has a groove that forms the fluid flow path 23, and the reforming catalyst (not shown) is formed on the surface of the groove.
Are formed, and the flat plates 20 and the flat plates 22 are alternately laminated. (The lower flat plate 20 and the flat plate 22 are hereinafter referred to as flat plates 20a, 20b ..., Flat plates 22a, 22b ...) Fluid flowing out of the fluid passage 21 in the flat plate 20 in the direction of arrow 24 (in this case, hydrogen) (Gas) exits through a hole 25 opened in the flat plate in connection with the flow path, passes through a hole 26 provided at the same position in the adjacent flat plate 23, and has the same structure as the flat plate 20 laminated further below. In the hole 25 provided in the flat plate 20a, the fluid merges with the fluid from the fluid flow path in the flat plate 20a. In the flat plate 25b, the merging is repeated in the same manner, and the fluid from the fluid flow path on each flat plate is discharged at the bottom of the laminated structure.

On the other hand, the fluid supply will be described by taking the flat plate 22 as an example. Contrary to the case of discharging, the fluid is supplied from the hole 27 provided in the flat plate 22 upstream of the fluid flow path 23 and connected to the fluid flow path, and the hole 28 provided in the adjacent flat plate 22 is supplied. Sent further upward through.

As described above, the holes connected to the fluid flow path and the holes not connected to the fluid flow path are provided at the same positions on both ends of each flat plate, so that the supply piping and the supply piping are provided to each system of the reforming reaction and the combustion reaction. It suffices to connect only one to each of the discharge pipes, which simplifies the pipes.

When the internal manifold as in the present invention is used, the fluid passages 21 and 23 can be parallel or orthogonal depending on the positions where the holes 25 and 26 and the holes 27 and 28 are provided. In particular, by making the fluid flow paths 21 and 23 parallel to each other and adjusting the fuel supply direction of catalytic combustion and the holes provided in the flat plate so that the reformed fuel flows in the same direction and the respective fuel supply directions, The temperature distribution above becomes uniform, and the reforming reaction proceeds more efficiently.

As in the present invention, in a reformer in which a layer that causes an exothermic reaction due to catalytic combustion (catalyst combustion layer) and a layer that causes endothermic reaction due to a reforming reaction (reforming layer) are stacked, the entire reformer is used. When the temperature rises to a target temperature sufficient for the reforming reaction to occur efficiently in the reforming layer, it is preferable to intermittently supply or adjust the fuel to keep the temperature constant.
As a result, the fuel supplied to the catalytic combustion layer is wasted,
In addition, it is possible to prevent a danger due to an excessive rise in temperature. As a method of sending fuel from the fuel tank to the catalytic combustion layer or the reforming reaction layer of the reformer, a valve provided in the pipe connecting the fuel tank and the reformer and a valve regulator for adjusting the fuel supply amount are used. There is a method of controlling in some way and supplying the required amount of fuel. In particular, downsizing can be achieved by using a micropump manufactured by a fine processing technique.

Further, the fuel tank is uniformly pressurized, a part of the pipe connecting the fuel tank and the reformer is made of a shape memory alloy, and the alloy pipe is deformed by a temperature change,
It is also possible to adjust the fuel supply amount. This will be specifically described below.

FIG. 8 is a conceptual diagram showing an example of a reforming system using a pipe made of a shape memory alloy. Fuel tank 4
Part of the pipes (43 and 44 in the figure) for supplying fuel from 1 to the reformer 42 of the present invention is formed of a shape memory alloy. In the figure, 43 is a shape memory alloy pipe for supplying reformed fuel, and 44 is a shape memory alloy pipe for supplying catalytic combustion fuel. The reformer 42 is formed by stacking a catalytic combustion layer and a reforming layer, and fuel can be supplied to each layer from one location by an internal manifold. Such two reformers are stacked with the shape memory alloy pipes 43 and 44 sandwiched therebetween. The shape memory alloy pipes 43 and 44 are connected to the fuel supply holes of the reformer 42. The catalytic combustion fuel supply pipe 44 is opened when the temperature is low and closed when the temperature is high.

Further, the reformed fuel supply pipe 43 is closed when the temperature is low, and is opened when the temperature is high. Specifically, the shape memory alloy pipes 43 and 44 are opened and closed by squeezing, folding, when the pipes reach a certain temperature.
A change in shape such as crushing occurs, the pipe is closed, and the opposite change in shape causes the pipe to open. The shape memory alloy pipes 43 and 44 are laminated on the reformer 42 to open and close the pipes in response to changes in the temperature of the reformer 42 to adjust the amount of fuel to be supplied.

