HK1111266B - Reaction apparatus - Google Patents

Description

Reaction device

Technical Field

The present invention relates to a reaction apparatus for supplying reactants to cause a reaction.

Background

In recent years, fuel cells have been developed for mounting on automobiles, portable devices, and the like as clean power sources having high energy conversion efficiency. A fuel cell is a device that electrochemically reacts fuel with oxygen in the atmosphere to directly obtain electric energy from chemical energy.

Hydrogen is used as a fuel for a fuel cell, but since hydrogen is a gas at normal temperature and pressure, there is a problem in handling. On the other hand, in a reformer fuel cell that reforms (also referred to as reforming or reforming) a liquid fuel having a hydrogen atom such as alcohol or gasoline to generate hydrogen, the fuel can be easily stored in a liquid state. Such a reformer fuel cell needs to include a reaction device including a reaction section having a vaporizer for vaporizing a liquid fuel and water, a reformer (also referred to as a reformer or a reformer) for obtaining hydrogen necessary for power generation by reacting the vaporized liquid fuel with high-temperature steam, a carbon monoxide remover for removing carbon monoxide which is a by-product of the reforming reaction, and the like.

In order to miniaturize such a reforming fuel cell, a small-sized reactor called a microreactor has been developed in which a gasifier, a reformer, and a carbon monoxide remover are stacked. In such a microreactor, a reactor such as a gasifier, a reformer, or a carbon monoxide remover is formed by, for example, joining metal substrates each having a groove formed therein to serve as a flow path for fuel or the like. In such a reaction apparatus, since each reactor needs to be set at a predetermined operating temperature required for the reaction, each reactor may be provided with a heater using a heating wire to heat each reactor and set at a required temperature. Here, the operating temperature of each reactor is relatively high, and in order to suppress heat dissipation to the outside and reduce heat loss to improve thermal efficiency, it is sometimes necessary to provide a heat insulating container and house each reactor in the heat insulating container. However, if a heater is provided in the reaction apparatus to heat the reaction apparatus, a lead wire for applying a voltage to the heating wire of the heater needs to be drawn out from the heat-insulating container to the outside, and heat of the reactor needs to be conducted to the outside through the lead wire, thereby generating heat loss.

On the other hand, among Fuel cells, Solid Oxide Fuel cells (hereinafter referred to as SOFC) have been developed which can improve power generation efficiency for high-temperature operation. In this case, a power generation element (generation cell) in which a fuel electrode is formed on one surface of a solid oxide electrolyte and an oxygen electrode is formed on the other surface thereof can be used. Since the SOFC reaction proceeds at a relatively high temperature (about 500 to 1000 ℃), the power generating element is housed in the heat insulating container, and the piping serving as a supply passage for the fuel gas or oxygen and a discharge passage for the exhaust gas, or the anode output electrode and the cathode output electrode penetrate the heat insulating container and are connected to the power generating element in the heat insulating container. However, in the SOFC, since the operating temperature of the power generating element is relatively high, the temperature difference between the power generating element and the anode output electrode and the cathode output electrode exposed to the outside is large, and heat loss through these electrodes tends to increase.

Disclosure of Invention

The present invention relates to a reaction apparatus having a structure in which a reactor of a reaction part is set at a predetermined temperature, the reaction apparatus including a heat-insulating container for accommodating the reaction part, and the reaction apparatus having an advantage of being capable of reducing heat loss due to heat conduction from the reactor inside the heat-insulating container to the outside.

The first reaction apparatus of the present invention for achieving the above advantages comprises: a reaction section to which a reactant is supplied and which is set at a predetermined temperature to cause a reaction; a plurality of electrodes provided on the reaction section; a heat insulating container which accommodates the reaction part therein via a heat insulating space; and a supply/discharge unit which is composed of a conductor, has one end connected to the reaction unit and the other end led to the outside through a wall surface of the heat insulating container, and supplies a reactant to the reaction unit and discharges a reaction product from the reaction unit, wherein at least one of the plurality of electrodes is electrically connected to the supply/discharge unit.

The second reaction apparatus of the present invention for achieving the above advantages includes: a reaction section having a power generating element which has two electrodes of a positive electrode and a negative electrode, is set at a predetermined temperature, and receives electric power from each of the electrodes by an electrochemical reaction of a reactant; a heat-insulating container which accommodates the reaction part therein via a heat-insulating space; a supply/discharge unit which is composed of a conductor, has one end connected to the reaction unit and the other end led out to the outside after penetrating the wall surface of the heat insulating container to connect between the heat insulating container and the reaction unit, and supplies the fuel for power generation to the reaction unit and discharges the reaction product from the reaction unit; wherein one of the two electrodes in the power generating element is electrically connected to the supply/discharge portion.

An electronic device according to the present invention for achieving the above advantages includes a reaction device and a load, the reaction device including: a reaction section to which a reactant is supplied and which is set at a predetermined temperature to cause a reaction; a plurality of electrodes provided on the reaction section; a heat insulating container which accommodates the reaction part therein via a heat insulating space; a supply/discharge unit which is composed of a conductor, has one end connected to the reaction unit and the other end led out to the outside after penetrating the wall surface of the heat insulating container to connect between the heat insulating container and the reaction unit, supplies a reactant to the reaction unit and discharges a reaction product from the reaction unit, and is electrically connected to one electrode of the reaction unit; a power generation element that obtains electric power by an electrochemical reaction of a reactant, wherein at least one of the plurality of electrodes is electrically connected to the supply and discharge portion; the load is driven by the electric power obtained from the power generation element.

Drawings

FIG. 1 is an exploded perspective view of a microreactor module (reaction apparatus) and a heat-insulating box covering the microreactor module in embodiment 1 of the reaction apparatus of the present invention.

Fig. 2 is a schematic side view of the micro-reactor module according to embodiment 1 divided for each function.

Fig. 3 is a plan view showing the vicinity of a joint between the heating wire and the tube on the lower surface of the micro-reactor module according to embodiment 1.

Fig. 4 is an IV-IV sectional view of fig. 3.

FIG. 5 is a plan view showing a modification example 1 of the vicinity of a joint between a heating wire and a tube material on the lower surface of a micro-reactor module according to embodiment 1.

Fig. 6 is a sectional view in the direction VI-VI in fig. 5.

FIG. 7 is a plan view showing a modification example 2 of the vicinity of a joint between a heating wire and a tube on the lower surface of a micro-reactor module according to embodiment 1.

Fig. 8 is a sectional view taken along line VIII-VIII of fig. 7.

FIG. 9 is a plan view showing a modification example 3 of the vicinity of the joint between the heating wire and the tube on the lower surface of the micro-reactor module according to embodiment 1.

Fig. 10 is an X-X sectional view of fig. 9.

Fig. 11 is a perspective view showing an example of a power generation unit (generator unit) including the micro-reactor module according to embodiment 1.

FIG. 12 is a sectional view showing an example 1 of a wiring structure of an assembly portion in a power generation cell of a micro-reactor module according to embodiment 1.

FIG. 13 is a sectional view showing a 2 nd example of a wiring structure of an assembly portion in a power generation cell of a micro-reactor module according to embodiment 1.

Fig. 14 is a perspective view showing an example of an electronic device using a power generation unit as a power source.

FIG. 15 is a block diagram showing the structure of an electronic apparatus according to embodiment 2 of the reaction apparatus of the present invention.

Fig. 16 is a schematic view of a power generating element of embodiment 2.

Fig. 17 is a schematic diagram showing an example of stacking of power generating elements.

FIG. 18 is a perspective view of a reaction apparatus according to embodiment 2.

Fig. 19 is a view from XIX in fig. 18.

FIG. 20 is a perspective view showing the internal structure of a heat-insulating box of the reaction apparatus according to embodiment 2.

