Heating device

Abstract

To provide a heating device high in thermal efficiency and heat exchange efficiency, and high in durability.SOLUTION: A heating device of the present invention includes: a flat plate-like heating body 5 for generating heat by storage and release of hydrogen; a first flow passage 6 for supplying hydrogen to the heating body 5, to which hydrogen-based gas containing the hydrogen is introduced; and a second flow passage 7 in which transmission gas containing the hydrogen transmitted through the heating body 5 flows. The heating device is configured by disposing the first flow passage 6 and the second flow passage 7 on both sides of the heating body 5 respectively, and a support 25 for receiving the deformed heating body 5 is disposed protruding toward the heating body 5 on a first partition wall 24 for forming the second flow passage 7 between the heating body 5 and itself. The support 25 is composed of a plurality of metal pins or plates.SELECTED DRAWING: Figure 5

Description

[Technical Field]

[0001] The present invention relates to a heat generating device having a heat generating element that generates heat by absorbing and releasing hydrogen. [Background technology]

[0002] Hydrogen storage alloys have the property of repeatedly absorbing and releasing large amounts of hydrogen under certain reaction conditions, and it is known that the absorption and release of hydrogen involves a considerable amount of reaction heat. Heat utilization systems and hydrogen storage systems, such as heat pump systems, heat transport systems, and cold (refrigeration) systems, that utilize this reaction heat have been proposed (see, for example, Patent Documents 1 and 2).

[0003] Meanwhile, the present applicant and others have discovered that in a heat generating device equipped with a heat generating element using a hydrogen storage alloy or the like, by configuring the heat generating element with a support and a multilayer film supported on this support, heat is generated when hydrogen is absorbed into the heat generating element and when hydrogen is released from the heat generating element. Based on this discovery, the present applicant and others have previously proposed a heat utilization system and a heat generating device (see Patent Document 3).

[0004] Specifically, the support provided on the heating element of the heating device is composed of at least one of a porous body, a hydrogen-permeable membrane, and a proton dielectric, and the multilayer film supported on this support is composed, for example, by alternately stacking a first layer less than 1000 nm thick made of a hydrogen-storing metal or hydrogen-storing alloy and a second layer less than 1000 nm thick made of a hydrogen-storing metal, hydrogen-storing alloy, or ceramic different from the first layer. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 56-100276 [Patent Document 2] Japanese Patent Application Publication No. 58-022854 [Patent Document 3] Patent No. 6749035 Summary of the Invention [Problem to be solved by the invention]

[0006] However, in the heat generating device proposed in Patent Document 3, the heat generating elements are not incorporated in a densely packed state, so the heat generating elements cannot generate heat efficiently, and there is still room for improvement.

[0007] 15 , a first flow path 106 for introducing a hydrogen-based gas containing hydrogen into the heating element 105 and a second flow path 107 into which hydrogen that has permeated through the heating element 105 flows are arranged on both sides of the heating element 105, and the heating element 105, the first flow path 106, and the second flow path 107 are stacked at high density to make the heating device 101 small and compact, with high heat generation efficiency and high output. In the heating device 101 having such a configuration, hydrogen introduced into the first flow path 106 permeates the heating element 105, causing the heating element 105 to generate heat. In this case, hydrogen that has permeated the heating element 105 (hereinafter sometimes referred to as "permeated hydrogen") flows into the second flow path 107, and therefore the pressure in the second flow path 107 is lower than the pressure in the first flow path 106.

[0008] Here, the heating element 105 is made of a very thin and flexible hydrogen-absorbing metal or alloy. Therefore, as shown in FIG. 16, the heating element 105 bends and deforms into an arc-shaped curve, bulging toward the second flow path 107, where the pressure is lower, while simultaneously being subjected to tensile stress in the lateral direction of the membrane surface. If this stress exceeds the yield stress of the material of the heating element 105, the heating element 105 undergoes significant plastic deformation. Therefore, the amount of hydrogen permeated through the heating element 105 and the cross-sectional shapes of the first flow path 106 and the second flow path 107 may change, resulting in changes in the hydrogen flow rate and pressure loss from their initial values. In the worst case scenario, the second flow path 107 may be blocked, causing the flow of hydrogen to stop. Alternatively, a crack may develop in the heating element 105, causing a large amount of hydrogen to leak from the first flow path 106 to the second flow path 107. Furthermore, the pressure difference between the first flow path 106 and the second flow path 107 may be significantly reduced, potentially resulting in the heating device shutting down. In order to prevent such a problem, it is conceivable to increase the thickness of the heating element 105, but if the thickness of the heating element 105 is increased, the diffusion of hydrogen in the heating element 105 will be hindered, resulting in the problem that the required amount of heat cannot be generated.