Since the temperature of the reformer 42 is low immediately after the start of the operation, the catalyst combustion fuel supply pipe 44 is opened and fuel is supplied to the catalyst combustion layer in the reformer 42. Catalytic combustion occurs in the layer, the temperature of the reformer 42 rises, and the reforming fuel supply pipe 4
3, the fuel is supplied to the reforming layer of the reformer 42. Further, when the fuel is excessively supplied to the catalyst layer and the temperature of the reformer 42 rises too much, the pipe 44 is closed and the fuel supply is reduced. As described above, the pipes 43 and 44 adjust the amount of fuel supplied according to the change in the temperature of the reformer 42, keep the temperature of the reformer and the amount of reforming constant, and eliminate waste of fuel supply.

Further, the fuel supply pipe using the shape memory alloy, when applied to a fuel cell system in which a reformer and a fuel cell are combined, changes the reformer according to the amount of hydrogen supplied to the fuel cell. It is also possible to add a function of adjusting the fuel supply amount to the fuel tank. This will be specifically described below.

FIG. 9 shows a fuel cell system to which a fuel supply pipe made of a shape memory alloy is applied. 41 in FIG.
Is a fuel tank, 42 is a reformer, and 45 is a fuel cell.
A part of the pipe for supplying the fuel from the fuel tank to the reformer is a pipe 46 made of a shape memory alloy. A heater 47 is installed around the pipe 46 so that the pipe 46 can be heated. The pipe 46 is a pipe that is opened when the heater 47 is not operated and is closed when the heater 47 is operated. The hydrogen generated in the reformer 42 is supplied to the fuel cell through the pipe 48. A pressure sensor is installed in the hydrogen supply hole of the fuel cell 45. The pressure sensor 49 is set to operate the heater 47 around the pipe 46 according to the hydrogen supply amount of the fuel cell. In such a fuel cell system, for example, when hydrogen is supplied from the reformer 42 in excess of the capacity of the fuel cell, the hydrogen pressure in the hydrogen supply hole rises, so the pressure sensor 49 operates and the heater 47 operates. To do. Accordingly, the pipe 46 is closed and the supply of fuel to the reformer is stopped. Further, when the supply of hydrogen becomes low and the hydrogen pressure in the hydrogen supply hole decreases, the operation of the heater 47 stops, the pipe 46 opens, and the fuel is supplied to the reformer 42.

In the above fuel cell system, the operating pressure of the pressure heater and the temperature setting of the heater 47 may be appropriately selected according to the operating conditions of the fuel cell system. A temperature sensor may be used instead of the pressure sensor.

By using the shape memory alloy in the pipe as described above, a compact and lightweight reforming system or a fuel cell system can be obtained without using a valve adjusting device for adjusting fuel. In addition, it is possible to efficiently operate the fuel without wasting fuel.

On the other hand, since the reformer having the structure of the present invention is composed of a flat plate laminated body, it is laminated together with the fuel cell stack (at least the fuel electrode, the oxidant electrode, and the electrolyte plate sandwiched between both electrodes). Therefore, a fuel cell system in which the reformer and the fuel cell are integrated can be provided. Thereby, a compact power generator can be obtained.

FIG. 10 shows a schematic diagram of a fuel cell system comprising a laminate of a reformer and a fuel cell stack of the present invention. In FIG. 10, reference numeral 30 denotes a reformer of the present invention in which a flat plate on which a combustion catalyst or a reforming catalyst is formed is laminated. Further, 31 is an electrolyte plate, 32 is a fuel electrode, and 33 is an oxidizer electrode. The fuel electrode 32 and the oxidant electrode 33 are provided with hydrogen gas and oxidant gas passages 34 and 35, respectively.

In the flow path having the reforming catalyst of the reformer 30,
A fuel comprising a mixture of a compound having a hydrocarbon group such as methanol and steam is supplied. The product hydrogen gas is supplied to the fuel electrode 32 of the fuel cell through the flow path of another system. Further, if the flow path having the reforming catalyst is formed adjacent to the fuel electrode and hydrogen generated in the flow path is directly supplied to the oxidant gas flow path of the adjacent fuel electrode, the piping is simplified. To be done. In this case, it is preferable to provide the hydrogen gas selective permeable membrane 37 between the fuel electrode and the flat plate on which the reforming catalyst is formed, because only pure hydrogen is supplied to the fuel electrode. In addition, the reformer 3
Into the flow path having the combustion catalyst of 0, the air is taken in from the outside as the fuel and the air for combustion, or the waste gas from the air electrode 33 of the fuel cell or a mixture thereof is supplied. As the fuel for combustion supplied to the flow passage, hydrocarbons from the outside or waste gas from the fuel electrode (unreacted hydrogen)
To supply.