Fig. 21 is a perspective view of the internal structure of the reaction apparatus of fig. 20 as viewed from the lower side.

Fig. 22 is a view in section from XXII to XXII in fig. 18.

FIG. 23 is a schematic view showing an electron flow pattern in the reaction apparatus according to embodiment 2.

Fig. 24 is a bottom view of the connection part, the reformer, and the fuel cell part in the reaction apparatus of embodiment 2.

Fig. 25 is a view in section from XXV to XXV of fig. 24.

Fig. 26 is a view in elevation of XXIV-XXIV of fig. 24.

Fig. 27 is a view in section from XXVII to XXVII in fig. 26.

Fig. 28 is a schematic view showing the temperature distribution in the heat-insulating box during steady operation in the reaction apparatus according to embodiment 2.

Fig. 29 is a simulation diagram showing the deformation of the anode output electrode due to a temperature rise in the reaction device according to embodiment 2.

Fig. 30, 31, 32, and 33 are perspective views showing modifications of the internal structure of the heat insulating box in the reaction apparatus according to embodiment 2.

Detailed Description

Hereinafter, the reaction apparatus of the present invention will be described in detail based on the embodiments shown in the drawings. However, in the embodiments described below, various technically preferable limitations are added to practice the present invention, but the scope of the present invention is not limited to the embodiments and the illustrated examples below.

< embodiment 1 >

First, embodiment 1 of the reaction apparatus of the present invention will be described.

FIG. 1 is an exploded perspective view of a microreactor module (reaction apparatus) and a heat-insulating box covering the microreactor module in embodiment 1 of the reaction apparatus of the present invention.

Fig. 2 is a schematic side view of the microreactor module according to the present embodiment separated for each function.

The micro-reactor module 600 is built in an electronic device such as a notebook computer, a PDA, an electronic notebook, a digital camera, a cellular phone, a watch, a recorder, a projector, etc., and generates hydrogen gas used in a fuel cell.

As shown in fig. 2, the microreactor module 600 includes: a supply and discharge part 602 for supplying a reactant or discharging a product, a high temperature reaction part (1 st reaction part) 604 set at a relatively high temperature (1 st temperature) to cause a shift reaction, a low temperature reaction part (2 nd reaction part) 606 set at a temperature (2 nd temperature) lower than the set temperature of the high temperature reaction part 604 to cause a selective oxidation reaction, and a connection part 608 for transferring the reactant or the product between the high temperature reaction part 604 and the low temperature reaction part 606, and the microreactor module 600 is housed in an insulating box (insulating container) 791.

In the supply and discharge portion 602, supply of the reactant from the outside of the insulated casing 791 into the micro-reactor module 600 or discharge of the product from the micro-reactor module 600 to the outside of the insulated casing 791 are performed.

As shown in fig. 2, the supply/discharge section 602 includes a vaporizer 610 and a 1 st combustor 612, and 5 pipes 626, 628, 630, 632, and 634 arranged around the combustors.

Water and liquid fuel (for example, methanol, ethanol, dimethyl ether, butane, gasoline, etc.) are supplied from a fuel container to the vaporizer 610 in a state of being separated or mixed, and the water and the liquid fuel are vaporized in the vaporizer 610 by the combustion heat in the 1 st burner 612.

Air and a gaseous fuel (e.g., hydrogen, methanol, ethanol, dimethyl ether, butane, gasoline, etc.) are supplied to the 1 st burner 612 in the form of separate or mixed gases, respectively, and heat is generated by catalytic combustion thereof.

The 5 tubes 626, 628, 630, 632, 634 serve as flow paths for supplying reactants to the microreactor module 600 or flow paths for discharging products from the microreactor module 600. For example, the flow path is a flow path for supplying fuel and air to the 1 st burner 612 and the 2 nd burner 614 described later, a flow path for discharging exhaust gas from the 1 st burner 612 and the 2 nd burner 614, a flow path for supplying oxygen to the carbon monoxide remover 500 described later, and a flow path for supplying the mixed gas (hydrogen-rich gas) in which carbon monoxide is removed in the carbon monoxide remover 500 to the fuel cell.

The 5 tubes 626, 628, 630, 632, 634 are made of a conductor and also function as leads for applying voltage to the heating wires 720, 722 described later.

The high-temperature reaction section 604 is mainly provided with a 2 nd burner (heating section) 614 and a reformer 400 provided on the 2 nd burner 614.

Air and a gaseous fuel (e.g., hydrogen, methanol, ethanol, dimethyl ether, butane, gasoline, etc.) are supplied to the 2 nd burner 614 in the form of separate or mixed gases, respectively, and heat is generated by catalytic combustion thereof.

The mixed gas obtained by vaporizing water and the liquid fuel is supplied from the vaporizer 610 to the reformer 400, and the reformer 400 is heated by the 2 nd burner 614. In the reformer 400, hydrogen gas or the like is generated from the water vapor and the vaporized liquid fuel by a catalytic reaction, and a small amount of carbon monoxide gas is generated. When the fuel is methanol, chemical reactions of the following formulas (1) and (2) occur. Further, the reaction of generating hydrogen is an endothermic reaction, and combustion heat of the 2 nd burner 614 is used.

CH₃OH+H₂O→3H₂+CO₂(1)

2CH₃OH+H₂O→5H₂+CO+CO₂(2)

The low-temperature reaction section 606 is mainly provided with the carbon monoxide remover 500.

A mixed gas containing hydrogen gas and a slight amount of carbon monoxide gas generated by the chemical reaction in the above (2) is supplied from the shift converter 400 to the carbon monoxide remover 500, and air is also supplied. In the carbon monoxide remover 500, carbon monoxide in the mixed gas is selectively oxidized by heating by the 1 st burner 612, thereby removing carbon monoxide. The mixed gas (hydrogen-rich gas) from which carbon monoxide has been removed is supplied to the fuel electrode of the fuel cell.

The connection portion 608 is provided with a flow path for supplying a reactant to the high-temperature reaction portion 604 or a flow path for transferring a product in the high-temperature reaction portion 604 to the low-temperature reaction portion 606. Specifically, the 2 nd burner 614 is provided with a flow path for supplying fuel and air, a flow path for discharging the exhaust gas from the 2 nd burner 614, a flow path for supplying water and fuel vaporized in the vaporizer 610 to the shift converter 400, and a flow path for supplying the product of the shift converter 400 to the carbon monoxide remover 500.

The heating wires (heating portions) 720 and 722 are formed by patterning a metal film, for example. As shown in fig. 1 and 2, the heating wire 720 is arranged in a serpentine shape on the lower surface of the low-temperature reaction part 606, and the heating wire 722 is arranged in a serpentine shape on the lower surface from the low-temperature reaction part 606 to the high-temperature reaction part 604 through the connection part 608. Here, when the low temperature reaction portion 606, the connection portion 608, and the high temperature reaction portion 604 are made of a conductor, an insulating layer 640 such as silicon nitride or silicon oxide is formed on the lower surfaces thereof, and the heating wires 720 and 722 are formed on the surface of the insulating layer 640. By patterning the heating wires 720, 722 on the insulating layer 640, the voltage to be applied is not short-circuited.

In addition, when the lower surfaces of the low temperature reaction portion 606, the connection portion 608, and the high temperature reaction portion 604 are made of an insulator such as ceramic, the insulating layer 640 is not necessary, and the heating wires 720 and 722 can be directly patterned.

The heating wire 720 heats the low temperature reaction part 606 when activated, and the heating wire 722 heats the high temperature reaction part 604 and the connection part 608 when activated.

Both ends of the heating wire 720 are connected to the pipes 630 and 632. The ends of the heating wire 722 are connected to the pipes 626 and 634. Next, the structure of the connection portion will be described.