[0009] Furthermore, the heat generated by the heating element 105 is transmitted to the outside through solid thermal conduction at the joint between the heating element 105 and the container (not shown), and through thermal radiation and hydrogen gas convection and thermal conduction in the first flow path 106 and second flow path 107 inside the container. The thermal conductivity per unit area due to radiation and hydrogen gas convection and thermal conduction is relatively smaller than that of solid thermal conduction such as metal. Under operating conditions where the density (pressure) of the hydrogen gas is reduced to prevent deformation of the heating element 105 as described above, thermal conduction becomes even smaller, making it difficult to obtain a heat flow sufficient to maintain the temperature of the heating element 105 at an appropriate level. In other words, there is a possibility that the heating element 105 may overheat.

[0010] The present invention has been made in view of the above problems, and has as its object to provide a heat generating device that has high heat generation efficiency and heat exchange efficiency and is highly durable. [Means for solving the problem]

[0011] In order to achieve the above object, the heat generating device of the present invention comprises a flat heating element that generates heat by absorbing and releasing hydrogen, a first flow path through which a hydrogen-based gas containing the hydrogen is introduced and supplies hydrogen to the heating element, and a second flow path through which a permeated gas containing hydrogen that has permeated the heating element flows, the first flow path and the second flow path being disposed on both sides of the heating element, and a support for receiving a deformed heating element is provided on a first partition wall that forms the second flow path between the heating element and the first partition wall, and protrudes toward the heating element. [Effects of the Invention]

[0012] According to the present invention, even if the heating element is deflected and deformed so as to bulge toward the second flow path where the pressure is lower due to the pressure difference between the first flow path and the second flow path, the deflection of the heating element is kept small by the support that supports the heating element. As a result, the stress caused by the deformation of the heating element is kept small, the durability of the heating element is increased, and the heating action of the heating element is not hindered by the deformation, so the heating element can perform the heat action stably, resulting in high heat generation efficiency and heat exchange efficiency. [Brief explanation of the drawings]

[0013] [Figure 1] 1 is a block diagram showing a basic configuration of a heat generating device according to the present invention. [Figure 2] 1 is an exploded perspective view of a heat generating module of a heat generating device according to the present invention; [Figure 3] 1 is an exploded perspective view of a laminated structure of a heat generating device according to the present invention; [Figure 4] 1 is a plan view of an electric heater of a heat generating device according to the present invention. [Figure 5] FIG. 2 is an enlarged detailed view of part A in FIG. [Figure 6] FIG. 6 is a cross-sectional view taken along line BB in FIG. 5. [Figure 7] 5, showing another embodiment of the heat generating device according to the present invention. [Figure 8] 1 is a cross-sectional view showing the configuration of a heat generating element of a heat generating device according to the present invention. [Figure 9]3A and 3B are schematic diagrams illustrating the mechanism by which excess heat is generated in the heat generating element of the heat generating device according to the present invention. [Figure 10] FIG. 10 is a cross-sectional view showing a first modified example of the configuration of the heating element. [Figure 11] FIG. 10 is a cross-sectional view showing a second modified example of the configuration of the heating element. [Figure 12] 3A and 3B are schematic cross-sectional views illustrating deflection deformation of a heat generating element of a heat generating device according to the present invention and a mechanism for suppressing this deformation. [Figure 13] 10A and 10B are schematic cross-sectional views illustrating deflection deformation of a heat generating element of a heat generating device according to another embodiment of the present invention and a mechanism for suppressing this deflection deformation. [Figure 14] 1 is a block diagram showing the configuration of a heat utilization system including a heat generating device according to the present invention. [Figure 15] 1 is a cross-sectional view showing the basic configuration of a heat generating device having a flat plate-shaped heat generating element. [Figure 16] 16 is a schematic cross-sectional view showing deformation of the heat generating element of the heat generating device shown in FIG. 15. FIG. DETAILED DESCRIPTION OF THE INVENTION

[0014] Hereinafter, an embodiment of the present invention will be described with reference to the accompanying drawings.

[0015] [Heat generating device] 1 is a block diagram showing the basic configuration of a heat generating device according to the present invention, and the illustrated heat generating device 1 comprises a heat generating module M, a temperature adjusting unit T, a hydrogen circulation line L1, a control unit 2, and a sealed container 3. In FIG. 1, the connection points indicated by black circles indicate the connection points of multiple pipes.

[0016] The heat generating module M is housed inside a sealed container 3 and includes two laminated structures 4 and one electric heater 9. Each laminated structure 4 has a heat generating element 5 that generates heat by absorbing and releasing hydrogen, a first flow path 6 through which a hydrogen-based gas containing hydrogen is introduced and supplies the hydrogen to the heat generating element 5, a second flow path 7 through which a hydrogen-based gas containing hydrogen (hereinafter referred to as a "permeated gas") that has permeated the heat generating element 5 (hereinafter referred to as "permeated hydrogen") flows, and a third flow path 8 through which a heat medium flows that exchanges heat with the permeated gas flowing through the second flow path 7. The second flow path 7, the heat generating element 5, and the first flow path 6 are sequentially and symmetrically stacked on both sides of the third flow path 8 in this order from the third flow path 8. The electric heater 9 is an example of a heating means for heating the heat generating element 5, and is not limited thereto.