In the reformer of the present invention, an exothermic reaction occurs in the flat plate on which the combustion catalyst is formed, and the heat is used for the endothermic reaction on the flat plate on which the reforming catalyst is formed. Further, in the fuel cell, although heat is generated during power generation, it can be used for heating up to an operating temperature at the time of start-up or heating up to an appropriate temperature during power generation.

By stacking the fuel cell and the reformer of the present invention, not only can the size be reduced, but also the heat generated by each can be easily utilized mutually, and the heat utilization rate can be improved. .

In FIG. 10, one fuel cell stack is described as an example, but a plurality of fuel cells and reformers may be alternately stacked. A plurality of fuel cell stacks stacked in series and a reformer may be stacked.

Further, the flat plate forming the reformer is made of a material having electrical conductivity and laminated with the fuel cell stack, so that the fuel cell stack is electrically connected through the laminated flat plate of the reformer. Are connected in series. Therefore, the wiring between the stacks of the fuel cells stacked via the reformer becomes unnecessary, and the electric power of the entire system can be taken out at both ends of the entire stacked structure.

In the present invention, the type of fuel cell to be stacked is not limited, and any fuel cell using a hydrocarbon reformed fuel may be used. For example, a solid polymer electrolyte membrane (for example, trade name Nafion Du Pont),
Fuel cells using hydrogen ion conductors (eg, hydronium or ammonium β-alumina or β-gallia, sintered body of cerium strontium trioxide) as electrolytes, fuel cells using oxygen ion conductors (eg, stabilized zirconium) as electrolytes And so on.

Further, in FIG. 10, when a laminated body of a reformer and a fuel cell using a flat plate made of an electrically conductive material is formed, the fluid passage having the reforming catalyst of the reformer is changed to the fluid passage. And a hydrogen ion (proton) conductive film 37 having catalytic activity and electric conductivity on both sides between the fluid flow path 36 and the hydrogen gas flow path 34 of the fuel cell fuel electrode. It is possible to selectively move hydrogen into the fluid of the fuel electrode of the fuel cell to cause reaction in the fuel electrode of the fuel cell by selectively moving hydrogen from the fluid reformed in (1). In the fluid flow path 36 having a reforming catalyst, a compound containing a hydrocarbon group is reformed to generate hydrogen, carbon monoxide, and carbon dioxide, but unreacted hydrocarbons and water also remain in the fluid. There is. When a hydrogen ion (proton) conductive film 37 having catalytic activity and electrical conductivity on both sides is installed between this fluid and the fluid of the fuel cell fuel electrode, the surface of the film in contact with the flow path 36 having the reforming catalyst serves as an anode. , A potential difference is generated with the surface of the membrane on the side of the fuel cell fuel electrode in contact with the flow path 34 as the cathode. At this time, the following reactions occur at the anode and cathode of the film. Anode: H ₂ → 2H ⁺ + 2e CO + H ₂ O → CO ₂ + 2H ⁺ + 2e cathode; 2H ⁺ + 2e → H ₂ 2H ⁺ + 2e → H ₂

By this reaction, the partial pressures of hydrogen and carbon monoxide in the fluid in the flow path of the reforming catalyst layer are lowered, and the progress of the reforming reaction is promoted. Further, only hydrogen is produced on the surface of the membrane on the side of the fuel cell fuel electrode that is in contact with the flow path 36, and high-purity hydrogen is used for power generation at the fuel cell fuel electrode. The potential difference between the two sides of the membrane is generated by consuming a part of the electric power generated from the fuel cells that are electrically and structurally stacked, and thus does not require external power supply. Further, since the reformer has electrical conductivity, it can be electrically stacked with the fuel cell stack, and no electrical wiring is required. According to the present invention, since the reforming reaction and the electrode reaction of the fuel cell are promoted,
It is possible to improve the utilization efficiency of hydrocarbons and make the device compact. Furthermore, in the present invention, by electrically connecting a capacitor or a secondary battery in parallel to each of the fuel cell stacks, power is supplied to the outside even when power generation at the fuel cell electrodes is insufficient, such as when the system is started. Is possible. Further, the condenser and the secondary battery also serve as a power source at the time of starting when hydrogen is supplied to the fuel cell fuel electrode from the reformer passage through the hydrogen ion conductive film, and thus the system can be easily started. Become.

[0057]

EXAMPLES The reformer of the present invention will be described below with reference to examples. (Example 1)

A photosensitive resist is applied to a nickel plate having a thickness of 0.1 mm, exposed and developed at intervals of 0.15 mm at a pitch of 0.3 mm, and then etched to give a width of 0.18 mm and a depth of 0.6 m.
A plurality of nickel flat plates having grooves with a pitch of 0.3 mm at m were formed.