Fig. 3 is a plan view showing the vicinity of the junction between the heating wire and the tube on the lower surface of the microreactor module according to the present embodiment.

Fig. 4 is an IV-IV sectional view of fig. 3.

As shown in fig. 3 and 4, an insulating layer 640 is provided on the lower surface of the low-temperature reaction portion 606, and a heating wire 720 is formed on the surface of the insulating layer 640.

An adhesive layer 730 is provided on the surface of the insulating layer 640 at the connection portion with the pipe 630 of the low-temperature reaction portion 606. The adhesive layer 730 is formed such that a portion thereof overlaps with the end of the previously formed heating wire 720. The adhesive layer 730 is provided with a through-hole 731 at the same position as the hole 606a leading to the inside of the low-temperature reaction portion 606. The adhesive layer 730 has excellent adhesion to the insulating layer 640, and the end of the tube 630 is brought into close contact with the surface opposite to the insulating layer 640, whereby the tube 630 is bonded to the low-temperature reaction part 606, and the channel 630a in the tube 630 is connected to the hole 606 a.

The adhesive layer 730 has conductivity, and conducts the heating wire 720 and the tube 630. As such an adhesive layer 730, for example, gold plating can be used.

Similarly, the tube 632 is electrically connected to the heating wire 720, and similarly, the tubes 626 and 634 are electrically connected to the heating wire 722.

Thus, the low-temperature reaction portion 606 can be heated by applying a voltage between the pipe members 630 and 632, and the high-temperature reaction portion 604 can be heated by applying a voltage between the pipe members 626 and 634.

Next, a modification of the connection portion between the heating wire and the tube in the microreactor module according to the present embodiment will be described.

[ modification 1]

Fig. 5 is a plan view showing a modification example 1 in the vicinity of a joint between a heating wire and a tube on the lower surface of a micro-reactor module according to the present embodiment.

Fig. 6 is a sectional view in the direction VI-VI in fig. 5.

In the above fig. 3 and 4, the adhesive layer 730 is formed so as to overlap the end portions of the heating wires 720 and 722 formed previously, but for example, as shown in fig. 5 and 6, the heating wires 720 and 722 may be formed after the adhesive layer 730 is formed, and the end portions of the heating wires 720 and 722 may be overlapped with the adhesive layer 730 formed previously.

[ modification 2]

FIG. 7 is a plan view showing a modification example 2 of the vicinity of a joint between a heating wire and a tube on the lower surface of a micro-reactor module according to the present embodiment.

Fig. 8 is a sectional view taken along line VIII-VIII of fig. 7.

As shown in fig. 7 and 8, the heating wires 720 and 722 and the adhesive layer 730 may be provided on the surface of the insulating layer 640 at intervals, and then the heating wires 720 and 722 and the adhesive layer 730 may be connected by a conductive wire 740, and the heating wires 720 and 722 and the adhesive layer 730 may be electrically connected by the wire 740. Here, the wire 740 may be 1 wire or a plurality of wires.

[ modification 3]

FIG. 9 is a plan view showing a modification example 3 of the vicinity of a joint between a heating wire and a tube on the lower surface of a micro-reactor module according to the present embodiment.

Fig. 10 is an X-X sectional view of fig. 9.

As shown in fig. 9 and 10, the heating wires 720 and 722 and the adhesive layer 730 may be provided on the surface of the insulating layer 640 at intervals, and then a conductive solder 750 may be provided between the heating wires 720 and 722 and the adhesive layer 730, so that the heating wires 720 and 722 and the adhesive layer 730 are electrically connected by the solder 750.

The following explains the heat-insulating box in the reaction apparatus of the present embodiment.

As shown in fig. 1, the micro-reactor module 600 includes a heat insulating box 791. The heat insulating box 791 is constituted by a rectangular cover 792 having an open lower surface and a plate 793 blocking the lower surface opening of the cover 792. In a state where the supply/discharge portion 602 is inserted into the holes 794, 795 provided in the plate 793, the plate 793 is joined to the cover 792, and the high-temperature reaction portion 604, the low-temperature reaction portion 606, and the connection portion 608 are accommodated in the heat insulating box 791.

The heat-insulating box 791 reflects heat radiation from the microreactor module 600 and suppresses transmission to the outside of the heat-insulating box 791. The internal space between the heat insulating box 791 and the microreactor module 600 is depressurized and exhausted so that the internal pressure of the heat insulating box reaches 1Pa or less, thereby forming a heat insulating space. The supply/discharge portion 602 is exposed from the heat insulating box 791 and connected to a power generation unit 801 described later.

Gaps between the liquid fuel introduction pipe 622 and the pipe members 626, 628, 630, 632, 634 and the holes 794, 795 are sealed with a sealing material 796 so that the gaps do not occur in which external air enters the inside of the heat insulation box 791 from the holes 794, 795 into which the liquid fuel introduction pipe 622 and the pipe members 626, 628, 630, 632, 634 are inserted and the internal pressure rises (see fig. 12).

When the heat insulating box 791 is a conductor, a glass material or an insulating sealing material, which is an insulator, can be used as the sealing material 796. On the other hand, when the heat insulating box 791 is an insulator such as ceramics, a brazing alloy as a conductor may be used as the sealing material 796 in addition to a glass material and an insulating sealing material.

Next, a power generation unit including the micro-reactor module according to the present embodiment will be described.

Fig. 11 is a perspective view showing an example of a power generation unit including the microreactor module of the present embodiment.

As shown in fig. 11, the above-described microreactor module 600 can be incorporated into a power generation unit 801 and used in a state of being housed in a heat-insulating box 791. The power generation unit 801 includes: such as the frame 802; a fuel container 804 that is removable with respect to the frame 802; a flow rate control unit 806 having a flow path, a pump, a flow sensor, a valve, and the like; a micro-reactor module 600 in a state of being accommodated in the heat insulating box 791; a power generation element 808 having a fuel cell, a humidifier, a recoverer, and the like; an air pump 810; and a power supply unit 812 having a secondary battery, a DC-DC converter, an external interface, and the like. By supplying the mixed gas of water and liquid fuel in the fuel container 804 to the micro-reactor module 600 by the flow rate control unit 806, hydrogen gas is generated as described above and supplied to the fuel cell of the power generation element 808, and the generated electricity is stored in the secondary cell of the power supply unit 812.

An example of the wiring structure of the assembly portion of the microreactor module 600 on the power generation unit 801 is explained below.

FIG. 12 is a sectional view showing example 1 of a wiring structure of an assembly portion of a micro-reactor module of the present embodiment on a power generation cell.

FIG. 13 is a sectional view showing a 2 nd example of a wiring structure of an assembly portion of a microreactor module on a power generation unit according to the present embodiment.

The wiring structure of the assembly portion of the microreactor module 600 on the power generation unit 801 may be formed into a structure such as that shown in fig. 12. That is, the pipe member 630 penetrating the bottom plate 793 is connected to the pipe 814 provided in the power generation unit 801. The pipe 814 is made of an insulating material such as silicone rubber, and connects the pipe member 630 to a not-shown flow path provided in the power generation unit 801.

Similarly, by connecting the same pipes to the other pipes 626, 628, 630, 632, 634 as well, the reactant can be supplied from the power generation unit 801 to the microreactor module 600 or the product can be discharged from the microreactor module 600.

In addition, the tubes 626, 630, 632, and 634 other than the tube 628 are connected to the lead 816 for applying voltage to the heating wires 720 and 722. The lead 816 is connected to a control device, not shown, provided in the power generation unit 801. The control device applies a voltage between the tubes 630, 632 and 626, 634 via the wire 816 as described below.

Further, since the pipes connected to the pipe members 626, 628, 630, 632, 634 are made of an insulating material, when a voltage is applied between the pipe members 630, 632 and between the pipe members 626, 634, a current does not flow to other portions of the power generation unit 801.