[0017] Here, the hydrogen-based gas includes hydrogen isotopes, and includes at least one of protium gas and deuterium gas. Protium gas includes a mixture of naturally occurring protium and deuterium, i.e., a mixture with a protium content of 99.985% and a deuterium content of 0.015%. In FIG. 1, the hydrogen-based gas that supplies hydrogen to the heating element 5 is labeled "hydrogen," and the permeated gas containing permeated hydrogen that has permeated the heating element 5 is labeled "permeated hydrogen." Note that, in manufacturing the heating module M, it is desirable to diffusion bond each component. Details of the heating module M will be described later.

[0018] The temperature adjustment unit T adjusts the temperature of the heating element 5 to maintain it at a temperature at which the heating element 5 can generate heat (for example, 50°C to 1500°C). The temperature adjustment unit T includes an electric heater 9, a power supply 10 that supplies power to the electric heater 9, a temperature sensor 11 such as a thermocouple that detects the temperature of the electric heater 9, and a control unit 2 that controls the output of the power supply 10 based on the temperature detected by the temperature sensor 11.

[0019] The hydrogen circulation line L1 introduces a hydrogen-based gas containing hydrogen into the first flow path 6 provided in each laminate structure 4 of the heat generating module M, and repeatedly recovers the permeated gas containing permeated hydrogen that passes through the heating element 5 from the first flow path 6 and is used to generate heat in the heating element 5, flowing into the second flow path 7, and returns it to the first flow path 6.

[0020] The hydrogen circulation line L1 has an inlet pipe 12 that introduces a hydrogen-based gas into a first flow path 6 provided in the laminate structure 4 of the heat generating module M, a recovery pipe 13 that recovers permeated gas from a second flow path 7 provided in the laminate structure 4 of the heat generating module M, and a circulation pump 14 connected to the inlet pipe 12 and the recovery pipe 13. In the heat generating device 1, the heat generating module M and the hydrogen circulation line L1 form a closed loop in which the hydrogen-based gas circulates.

[0021] The inlet pipe 12 extends from the discharge side of the circulation pump 14 and is connected by branch pipes 15 to each of the first flow paths 6 provided in each of the laminate structures 4 of the heat generating module M. Therefore, the hydrogen-based gas is introduced from the inlet pipe 12 through the branch pipes 15 into each of the first flow paths 6.

[0022] The recovery pipe 13 is connected to the intake port of the circulation pump 14, and is connected by branch pipes 16 to each of the second flow paths 7 provided in each of the laminate structures 4 of the heat generating module M. Therefore, the permeated gas flowing through the second flow paths 7 is heated by the heat generating element 5 to a high temperature, and is recovered into the recovery pipe 13 via each branch pipe 16 and reused as a hydrogen-based gas for supplying hydrogen to the heat generating element 5.

[0023] The circulation pump 14 circulates the hydrogen-based gas between the heat generating module M and the hydrogen circulation line L1, which form a closed loop, and is, for example, a metal bellows pump. The circulation pump 14 is electrically connected to the control unit 2, and its operation is controlled by a control signal from the control unit 2.

[0024] A buffer tank 17, a pressure regulating valve 18, and a filter 19 are provided along the inlet pipe 12. The buffer tank 17 is for storing the hydrogen-based gas and absorbing fluctuations in the flow rate of the hydrogen-based gas. The pressure regulating valve 18 is electrically connected to the control unit 2, and its opening is adjusted by a control signal from the control unit 2, thereby adjusting the pressure of the hydrogen-based gas supplied from the buffer tank 17.

[0025] The filter 19 is used to remove impurities contained in the hydrogen-based gas. Here, the amount of hydrogen that permeates the heating element 5 provided in each laminate structure 4 of the heating module M (hydrogen permeation amount) depends on the temperature of the heating element 5, the pressure difference between both sides of the heating element 5, and the surface condition of the heating element 5. If impurities are contained in the hydrogen, the impurities may adhere to the surface of the heating element 5 and deteriorate the surface condition of the heating element 5. If the surface condition of the heating element 5 deteriorates, the adsorption and dissociation of hydrogen molecules on the surface of the heating element 5 is hindered, resulting in a problem of a decrease in the hydrogen permeation amount. Possible substances that hinder the adsorption and dissociation of hydrogen molecules on the surface of the heating element 5 include, for example, water (including water vapor), hydrocarbons (methane, ethane, methanol, ethanol, etc.), C, S, and Si. The filter 19 removes water (including water vapor), hydrocarbons, C, S, Si, etc., as impurities contained in hydrogen, thereby suppressing a decrease in the hydrogen permeation amount through the heating element 5.