After masking the obtained flat plate, platinum was used as a target and sputtered for 10 seconds in an argon atmosphere containing 10 ^-3 Torr of pressure and 1% of oxygen to form an average thickness of 0.5 μm on the surface of the groove of the flat plate. An island-shaped combustion catalyst was formed. Ten flat plates (hereinafter referred to as flat plate 2) on which combustion catalysts were formed by the same method were prepared. On the other hand, after masking a nickel flat plate etched by the same method as above, an alloy of copper and zinc was added. Target, pressure 10 ^-3 Torr
r, sputter for 10 seconds in an argon atmosphere of 1% hydrogen,
An island-shaped reforming catalyst having an average thickness of 0.5 μm was formed on the surface of the groove of the flat plate. Ten flat plates (hereinafter referred to as flat plate 1) on which the reforming catalyst was formed were prepared by the same method. The flat plate 1 and the flat plate 2 obtained by the above method were alternately laminated as shown in FIG. 1, and the exterior was wound with glass cotton and aluminum foil to obtain a reformer.

Next, the reformer thus obtained was operated. When a mixed fuel of methanol and air was made to flow through the fluid channel 4 having a combustion catalyst on the surface of the groove, the temperature in the fluid channel 4 rose to about 200 ° C., so that methanol and water were mixed in the fluid channel 3. The fuel mixed with 1: 1 was flowed. As a result, methanol and water were vaporized and further hydrogen was converted. The conversion rate of methanol to hydrogen was 60% to 70%. (Example 2)

Example 1 except that the gas atmosphere during sputtering when forming the reforming catalyst and the combustion catalyst on the flat plate having the grooves was an argon atmosphere containing a pressure of 10 ⁻³ Torr and 1% oxygen. A reformer was obtained in the same manner as in.

The reformer thus obtained was actually operated. When a mixed fuel of methanol and air was made to flow through the fluid passage 4 having a combustion catalyst on the surface of the groove, the fluid passage 4 was formed at the time when a fuel having a volume five times as large as that in the case of Example 1 was made to flow.
Temperature of about 200 ℃. Next, a fuel in which methanol and water were mixed at a ratio of 1: 1 was flown through the fluid passage 3. As a result, methanol and water were vaporized and further converted to hydrogen. The conversion rate of methanol to hydrogen was 15% to 25%. (Example 3)

In this embodiment, the reformer is provided with an internal manifold to supply fuel to the fluid passage having the reforming catalyst.
An example is shown in which the product discharge direction and the fuel supply / product discharge direction to the fluid passage having the combustion catalyst are orthogonal to each other.

First, a silicon wafer ((100) plane, 5
The surface of SiO _{2 is}
Was formed, and a predetermined pattern was transferred using a lithography technique, and then SiO ₂ was selectively removed with hydrofluoric acid. Next, anisotropic etching is performed using an ethylenediamine-based aqueous solution, so that the wafer surface shown in FIG.
A trapezoidal groove 52 was formed as shown in FIG. At this time, the depth of the grooves was about 100 μm, and the pitch was about 1 mm. Both ends of the groove are deep grooves 5 so that the fluids passing through each groove are mixed.
3, 54 are formed, one of which is open for connection with the flow path from below, and the other of which is open only for connection with the upper part. Further, an open groove 55 was formed for connection of one fluid path when the present wafer was alternately laminated for fuel gas and heating fluid. After the completion of each etching step, the entire silicon substrate 51 was shaped as shown in FIG. 11 by dicing.

On the silicon substrate 51 having the fluid path formed as described above, a combustion catalyst layer was formed in the path by a sputtering method or the like. In addition, a method similar to that for the silicon substrate 51 is separately used in FIG.
Silicon substrates 56 to 60 having a shape as shown in 2 were manufactured. A combustion catalyst was formed on the silicon substrates 56 and 58, and a reforming catalyst was formed on the silicon substrate 57. As shown in FIG. 12, the respective wafers were bonded and laminated by the direct bonding method so that the modification reaction substrate 57 and the catalytic combustion substrate 56 were orthogonal to each other.
By directly adhering, for example, by adhering the substrates 56 and 57, the groove formed on the surface of the substrate 56 becomes one flow path by the bottom surface of the substrate 57.

With the structure in which the upper and lower sides of the reforming reaction substrate 57 are the medium burning substrates 56 and 58, the reforming portion of the fuel gas can be heated uniformly. Further, a fuel gas inlet 62, a hydrogen-containing gas outlet 64 after reforming, a heating gas inlet 61, and an outlet 63 are formed in the lowermost and uppermost portions of the laminated structure for piping of each fluid as shown in FIG.