Further, the interface of the power generation unit 801 to which the microreactor module 600 is attached may be configured as shown in fig. 13, for example.

That is, on the power generation unit 801 side, an insertion opening 820 into which pipe members 626, 628, 630, 632, 634 are inserted is provided in an insulating base plate 818 that is in contact with a plate 793 of an insulating box 791. The insertion port 820 communicates with a flow path 822 provided in the substrate 818. By inserting the pipes 626, 628, 630, 632, 634 into the insertion port 820, the reactant can be supplied from the power generation unit 801 to the microreactor module 600 or the product can be discharged from the microreactor module 600 through the flow path 822.

Further, terminals (not shown) which come into contact with the pipe 630 are provided on the inner wall surface of the insertion port 820 into which the pipes 626, 630, 632, 634 other than the pipe 628 are inserted. The terminals are electrically connected to a wiring 824 provided in the substrate 818, and the wiring 824 is connected to a control device, not shown, provided in the power generation unit 801. As described later, the control device applies a voltage between the tubes 630 and 632 and between the tubes 626 and 634 through the wiring 824.

Further, since the terminals and the wiring 824 provided in the insertion port 820 are provided on the insulating substrate 818, when a voltage is applied between the pipes 630 and 632 and between the pipes 626 and 634, a current does not flow to other portions of the power generation unit 801.

In any of the above configurations, the control device measures the voltage applied to the heating wires 720 and 722 and the current flowing through the heating wires 720 and 722, as will be described later, thereby measuring the resistance values of the heating wires 720 and 722. The control device stores the relationship between the resistance values of the heating wires 720 and 722 and the temperatures, so that the temperature of the micro-reactor module 600 can be measured from the resistance values of the heating wires 720 and 722. In addition, the control device may perform temperature control of the micro-reactor module 600 by feedback-controlling the voltage applied to the heating wires 720 and 722.

Next, the operation of the microreactor module 600 in the present embodiment will be described.

First, when a voltage is applied between the pipe members 630 and 632 and between the pipe members 626 and 634, the heating wires 720 and 722 generate heat, thereby heating the low temperature reaction part 606, the high temperature reaction part 604, and the connection part 608. The temperature of the liquid fuel introduction pipe 622, the high temperature reaction portion 604, and the low temperature reaction portion 606 is measured by measuring the current and voltage of the heating wires 720 and 722 with a control device, not shown, and the measured temperature is fed back to the control device, and the temperature of the micro-reactor module 600 is controlled by controlling the voltage of the heating wires 720 and 722 with the control device.

Then, in a state where the micro-reactor module 600 is heated by the heating wires 720 and 722, a mixed liquid of the liquid fuel and water is continuously or intermittently supplied to the liquid fuel introduction pipe 622 by a pump or the like, and is gasified in the gasifier 610. The mixed gas obtained by the gasification flows into the converter 400 through the low-temperature reaction portion 606 and the connection portion 608.

Then, the mixed gas is heated in the reformer 400 to perform a catalytic reaction, thereby generating hydrogen gas or the like (see the above chemical reaction formulae (1) and (2) when the fuel is methanol).

The mixed gas (containing hydrogen gas, carbon dioxide gas, carbon monoxide gas, and the like) generated in the reformer 400 flows into the carbon monoxide remover 500 through the connection part 608. On the other hand, air is supplied to the carbon monoxide remover 500 through the pipe 634 by a pump or the like, and mixed with a mixed gas such as hydrogen. In addition, the carbon monoxide gas in the mixed gas is selectively oxidized and removed in the carbon monoxide remover 500.

Then, the mixed gas from which carbon monoxide has been removed is supplied to a fuel electrode of a fuel cell or the like via a pipe 626. In the fuel cell, electricity is generated by an electrochemical reaction of hydrogen gas, and off gas containing unreacted hydrogen gas and the like is discharged from the fuel cell.

The above operation is an initial stage operation, and thereafter, the mixed liquid is continuously supplied to the liquid fuel introduction pipe 622. Air is mixed with the off gas discharged from the fuel cell, and the mixed gas (hereinafter referred to as combustion mixed gas) is supplied to the pipe 632 and the pipe 628. The combustion mixture gas supplied to the pipe 632 flows into the 1 st burner 612 and is catalytically combusted. Combustion heat is generated thereby, and the liquid fuel introduction pipe 622 and the low temperature reaction portion 606 are heated by the combustion heat.

On the other hand, the combustion mixture supplied to the pipe 628 flows into the 2 nd burner 614, and is catalytically combusted. Combustion heat is generated thereby, and the converter 400 is heated by the combustion heat.

The exhaust gases that have been catalytically combusted in the 1 st burner 612 and the 2 nd burner 614 are discharged through the pipe 630.

Alternatively, the liquid fuel stored in the fuel container may be vaporized, and a combustion mixture gas of the vaporized fuel and air may be supplied to the pipes 628 and 632.

In a state where the mixed liquid is supplied to the liquid fuel introduction pipe 622, that is, in a state where the combustion mixed gas is supplied to the pipe members 628 and 632, the controller controls the pump and the like while controlling the voltage applied to the heating wires 720 and 722 while measuring the temperature by the heating wires 720 and 722. If the pump is controlled by the control device, the flow rate of the combustion mixture gas supplied to the pipes 628, 632 can be controlled, thereby controlling the combustion heat of the burners 612, 614. By controlling the heating wires 720 and 722 and the pump by the control device in this way, the temperature of the liquid fuel introduction pipe 622, the high temperature reaction section 604, and the low temperature reaction section 606 can be controlled. Here, the temperature of the high temperature reaction part 604 was controlled to 375 ℃ and the temperature of the low temperature reaction part 606 was controlled to 150 ℃.

[ electronic apparatus ]

Next, an example of an electronic device using the power generating unit as a power source will be described.

Fig. 14 is a perspective view showing an example of an electronic device using a power generation unit as a power source.

The electronic device 851 is a portable electronic device, particularly a notebook computer. The electronic device 851 includes a lower housing 854 and an upper housing 858 provided with a liquid crystal display 856, and the lower housing 854 houses a CPU, a RAM, a ROM, and an arithmetic processing circuit including other electronic components and is provided with a keyboard 852. It is constituted as follows: the lower housing 854 and the upper housing 858 are coupled by a hinge, and the upper housing 858 can be folded in a state where it is overlapped with the lower housing 854 so that the liquid crystal display 856 faces the keyboard 852. A mounting portion 860 for mounting the power generation unit 801 is recessed from the right side surface to the bottom surface of the lower housing 854, and if the power generation unit 801 is mounted on the mounting portion 860, the electronic device 851 is operated by the power of the power generation unit 801.

The present invention is not limited to the above-described embodiments, and various modifications and design changes may be made without departing from the scope of the present invention.

For example, in the above embodiment, two pipes are connected to both ends of the heating wire, but the present invention is not limited to this, and for example, another electric wiring such as a vacuum sensor may be further provided in the heat-insulating box, and any 2 pipes may be connected thereto.

< embodiment 2 >

Next, embodiment 2 of the reaction apparatus of the present invention will be described.

FIG. 15 is a block diagram showing the structure of an electronic apparatus according to embodiment 2 of the reaction apparatus of the present invention.

The electronic device 1100 shown in fig. 15 is a portable electronic device such as a notebook computer, a PDA, an electronic notebook, a digital camera, a mobile phone, a watch, a recorder, or a projector.

The electronic device 1100 includes a fuel cell device 1001, a DC/DC converter 1902, a secondary battery 1903, and an electronic device main body 1901, and the fuel cell device 1001 includes a reaction device 1101, a fuel container 1002, and a pump 1003 according to the present embodiment.

The fuel container 1002 of the fuel cell device 1001 is detachably provided to the electronic apparatus 1100, for example, and the pump 1003 and the reaction device 1101 are built in the main body of the electronic apparatus 1100, for example.

A mixed liquid of liquid raw fuel (for example, methanol, ethanol, or dimethyl ether) and water is stored in the fuel container 1002. Alternatively, the liquid raw fuel and water may be stored in separate containers.

The pump 1003 sucks the mixed liquid in the fuel container 1002 and sends the mixed liquid to the vaporizer 1004 in the reaction apparatus 1101.

The reactor 1101 includes a box-shaped heat-insulating box 1010, and the gasifier 1004, the converter 1006, the power generation element 1008, and the catalytic combustor 1009 are accommodated in the heat-insulating box 1010. The pressure in the insulated cabinet 1010 is maintained at a vacuum pressure (for example, 10Pa or less) lower than the atmospheric pressure.

The vaporizer 1004, the reformer 1006, and the catalytic combustor 1009 are provided with electric heater/temperature sensors 1004a, 1006a, and 1009a, respectively. Since the resistance values of the electric heater/temperature sensors 1004a, 1006a, 1009a depend on the temperature, the electric heater/temperature sensors 1004a, 1006a, 1009a also function as temperature sensors for measuring the temperatures of the vaporizer 1004, the reformer 1006, and the catalytic combustor 1009.

The mixed liquid sent from the pump 1003 to the vaporizer 1004 is heated to about 110 to 160 ℃ by heat of the electric heater/temperature sensor 1004a or the catalytic combustor 1009, and is evaporated. The mixed gas obtained by gasification in the gasifier 1004 is sent to the reformer 1006.

A flow path is formed inside the converter 1006, and a catalyst is supported on a wall surface of the flow path. The mixed gas sent from the vaporizer 1004 to the reformer 1006 flows through the flow path of the reformer 1006, is heated to about 300 to 400 ℃ by the heat of the electric heater/temperature sensor 1006a or the catalytic combustor 1009, and reacts with the catalyst. A mixed gas (converted gas) of hydrogen, carbon dioxide, and a trace amount of carbon monoxide as a by-product can be generated as a fuel by a catalytic reaction of the raw fuel and water.

When the raw fuel is methanol, the steam reforming reaction represented by the above formula (1) mainly occurs in the reformer 1006. In addition, carbon monoxide is produced in a slight amount as a by-product by the reaction of the following formula (3) which follows the chemical reaction formula (1).

H₂+CO₂→H₂O+CO(3)

The generated converted gas is sent out to the power generation element 1008.

Fig. 16 is a schematic view of the power generating element of the present embodiment.

Fig. 17 is a schematic diagram showing an example of stacking of power generating elements.

The power generation element 1008 is housed in a housing 1080, and includes: a solid oxide electrolyte 1081, a fuel electrode 1082 (anode) and an oxygen electrode 1083 (cathode) formed on both surfaces of the solid oxide electrolyte 1081, an anode collector electrode 1084 joined to the fuel electrode 1082 and having a flow path 1086 formed on a joint surface thereof, and a cathode collector electrode 1085 joined to the oxygen electrode 1083 and having a flow path 1087 formed on a joint surface thereof.

Only the cathode collector 1085 is in contact with the frame 1080, and the other oxygen electrode 1083, solid oxide electrolyte 1081, fuel electrode 1082, and anode collector 1084 are insulated from the frame 1080 by an insulating material 88 such as ceramic.

As the solid oxide electrolyte 1081, zirconium oxide-based (Zr) can be used_1-xY_x)O_2-x/₂(YSZ) lanthanum gallate-based (La)_1-xSr_x)(Ga_1-y-zMg_yCo_z)O₃Etc. for the fuel electrode 1082, La may be adopted_0.84Sr_0.16MnO₃、La(Ni，Bi)O₃、(La，Sr)MnO₃、In₂O₃+SnO₂、LaCoO₃For example, Ni + YSZ, etc. can be used for the oxygen electrode 1083, and LaCr (Mg) O can be used for the anode collector 1084 and the cathode collector 1085₃、(La，Sr)CrO₃、NiAl+Al₂O₃And the like.

The power generation element 1008 is heated to about 500 to 1000 ℃ by heat of the electric heater/temperature sensor 1009a or the catalytic combustor 1009, and causes a reaction described later.

Air is supplied to the oxygen electrode 1083 through the flow path 1087 of the cathode collector 1085.

In the oxygen electrode 1083, oxygen ions are generated as shown in the following formula (4) by oxygen and electrons supplied from the cathode output electrode 1021 b.

O₂+4e^-→2O^2-(4)

The solid oxide electrolyte 1081 has oxygen ion permeability, and oxygen ions generated in the oxygen electrode 1083 are transmitted therethrough to reach the fuel electrode 1082.

The reformed gas sent out from the reformer 1006 is sent to the fuel electrode 1082 via the flow path 1086 of the anode collector 1084. In the oxygen electrode 1083, the following reactions of the oxygen ions and the converted gas, which have permeated through the solid oxide electrolyte 1081, are caused as shown in the following formulas (5) and (6).

H₂+O^2-→H₂O+2e^-(5)

CO+O^2-→CO₂+2e^-(6)

The anode collector 1084 is connected to the anode output electrode 1021a, and the cathode collector 1085 is electrically connected to the cathode output electrode 1021b as described later. The anode output electrode 1021a and the cathode output electrode 1021b are connected to the DC/DC converter 1902. Therefore, electrons generated in the fuel electrode 1082 are supplied to the cathode collector electrode 1085 from the frame 1080 via the anode output electrode 1021a, an external circuit such as the DC/DC converter 1902, and the cathode output electrode 1021b, as will be described later.

As shown in fig. 17, a stack 1850 may be formed by connecting a plurality of power generation elements 1008, each of which is composed of an anode collector 1084, a fuel electrode 1082, a solid oxide electrolyte 1081, an oxygen electrode 1083, and a cathode collector 1085, in series.

In this case, as shown in fig. 17, only the anode collector 1084 of the power generating element 1008 at one end portion connected in series is brought into contact with the anode output electrode 1021a, and only the cathode collector 1085 of the power generating element 1008 at the other end portion is brought into contact with the housing 1080.

The DC/DC converter 1902 converts the electric energy generated by the power generation element 1008 into an appropriate voltage, and supplies the voltage to the electronic apparatus main body 1901. The DC/DC converter 1902 charges the secondary battery 1903 with the electric energy generated by the power generation element 1008, and supplies the electric energy stored in the secondary battery 1903 to the electronic apparatus main body 1901 when the power generation element 1008 is not operated.

The converted gas (off gas) passing through the flow path of the anode collector 1084 also contains unreacted hydrogen. The off-gas is supplied to the catalytic combustor 1009.

The exhaust gas is supplied to the catalytic combustor 1009, and the air passing through the flow path 1087 of the cathode collector 1085 is also supplied. A flow path is formed inside the catalytic combustor 1009, and a Pt-based catalyst is supported on a wall surface of the flow path.

An electric heater/temperature sensor 1009a made of an electric heating material is provided in the catalytic combustor 1009. The electric heater/temperature sensor 1009a also has a function as a temperature sensor for measuring the temperature of the catalytic combustor 1009 because the resistance value of the electric heater/temperature sensor 1009a depends on the temperature.

The mixed gas (combustion gas) of the exhaust gas and the air flows through the flow path of the catalytic combustor 1009 and is heated by the electric heater/temperature sensor 1009 a. The hydrogen in the combustion gas flowing through the flow path of the catalytic combustor 1009 is combusted by the catalyst, and combustion heat is generated. The burned exhaust gas is discharged from the catalytic combustor 1009 to the outside of the heat insulating box 1010.