A sectional view of the reformer according to the present invention is shown in FIG. The substrates laminated as described above were fixed in the reforming apparatus by fixing jigs 65 and 66 produced by etching silicon. Minute holes for fuel gas and heating fluid were formed in the fixing jig, and the fixing jig was connected to the pipe with a low melting point glass or the like.

Further, the micro pump 7 manufactured by the fine processing technique is provided in the path from the fuel supply tank to the reformer.
2,73 were installed. This micropump is made by anodic bonding silicon and Pyrex glass. A fluid flow path is formed by etching silicon, and a diaphragm is formed on the Pyrex glass by etching, and a piezoelectric actuator is attached to the upper portion of the diaphragm. By applying a voltage to this actuator, the diaphragm moves up and down to allow a predetermined amount of fluid to flow. (Example 4) An example of a reformer using a porous material in which the supported catalyst has a gradient concentration distribution will be described.

33 g of aluminum oxide (melting point 2050 ° C.) powder was put into a hopper with an opening diameter of 1 mm and allowed to fall naturally, and 10 g of nickel metal powder (melting point 1455 ° C.) was put into a hopper with an opening diameter of 0.1 mm and reciprocated at 50 mm / sec. Tungsten heated to 2500 ° C (melting point 33
(70 ° C) Drop it evenly on the plate. Tungsten heated to 2500 ° C on both sides of the powder drop point (melting point 33
70 ° C.) A roll of nickel-supported aluminum oxide having a thickness of 2 mm is formed while depressurizing the roll from a load of 10 kg to 100 g per second. Similarly, a platinum-supported aluminum oxide rolled body is formed using platinum (melting point: 1773 ° C.) instead of nickel metal powder. The rolled bodies are peeled from the tungsten plate, and the rolled body surface peeled from the tungsten plate is immersed in the molten copper (melting point 1083 ° C.) to the side surface, infiltrated, and then taken out, and the pair of both side surfaces are cut off and cut off. The surfaces that were wet with copper were stacked so that they crossed each other and bonded by thermocompression bonding.

Assembling a reformer by stacking 6 sheets of the shaped plate on the nickel-supported aluminum oxide rolled body surface on the nickel-supported aluminum oxide rolled body surface and the platinum-supported aluminum oxide rolled body surface on the platinum-supported aluminum oxide rolled body surface. It was

Methanol vapor and excess air were made to flow at 2 atm from the cut-off surface of the platinum-supported aluminum oxide porous rolled body having a through passage, while methanol was flown from the cut-off surface of the nickel-supported aluminum oxide porous rolled body having a through passage. Steam equimolar to steam is made to flow at 2 atm.
When a part of the reformer was heated to 150 ° C. or higher and ignited with methanol and oxygen, no change in the hydrogen generation concentration was observed for 100 hours or longer. (Example 5)

In this example, a fuel cell system in which a pipe made of a shape memory alloy is applied to a pipe for supplying fuel from a fuel tank to the reformer in the reformer of the present invention will be described.

As shown in FIG. 14, four holes having a diameter of 5 mm were preliminarily provided as replenishment holes 92, exhaust holes 93, and ventilation holes 94 in thin nickel having a thickness of 0.2 mm and a size of 100 × 300 mm plated on the front and back sides. . Further, the surface was etched to form a pitch of 1 mm, a length of 70 mm, a width of 0.5 mm, a depth of 0.1 mm, a narrow groove 89, a refueling groove 90 and an exhaust groove 91 having a width of 10 mm and a depth of 0.1 mm. For reforming,
Three sheets were prepared for burning each. A cover was attached to the surface of the substrate thus formed except for the irregularities of the fine grooves and each groove, and an oxidation catalyst for combustion and a reforming catalyst for reforming were thinly deposited by sputtering. These are stacked alternately 23
It was pressed at 0 ° C. and laminated to form a reformer. Using the reformer obtained by the above method, a fuel cell system was prepared as shown in FIG.

41 is a fuel tank 42 is the above reformer, 45
Is a fuel cell. In the piping system, a shape memory alloy piping 46 is used as a part of the piping for supplying fuel from the fuel tank 41 to the reformer 42 so that the pressure can be uniformly applied. A heater 47 is wound around the shape memory alloy pipe 46. The shape memory alloy pipe 46 is closed at room temperature, and the heater 47
Open by heating. The shape memory alloy pipe 46 is connected to a forked pipe 80. One of the pipes 80 is connected to the combustion fuel supply shape memory alloy pipe 44 and is connected to the fuel supply hole portion. Shape memory alloy pipe for combustion fuel supply 4
4 is open at room temperature and closes when the temperature reaches the target temperature. An air supply pipe 81 is provided between the combustion fuel supply shape memory alloy pipe 44 and the fuel supply hole 92. The reformed fuel supply shape memory alloy pipe 43 is connected to the region of the pipe 80, and is connected to the reforming fuel supply hole 92. The reformed fuel supply shape memory alloy pipe 43 is closed at room temperature and opened when the temperature rises. The hydrogen gas reformed in the reforming section is supplied to the fuel cell body 45. A pressure sensor 48 is attached to the fuel cell, and when the pressure of the reformed gas exceeds the target pressure, the heater 47 is turned off and the fuel adjustment shape memory alloy pipe 46 is closed. When the pressure decreases, the heater 47 is turned on and the fuel adjusting shape memory alloy pipe 46 is opened again.