The combustion heat generated by the catalytic combustor 1009 is used to maintain the temperature of the power generating element 1008 at a high temperature (approximately 500 to 1000 ℃). The heat of the power generation element 1008 is transferred to the reformer 1006 and the gasifier 1004, and is used for evaporation in the gasifier 1004 and a steam reforming reaction in the reformer 1006.

Next, a specific configuration of the reaction apparatus 1101 will be described.

Fig. 18 is a perspective view of the reaction apparatus of the present embodiment.

Fig. 19 is a view from XIX in fig. 18.

FIG. 20 is a perspective view showing the internal structure of the heat-insulating box of the reaction apparatus of the present embodiment.

Fig. 21 is a perspective view of the internal structure of the reaction apparatus of fig. 20 as viewed from the lower side.

Fig. 22 is a view in section from XXII to XXII in fig. 18.

As shown in fig. 18, an inlet of the vaporizer 1004, a connection part 1005, and an anode output electrode 1021a penetrate through one wall surface of an insulated box 1010 of the reaction apparatus 1101, and a cathode output electrode 1021b protrudes from the same wall surface.

As shown in fig. 20 to 22, a vaporizer 1004, a connection unit 1005, a converter 1006, a connection unit 1007, and a fuel cell unit 1020 are arranged in this order in an insulated box 1010 of a reaction apparatus 1101. Further, a housing 1080 for housing the power generation element 1008 and a catalytic combustor 1009 are integrally formed in the fuel cell unit 1020, and the exhaust gas is supplied from a fuel electrode 1082 of the power generation element 1008 to the catalytic combustor 1009.

The vaporizer 1004, the connection unit 1005, the converter 1006, the connection unit 1007, the frame 1080 for housing the power generation element 1008 of the fuel cell unit 1020, the catalytic burner 1009, the heat insulating box 1010, the anode output electrode 1021a, and the cathode output electrode 1021b are made of a metal having high-temperature durability and appropriate thermal conductivity, and may be made of a Ni-based nichrome alloy such as a nichrome 783, for example.

A radiation shielding film 1011 is formed on the inner wall surface of the heat insulating box 1010, and a radiation shielding film 1012 is formed on the outer wall surfaces of the vaporizer 1004, the connection portion 1005, the converter 1006, the connection portion 1007, and the fuel cell portion 1020. The radiation protective films 1011, 1012 are for preventing heat transfer by radiation, and for example, Au, Ag, or the like can be used. The radiation protective films 1011, 1012 are preferably provided with at least one of them, more preferably with both of them.

The vaporizer 1004 penetrates the wall surface of the insulated box 1010 together with the connection 1005, and is connected to the vaporizer 1004 and the reformer 1006 through the connection 1005. Converter 1006 and fuel cell portion 1020 are connected by connection portion 1007.

As shown in fig. 20 and 21, the vaporizer 1004, the connection unit 1005, the reformer 1006, the connection unit 1007, and the fuel cell unit 1020 are integrally formed, and the lower surfaces of the connection unit 1005, the reformer 1006, the connection unit 1007, and the fuel cell unit 1020 are formed on the same surface.

FIG. 23 is a schematic view showing an electron flow pattern in the reaction apparatus of the present embodiment.

As shown in fig. 23, electrons are supplied from the cathode collector electrode 1085 to the oxygen electrode 1083 via the heat insulating box 1010, the connection part 1005, the vaporizer 1004, the converter 1006, the connection part 1007, and the housing 1080 of the fuel cell unit 1020, which are electrically connected to the cathode electrode 21 b. On the other hand, the electrons generated in the fuel electrode 1082 are output to the outside via the anode output electrode 1021 a.

The cathode output electrode 1021b is connected to the Ground (GND), and the potential difference (V) between the anode output electrode 1021a and the cathode output electrode 1021b_out) Is the output voltage of the power generating element 1008.

Note that the cathode output electrode 1021b may not be separately provided, and the heat-insulating box 1010, or the vaporizer 1004 or the connection part 1005 protruding from the heat-insulating box 1010 may be used as an output electrode on the cathode side as it is.

Fig. 24 is a bottom view of the connection part, the conversion part, and the fuel cell part in the reaction device of the present embodiment.

Fig. 25 is a view in section from XXV to XXV of fig. 24.

In fig. 24 and 25, the anode output electrode 1021a and the cathode output electrode 1021b are omitted.

As shown in fig. 24 and 25, recesses 1061 and 1022 for disposing the anode output electrode 1021a are formed in the outer edge portions on the lower side of the converter 1006 and the fuel cell unit 1020.

The connection portion 1007 of the converter 1006 is connected to a portion retreated from the surface facing the fuel cell portion 1020. Therefore, by extending the connection portion 1007, heat transfer from the fuel cell portion 1020 to the converter 1006 can be reduced, and at the same time, by shortening the distance between the fuel cell portion 1020 and the converter 1006, the device can be downsized.

As shown in fig. 24, wiring patterns 1013 are formed on the lower surfaces of the connection unit 1005, the converter 1006, the connection unit 1007, and the fuel cell unit 1020 by an insulating treatment using ceramics or the like.

Wiring pattern 1013 is formed in a zigzag shape below vaporizer 1004, below reformer 1006, and below fuel cell unit 1020, and serves as electric heater/temperature sensors 1004a, 1006a, and 1009a, respectively. The electric heater/temperature sensors 1004a, 1006a, 1009a have one end connected to the common terminal 1013a and the other end connected to the 3 independent terminals 1013b, 1013c, 1013 d. These 4 terminals 1013a, 1013b, 1013c, and 1013d are formed at the end of the connecting portion 1005 on the outer side of the heat insulating box 1010.

In addition, an insulation treatment is performed on the portion of the insulation box 1010 penetrating the connection portion 1005 so that the electric heater/temperature sensors 1004a, 1006a, 1009a are not electrically connected to the insulation box 1010.

Fig. 26 is a sectional view from XXVI to XXVI in fig. 24.

Fig. 27 is a view in section from XXVII to XXVII in fig. 26.

The connecting portions 1005 and 1007 are provided with air supply passages 1051 and 1071 for supplying air to the oxygen electrode 1083 of the power generation element 1008, and exhaust gas discharge passages 1052a, 1052b, 1072a and 1072b for discharging exhaust gas from the catalytic combustor 1009. A gas fuel supply passage 1053 for sending the gas fuel from the vaporizer 1004 to the reformer 1006 is provided in the connection portion 1005, and a reformed gas supply passage 1073 for sending the reformed gas from the reformer 1006 to the fuel electrode 1082 of the power generation element 1008 is provided in the connection portion 1007.

Further, as shown in fig. 25, 4 flow paths 1071, 1072a, 1072b, and 1073 are provided inside the connection portion 1007, but in order to sufficiently increase the flow path of the exhaust gas discharged from the catalytic combustor 1009 with respect to the exhaust gas and the air supplied to the catalytic combustor 1009, two of the flow paths 1072a and 1072b are used as the flow paths of the exhaust gas discharged from the catalytic combustor 1009, and the other two flow paths are used as the reformed gas supply flow path 1073 for supplying the reformed gas to the fuel electrode 1082 of the power generation element 1008 and the air supply flow path 1071 for supplying the air to the oxygen electrode 1083.

The anode output electrode 1021a is connected to a position of the fuel cell unit 1020 that is farther from the wall surface of the heat insulating case 1010 through which the anode output electrode 1021a penetrates than the connection portion 1007, and is preferably connected to and drawn from an end opposite to the connection portion 1007.

As shown in fig. 30 and 31, the anode output electrode 1021a is drawn out from the anode collector 1084 through the frame 1080. Further, the space between the anode output electrode 1021a and the frame 1080 is sealed with an insulating material 1089 such as glass or ceramic.