The relationship between the laminated reformer 42 and the pipes is such that the laminated reformer 42 is centered around the combustion fuel supply shape memory alloy pipe 44 and the reformed fuel supply shape memory alloy pipe 43.
The shapes of the pipes 18 and 19 are changed according to the temperature change of the reformer. In addition, the heat insulating material 82 is wound around the outer side in this way to improve the thermal efficiency.

The fuel in which methyl alcohol and water were mixed at a molar ratio of 1: 1 was attached to the prepared apparatus. At the beginning of operation, electricity is supplied to heat the heater 47 to open the fuel supply shape memory alloy pipe 46 and supply fuel. It is divided by a forked pipe 80 for heating and reforming, passes through the shape-memory alloy pipe 44 for supplying fuel for combustion, which is open at room temperature, supplies air from the air supply pipe 81, mixes it with fuel, and sends it to the combustion section. The catalyst burned due to catalytic combustion.

The shape memory alloy was heated by the heat, and when the temperature exceeded 120 ° C., the shape memory alloy pipe 43 for supplying reformed fuel, which was closed, was opened and the fuel was supplied to the reforming section.
When the temperature exceeded 140 ° C, the shape-memory alloy pipe 44 for supplying the combustion fuel closed and the temperature rise stopped. The reformed and generated hydrogen was sent to the fuel cell main body 45 to start power generation. Due to the reformed hydrogen, the hydrogen pressure inside the battery is 2.1 kg / cm ^2. When it exceeds the limit, the heater 47 is cut off and the fuel supply shape memory alloy pipe 4
6 was closed and the supply of fuel was stopped. Pressure is 1.8kg /
cm ² In the following cases, the heater 47 was heated again and the fuel for supplying the shape memory alloy pipe 15 for fuel was opened and supplied. The temperature of 120 ° C. to 140 ° C., the reformed hydrogen pressure is 2.
1 kg / cm ² To 1.8 kg / cm ² The fuel cell could be operated continuously. (Embodiment 6) In this embodiment, a fuel cell system in which the reformer of the present invention and a fuel cell stack are stacked will be described.

FIG. 16 is a plan view of a flat plate forming the reforming portion of hydrocarbon fuel in the fuel cell system of this embodiment. The reforming section is a circular flat plate 120, 12 shown in FIG.
It is composed of 1,122. FIG. 16 is a view of the flat plate as viewed from above. Grooves and holes a to h that serve as fluid flow paths are formed in the flat plates 120, 121, and 122, respectively. The flat plates 120, 121, 122 are each made of aluminum and have a thickness of 2 mm and a diameter of 100 mm. Flat plates 120 and 1
A reforming catalyst is formed on the surface of the groove 22 and a combustion catalyst is formed on the surface of the groove of the flat plate 121.
The catalyst was formed on each flat plate by the method described below.

First, the flat plates 120 and 122 are formed with grooves and holes as shown in FIG. 16, and then the surfaces of the grooves are immersed in an aqueous solution of caustic soda to elute part of the aluminum on the surfaces, and then hydrogen peroxide is added. The aluminum layer on the surface was oxidized with an aqueous solution, washed with water and dried to form a porous alumina layer. The porous alumina layer was impregnated with an aqueous solution of copper nitrate and zinc nitrate, dried and calcined, and then subjected to a reduction treatment in a hydrogen stream to support a reforming catalyst. On the flat plate 121, a porous alumina layer is formed in the same manner as the flat plates 120 and 122, and then a similar porous alumina layer is impregnated with an aqueous palladium nitrate solution, dried and fired to carry a combustion catalyst. FIG. 17 is a plan view of a flat plate forming the fuel electrode and the oxidizer electrode of the fuel cell section in the fuel cell system of this embodiment.

The flat plate 123 is an oxidizer electrode, and the flat plate 124 is a fuel electrode. The flat plates 123 and 124 have the same size and the same material as the flat plates 120 to 122, and as shown in FIG.
h is formed.

On the other hand, a catalyst-supporting carbon powder, polytetrafluoroethylene (PTFE: trade name; Teflon) and a Nafion solution were kneaded on both sides of a perfluorocarbon sulfonic acid film (trade name: Nafion) having a thickness of 0.2 mm. Was hot-pressed together with a gold-plated nickel screen, and a hydrogen ion conductive membrane was prepared by pressing a porous carbon plate thereon. Different catalysts were formed on both sides of the membrane, one using platinum / ruthenium and the other platinum.

As an electrolyte plate for a fuel cell, a platinum catalyst-supporting carbon powder and polytetrafluoroethylene (PTFE: trade name; both sides of a perfluorocarbon sulfonic acid film (trade name: Nafion) having a thickness of 0.2 mm were used.
A kneaded mixture of Teflon) and Nafion solution was hot pressed together with a gold-plated nickel screen, and an electrolyte plate was prepared by pressing a porous carbon plate thereon.

From the top of the flat plates 120 to 124, the flat plate 123, the flat plate 124, the flat plate 120, the flat plate 121, and the flat plate 1 are arranged.
22 and the holes a to e provided in each flat plate are stacked so as to form one passage, and the electrolyte is provided between the flat plate 123 (oxidant electrode) and the flat plate 124 (fuel electrode). The plate was sandwiched, and the hydrogen ion conductive film was sandwiched between the flat plate 124 and the flat plate 120 to form one unit. On this occasion,
The surface of the hydrogen ion conductive film on which the platinum / ruthenium catalyst was formed was adjacent to the flat plate 120, and the surface of only the platinum was adjacent to the flat plate 124. Two units of this unit were stacked, and wiring was further performed on the upper and lower parts to form a fuel cell system.

FIG. 18 shows a schematic view of the fuel cell system according to this embodiment. In the figure, 125 is an electrolyte plate, and 126 is a hydrogen ion conductive membrane. Also, the hole a formed by each flat plate
The flow of the feed material and the waste material in the passage formed by ~ e are shown by arrows.

First, the flat plate 124 (fuel electrode) is passed through the hole g.
While supplying hydrogen to the groove of the flat plate 121 (flat plate on which the combustion catalyst is formed), hydrogen and air through holes e through the hole f, and d through the groove of the flat plate 122 (flat plate on which the reforming catalyst is formed). A mixture of methanol and water was fed. Air was also supplied to the flat plate 123 (oxidizer electrode) through the hole e.

On the flat plate 121 (flat plate on which a combustion catalyst was formed), combustion started at room temperature to generate heat. As a result, the reforming reaction also started on the flat plate 122. Hydrogen gas, carbon dioxide, carbon monoxide, and unreacted methanol water generated on the flat plate 122 were sent to the flat plate 120 through the holes h. The flat plate 12
4, the fuel cell unit including the flat plate 123 and the electrolyte plate 125 started power generation as the temperature increased. Operating temperature is 15
When the temperature reaches 0 ° C, the flat plate 124 is formed by the hole g (fuel electrode)
The supply of hydrogen to the plate was stopped, and the hydrogen supplied from the hole f to the flat plate 121 (the flat plate on which the reforming catalyst was formed) was switched to methanol. Power generation continued even after the hydrogen supply was completely stopped.

The temperature of the fuel system was maintained at 150 ° C. by adjusting the amount of methanol supplied to 121. The exhaust gas containing carbon dioxide, unreacted hydrogen and the like generated on the flat plate 120 (the flat plate on which the reforming catalyst was formed) was discharged to the outside through the hole c. Unreacted hydrogen generated on the flat plate 124 (fuel electrode) was discharged to the outside through the hole b, and water vapor generated on the flat plate 123 (oxidizer electrode) was discharged to the outside through the hole a. As described above in detail, a compact fuel cell system in which the reformer and the fuel cell are stacked can be obtained.

[0088]

As described above in detail, according to the present invention, the heat required for the reforming reaction can be supplied without using the equipment such as the burner, the reaction tank, the reaction tube and the like used in the conventional reformer. Therefore, the reformer can be downsized, and the reforming reaction can be efficiently caused. Further, the fuel cell system of the present invention can provide a compact power generation system by being integrated with the reformer.

[Brief description of drawings]

FIG. 1 is a block diagram of a reformer of the present invention.

FIG. 2 is a partial sectional view of a reformer of the present invention.

FIG. 3 is a partial cross-sectional view carrying a catalyst.

FIG. 4 is a configuration diagram of a reformer of the present invention.

FIG. 5 is a cross-sectional view of a catalyst carrier.

FIG. 6 is a cross-sectional view of a catalyst carrier.

FIG. 7 is a perspective view showing a part of the reformer of the present invention.

FIG. 8 is a schematic view of a reforming system using a pipe made of a shape memory alloy.

FIG. 9 is a schematic view of a fuel cell system using a pipe made of a shape memory alloy.