The anode output electrode 1021a is arranged along the fuel cell unit 1020 and the concave portions 1061, 1022 of the converter 1006, and is bent in the space between the inner wall surface of the heat insulating case 1010 and the converter 1006 as shown in fig. 20 and 21. The bent portion 1023 functions as a stress relaxation structure for relaxing stress between the fuel cell unit 1020 and the heat insulating case 1010 by deformation of the anode output electrode 1021 a.

An end of the anode output electrode 1021a protrudes outward from the same wall surface as the wall surface of the heat insulating box 1010 from which the inlet and the connecting portion 1005 of the vaporizer 1004 protrude. As shown in fig. 19, the space between the anode output electrode 1021a and the heat insulating box 1010 is sealed with an insulating sealing material 1014 such as sintered glass.

Fig. 28 is a schematic diagram showing the temperature distribution in the heat-insulating box during steady operation in the reaction apparatus of the present embodiment.

As shown in fig. 28, if the fuel cell portion 1020 is held at approximately 800 ℃, for example, heat moves from the fuel cell portion 1020 to the converter 1006 through the connection portion 1007, from the converter 1006 to the vaporizer 1004 through the connector 1005, and to the outside of the insulated box 1010. As a result, the temperature of the reformer 1006 is maintained at about 380 ℃ and the temperature of the gasifier 1004 is maintained at about 150 ℃.

Since the heat of the fuel cell unit 1020 also moves to the outside of the heat insulating case 1010 through the anode output electrode 1021a, the anode output electrode 1021a expands due to the temperature rise after the fuel cell device 1001 is started.

Fig. 29 is a simulation diagram showing the deformation of the anode output electrode due to a temperature rise in the reaction device of the present embodiment.

The anode output electrode 1021a expands due to the temperature rise of the fuel cell unit 1020, and changes from the shape shown by the broken line to the shape shown by the solid line in fig. 29.

At this time, the portion 1024 on the fuel cell section 1020 side has a higher temperature than the bent portion 1023 of the anode output electrode 1021a, and therefore has a larger elongation. Here, since one end of the anode output electrode 1021a is connected to the anode collector 1084 of the fuel cell unit 1020 and the other end is joined to the wall surface of the heat insulating box 1010 on the vaporizer 1004 side and protrudes to the outside, the anode output electrode 1021a receives stress due to this elongation. However, since the anode output electrode 1021a has the bent portion 1023, deformation due to elongation can be absorbed by the bent portion 1023, and therefore stress acting between the heat insulating case 1010 and the fuel cell unit 1020 can be relaxed.

Further, since the output electrode connected to the cathode collector electrode 1085 is replaced with a conductor in the vaporizer 1004, the connection unit 1005, the reformer 1006, the connection unit 1007, and the housing 1080, the cathode output electrode connected to the cathode collector electrode 1085 can be omitted, and therefore, the heat transfer path can be reduced, and the heat loss from the fuel cell unit 1020 to the heat insulating box 1010 can be reduced. Further, since the provision of the bent portion 1023 extends the heat transfer path of the anode output electrode 1021a, the heat loss from the fuel cell unit 1020 to the heat insulating case 1010 via the anode output electrode 1021a can be further reduced.

Next, a modified example of the internal structure of the heat insulating box in the reaction apparatus according to the present embodiment will be described.

Fig. 30, 31, and 32 are perspective views showing modifications of the internal structure of the heat insulating box in the reaction apparatus according to the present embodiment.

In the above embodiment, the anode output electrode 1021a having a rectangular cross-sectional shape is used, but as shown in fig. 30, for example, the anode output electrode 1025 having a triangular cross-sectional shape may be used. As shown in fig. 31, an anode output electrode 1026 having a circular cross-sectional shape may be used.

In the above embodiment, the anode output electrode 1021a is formed by bending the bent portion 1023 as the stress relaxation structure at 3 at right angle as shown in fig. 20 and 21, but the bent portion of the bent portion may be formed in an arc shape and smoothly bent as shown in fig. 30 and 31. In this case, stress concentration at the bent portion can be suppressed, stress can be dispersed over the entire bent portion, and damage due to stress can be suppressed. Alternatively, as shown in fig. 32, an anode output electrode 1027 having a stress relaxation structure formed in a spiral shape in a space between the inner wall surface of the heat-insulating box 1010 and the converter 1006 may be used.

When the thin vaporizer 1004, the reformer 1106, and the fuel cell portion 1120 are employed to make the heat insulating box 1010 thin, an anode output electrode 1028 having a zigzag bent portion 1029 may be employed as shown in fig. 33.

Claims (36)

1. A reaction apparatus is provided with:

a reaction section to which a reactant is supplied and which is set at a predetermined temperature to cause a reaction;

a plurality of electrodes provided on the reaction section;

a heat insulating container which accommodates the reaction part therein via a heat insulating space;

a supply/discharge unit which is composed of a conductor, has one end connected to the reaction unit and the other end led to the outside through the wall surface of the heat insulating container, and supplies a reactant to the reaction unit and discharges a reaction product from the reaction unit,

wherein at least one of the plurality of electrodes is electrically connected to the feeding portion;

the reaction part has a power generating element having two electrodes, a positive electrode and a negative electrode, which form the plurality of electrodes, and set at a predetermined temperature, and which obtains electric power from the respective electrodes by an electrochemical reaction of a reactant; one of the two electrodes is electrically connected with the feeding and discharging part;

the reaction part further comprises an output electrode, one end of which is connected to the other electrode of the power generating element and the other end of which is led out to the outside through the wall surface of the heat insulating container;

the output electrode has a stress relaxation structure having a plurality of bent portions.

2. The reaction apparatus according to claim 1, wherein the supply and discharge portion has a plurality of tubes made of a conductor, and at least one of the plurality of electrodes is electrically connected to at least one of the plurality of tubes.

3. The reaction apparatus according to claim 1, wherein the reaction section further comprises a heating section for heating the reaction section to set the reaction section at the predetermined temperature, the heating section comprises a heating wire for generating heat by receiving power supply, the plurality of electrodes are formed at both end portions of the heating wire, and at least one of the both end portions of the heating wire is electrically connected to the supply/discharge section.

4. The reaction apparatus of claim 3, wherein the heating wire is a metal thin film.

5. The reaction apparatus according to claim 3, further comprising a substrate for providing the reaction section on one surface, wherein the supply/discharge section includes a plurality of tubes made of a conductor, and wherein the plurality of tubes and the heating wire are provided on the other surface of the substrate.

6. The reaction apparatus according to claim 5, wherein the substrate has conductivity, and the plurality of tube members and the heating wire are provided on the other surface of the substrate via an insulating film.

7. The reaction apparatus according to claim 5, wherein the plurality of tubes are connected to the other surface of the substrate via an adhesive member having conductivity, and the adhesive member is electrically connected to at least one end portion of the heating wire of the heating portion.

8. The reactor apparatus of claim 7 wherein said adhesive means is a metal plating.

9. The reaction apparatus according to claim 5, wherein the plurality of tubes are connected to the other surface of the substrate via an adhesive member having conductivity, and one end portion of the adhesive member and at least one end portion of the heating wire of the heating portion are electrically connected via a connecting member.

10. The reaction apparatus according to claim 9, wherein the connecting member is an electrically conductive wire.

11. The reaction device of claim 9, wherein the connecting member is solder.

12. The reaction apparatus according to claim 1, wherein the reaction section comprises:

a 1 st reaction part set at a 1 st temperature by the heating part to cause a reaction of the reactants;

a 2 nd reaction part set at a 2 nd temperature lower than the 1 st temperature by the heating part to cause a reaction of a reactant;

and a connecting part which is arranged between the 1 st reaction part and the 2 nd reaction part and conveys a reactant and a reaction product generated by the reaction between the 1 st reaction part and the 2 nd reaction part.