FIG. 10 is a schematic view of a fuel cell system including a reformer and a fuel cell stack of the present invention in volume.

FIG. 11 is a perspective view of a silicon wafer.

FIG. 12 is a partial perspective view of a reformer according to a third embodiment.

FIG. 13 is a sectional view of a reformer according to a third embodiment.

FIG. 14 is a configuration diagram of a flat plate according to a fifth embodiment.

FIG. 15 is a schematic diagram of a fuel cell system according to a fifth embodiment.

FIG. 16 is a plan view of a flat plate forming a reforming section of a fuel cell system according to a sixth embodiment.

FIG. 17 is a plan view of a flat plate forming a fuel cell section of a fuel cell system according to a seventh embodiment.

FIG. 18 is a schematic diagram of a fuel cell system according to a seventh embodiment.

FIG. 19 is a schematic view of a conventional reformer.

[Explanation of symbols]

1, 2, 20, 22 ... Flat plate 3, 4, 15, 16, 2
1, 23, 36 ... Fluid flow path 5 ... Combustion catalyst 6 ... Reforming catalyst 11 ... Catalyst particles 12 ...
Porous substance 13 ... Combustion catalyst particles 14 ... Reforming catalyst particles 1
7 ... Separator 24 ... Arrow 2 showing the direction of fluid flow
5, 26, 27, 28 ... Hole 30, 42 ... Reformer 3
1, 25 ... Electrolyte plate 32 ... Fuel electrode 33 ... Oxidizer electrode 34, 35 ... Gas flow path 37 ... Hydrogen gas selective permeable membrane, hydrogen ion conductive membrane 4
DESCRIPTION OF SYMBOLS 1 ... Fuel tank 43 ... Shape memory alloy piping for reforming fuel supply 44 ... Shape memory alloy piping for catalytic combustion fuel supply
45 ... Fuel cell 46 ... Pipe made of shape memory alloy 47 ... Heater 4
8, 80 ... Piping 49 ... Pressure sensor 51 ... Silicon substrate 52, 55 ... Groove 53, 54 ... Deep groove 56, 58 ... Catalytic combustion substrate 57 ... Reforming reaction substrate
59, 60 ... Silicon substrate 61 ... Heating gas inlet 6
2 ... Fuel gas inlet 63 ... Heating gas outlet 64 ... Hydrogen-containing gas outlet 65, 66 ... Fixing jig 67, 68 ... Fluid inlet 6
9, 70 ... Fluid discharge port 71 ... Container 72, 73 ... Micro valve 81 ... Air supply piping 82, 102 ... Heat insulating material 89 ... Fine groove 90 ... Fuel supply groove 91 ... Exhaust groove 92 ... Supply hole 93 ... Exhaust hole 94 ... Vent 101 ...
Reforming tank body 103 ... Outer tube 104 ... Inner tube 105 ... Reforming catalyst 106 ... Burner 107 ... Fuel exchanger 108 ... Fuel tank 109 ... Pump 110 ... Reaction tube 120, 121, 122, 123, 124 ... Flat plate 12
6 ... Hydrogen ion conductive membrane

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kazuhiko Katsumatsu 1 Komukai Toshiba-cho, Kouki-ku, Kawasaki-shi, Kanagawa Toshiba Research Institute Co., Ltd. Toshiba Town No. 1 Incorporated company Toshiba Research Institute

Claims (5)

[Claims] 1. A plurality of flat plates having grooves are stacked to form a fluid passage, a reforming catalyst is formed on the surface of the groove of one of the adjacent flat plates, and a combustion catalyst is formed on the surface of the groove of the other flat plate. A reformer characterized by being formed. 2. A reformer having a structure in which a catalytic reaction layer that generates heat by catalytically reacting fuel and a reforming reaction layer that reforms fuel are stacked, and a catalytic reaction layer and a reforming reaction layer of the fuel are provided. A reformer characterized in that an internal manifold is used to introduce the gas into the reactor and discharge the product after the catalytic reaction and the product after the reforming reaction to the outside. 3. In a reformer equipped with a porous body carrying a catalyst for converting a fuel composed of a compound having a hydrocarbon group into hydrogen, the catalyst is distributed in the porous body with a concentration gradient. A reformer characterized by that. 4. A reformer comprising a fuel tank for containing fuel, a reformer for reforming the fuel to generate hydrogen, and a pipe for sending fuel from the fuel tank to the reformer,
A reforming system, wherein at least a part of the pipe is made of a shape memory alloy. 5. A fuel cell system comprising a reformer according to claim 1, wherein the flat plate is made of a conductor, and an oxidizer electrode, a fuel electrode, and an electrolyte plate sandwiched between the electrodes.