13. The reactor according to claim 12, wherein the supply and discharge part is connected to the 2 nd reaction part.

14. The reaction apparatus according to claim 12, wherein the 1 st reaction part is supplied with a 1 st reactant to produce a 1 st reaction product; the 2 nd reaction part is supplied with the 1 st reaction product to generate a 2 nd reaction product; the 1 st reactant is mixed gas obtained by gasifying water and liquid fuel containing hydrogen in the composition; the 1 st reaction part is a converter that causes a conversion reaction of the 1 st reactant, and the 1 st reaction product contains hydrogen and carbon monoxide; the 2 nd reaction part is a carbon monoxide remover for removing carbon monoxide contained in the 1 st reaction product.

15. The reaction device according to claim 1, wherein a solid oxide electrolyte is used in the power generating element.

16. The reaction device according to claim 1, wherein the reaction section further comprises a burner for burning unreacted fuel gas discharged from the power generation element to heat the power generation element.

17. The reaction apparatus according to claim 1, wherein the reaction section further comprises a converter for causing a conversion reaction after the 1 st reactant is supplied, thereby producing a 1 st reaction product; the power generation element takes the 1 st reaction product as a reactant to cause electrochemical reaction; the 1 st reactant is a mixed gas obtained by gasifying a raw fuel containing water and a liquid fuel containing hydrogen in composition, and the 1 st reaction product contains hydrogen and carbon monoxide.

18. The reaction device according to claim 17, wherein the converter performs the conversion reaction by heat conducted from the power generation element.

19. The reaction apparatus according to claim 17, wherein the supply and discharge unit comprises: a 1 st connection part connecting the heat insulating container and the converter, and a 2 nd connection part connecting the converter and the power generating element.

20. The reaction apparatus according to claim 19, wherein the reaction portion further comprises a vaporizer for supplying the raw fuel and vaporizing the raw fuel by heat transferred from the reformer to generate the mixed gas, and supplying the mixed gas to the reformer, the vaporizer being provided at the 1 st connecting portion.

21. The reaction apparatus according to claim 1, wherein the cross-sectional shape of the output electrode is any one of a quadrangle, a triangle, and a circle.

22. The reactor according to claim 1, wherein the stress relaxation structure is provided in the space for heat insulation between the wall surface of the heat insulating container from which the output electrode is drawn and the converter.

23. The reactor according to claim 1, wherein the output electrode is bent at the bending portion of the stress relaxation structure into any one of a right-angled shape, a circular arc shape, and a zigzag shape.

24. A reaction apparatus is provided with:

a reaction unit having a power generating element which has two electrodes, a positive electrode and a negative electrode, is set at a predetermined temperature, and receives electric power from the two electrodes by an electrochemical reaction of a reactant;

a heat insulating container which accommodates the reaction part therein via a heat insulating space;

a supply/discharge unit which is composed of a conductor, has one end connected to the reaction unit and the other end led out to the outside after penetrating the wall surface of the heat insulating container to connect between the heat insulating container and the reaction unit, and supplies the fuel for power generation to the reaction unit and discharges the reaction product from the reaction unit;

wherein one of the two electrodes in the power generating element is electrically connected to the supply/discharge portion;

the reaction part further comprises an output electrode, one end of which is connected to the other electrode of the power generating element and the other end of which is led out to the outside through the wall surface of the heat insulating container;

the output electrode has a stress relaxation structure having a plurality of bent portions.

25. The reaction device according to claim 24, wherein a solid oxide type electrolyte is used in the power generating element.

26. The reaction apparatus according to claim 24, wherein the reaction section further comprises:

a frame body for accommodating the power generating element and through which the output electrode penetrates,

wherein the output electrode and the frame body are made of the same material.

27. The reaction apparatus according to claim 24, wherein a distance from the wall surface of the heat-insulating container from which the output electrode is drawn to the other electrode of the power generating element connected to one end of the output electrode is larger than a distance from the wall surface of the heat-insulating container from which the output electrode is drawn to the one electrode of the two electrodes of the power generating element.

28. The reactor apparatus of claim 24,

the reaction part is also provided with a converter which is used for causing a conversion reaction after being supplied with the 1 st reactant so as to generate a 1 st reaction product;

the power generation element takes the 1 st reaction product as a reactant to cause electrochemical reaction;

the 1 st reactant is a mixed gas obtained by gasifying a raw fuel containing water and a liquid fuel containing hydrogen in the composition, and the 1 st reaction product contains hydrogen and carbon monoxide;

the supply and discharge unit includes a 1 st connection unit for connecting the heat insulating container and the converter, and a 2 nd connection unit for connecting the converter and the power generating element;

the distance from the wall surface of the heat insulating container from which the output electrode is drawn to the other electrode of the power generating element connected to one end of the output electrode is larger than the distance from the wall surface to the 2 nd connecting portion.

29. The reaction apparatus according to claim 28, wherein the reaction section further comprises a vaporizer for generating the mixed gas by vaporizing the raw fuel by heat transferred from the reformer after the raw fuel is supplied, and supplying the mixed gas to the reformer; the vaporizer is disposed on the 1 st connection part.

30. The reaction device according to claim 24, wherein the reaction section further comprises a burner for burning unreacted fuel gas discharged from the power generation element to heat the power generation element.

31. An electronic device provided with a reaction device and a load, the reaction device comprising:

a reaction section to which a reactant is supplied and which is set at a predetermined temperature to cause a reaction;

a plurality of electrodes provided on the reaction section;

a heat insulating container which accommodates the reaction part therein via a heat insulating space;

a supply/discharge unit which is made of a conductor, has one end connected to the reaction unit and the other end led out to the outside after penetrating the wall surface of the heat insulating container to connect between the heat insulating container and the reaction unit, and supplies a reactant to the reaction unit and discharges a reaction product from the reaction unit;

a power generation element that obtains electric power by an electrochemical reaction of a reactant,

wherein at least one of the plurality of electrodes is electrically connected to the feeding portion;

the reaction part further comprises an output electrode, one end of which is connected to the other electrode of the power generating element and the other end of which is led out to the outside through the wall surface of the heat insulating container;

the output electrode has a stress relaxation structure having a plurality of bent portions;

the load is driven by the electric power obtained from the power generation element.

32. The electronic device according to claim 31, wherein the power generating element is provided in the reaction portion, has two electrodes of a positive electrode and a negative electrode, and takes electric power from the two electrodes; one of the two electrodes of the power generation element is electrically connected to the supply/discharge portion.

33. The electronic device according to claim 32, wherein a solid oxide type electrolyte is used in the power generating element.

34. The electronic device of claim 32,

the reaction section in the reaction apparatus further has a converter for being supplied with a 1 st reactant to cause a conversion reaction to produce a 1 st reaction product;

the power generation element takes the 1 st reaction product as a reactant to cause electrochemical reaction;

the 1 st reactant is a mixed gas obtained by gasifying a raw fuel containing water and a liquid fuel containing hydrogen in the composition, and the 1 st reaction product contains hydrogen and carbon monoxide;

the supply and discharge unit includes a 1 st connection unit for connecting the heat insulating container and the converter, and a 2 nd connection unit for connecting the converter and the power generating element;

the distance from the wall surface of the heat insulating container from which the output electrode is drawn to the other electrode of the power generating element connected to one end of the output electrode is larger than the distance from the wall surface to the 2 nd connecting portion.

35. The electronic apparatus according to claim 34, wherein the reaction section further comprises a vaporizer for generating the mixed gas by supplying water and a liquid fuel containing hydrogen in composition to the reformer by vaporizing the water and the liquid fuel containing hydrogen in composition by heat conducted from the reformer; the vaporizer is disposed on the 1 st connection part.

36. The electronic device according to claim 32, wherein the reaction portion further includes a burner for burning unreacted fuel gas discharged from the power generation element to heat the power generation element.