[0026] The control unit 2 is electrically connected to and controls the operation of each part of the heat generating device 1. The control unit 2 includes a CPU (Central Processing Unit), and storage units such as a ROM (Read Only Memory) and a RAM (Random Access Memory), and the CPU executes various arithmetic operations using programs and data stored in the ROM and RAM.

[0027] The sealed container 3 is configured as a hollow container made of, for example, stainless steel (SUS). The material of the sealed container 3 is preferably a material having high corrosion resistance and pressure resistance, such as carbon steel, austenitic stainless steel, or corrosion-resistant non-ferrous alloy steel. The material of the sealed container 3 may also be a material that reflects radiant heat generated by the heating element 5 (described later), such as nickel (Ni), copper (Cu), or molybdenum (Mo). The shape of the sealed container 3 is a rectangular cylinder in this embodiment, but is not limited to this and may be a rectangular cylinder, a cylindrical cylinder, an elliptical cylinder, or the like.

[0028] (heat generating module) Next, the configuration of the heat generating module M will be described below with reference to FIGS.

[0029] 2 is an exploded perspective view of the heat generating module M, FIG. 3 is an exploded perspective view of the laminated structure 4 that constitutes the heat generating module M, and FIG.

[0030] As shown in Fig. 2, the heat generating module M is configured by stacking two laminated structures 4 in two stages in the vertical direction (Z-axis direction in Fig. 2). The first flow path 6 at the bottom of the upper laminated structure 4 and the first flow path 6 at the top of the lower laminated structure 4 face each other. In the example shown in Fig. 2, the heat generating module M is formed in a quadrangular prism shape. In the following description, for the heat generating device 1 and each of the components that make up the heat generating device 1, the upper surface in the Z-axis direction is referred to as the top surface, the lower surface in the Z-axis direction is referred to as the bottom surface, the left surface in the Y-axis direction is referred to as the front surface, the right surface in the Y-axis direction is referred to as the back surface, the right surface in the X-axis direction is referred to as the right side surface, and the left surface in the X-axis direction is referred to as the left side surface.

[0031] As shown in FIG. 3, the first flow path 6 is composed of a flat plate portion 6a and a wall portion 6b provided on the flat plate portion 6a. The flat plate portion 6a and the wall portion 6b are made of, for example, stainless steel. The flat plate portion 6a is formed in a quadrangular shape in a plan view. The wall portion 6b is provided on three of the four edge portions of the flat plate portion 6a. In FIG. 3, the wall portion 6b is provided on the left and right edge portions in the X-axis direction and the right edge portion in the Y-axis direction of the four edge portions of the flat plate portion 6a. The wall portion 6b forming the lower first flow path 6 protrudes upward in the Z-axis direction, and the wall portion 6b forming the upper first flow path 6 protrudes downward in the Z-axis direction. A hydrogen inlet 6c is provided on the front surface (the left surface in the Y-axis direction) of the first flow path 6, i.e., on one edge portion of the four edge portions of the flat plate portion 6a where the wall portion 6b is not provided. This hydrogen inlet 6c is connected to a branch pipe 15 of the hydrogen supply line L1 (see FIG. 1).

[0032] The second flow path 7 is composed of a flat plate portion 7a and a wall portion 7b provided on the flat plate portion 7a. The flat plate portion 7a and the wall portion 7b are made of, for example, stainless steel. The flat plate portion 7a is formed in a quadrangular shape in a plan view. The wall portion 7b is provided on three of the four edge portions of the flat plate portion 7a. In FIG. 3, the wall portion 7b is provided on the left and right edge portions in the X-axis direction and the left edge portion in the Y-axis direction of the four edge portions of the flat plate portion 7a. The wall portion 7b forming the lower second flow path 7 protrudes downward in the Z-axis direction, and the wall portion 7b forming the upper second flow path 7 protrudes upward in the Z-axis direction. A hydrogen recovery port 7c is provided on the back surface (the right surface in the Y-axis direction) of the second flow path 7, i.e., on one edge portion of the four edge portions of the flat plate portion 7a where the wall portion 7b is not provided. 3, the hydrogen recovery port 7c provided on the back surface of the lower second flow path 7 is hidden behind the paper surface. The hydrogen recovery port 7c is connected to a branch pipe 16 of the hydrogen circulation line L1 (see FIG. 1).

[0033] The third flow path 8 is formed in a flat plate shape and includes two flat plate portions 8a arranged with a gap between them and two wall portions 8b arranged with a gap between them. The flat plate portions 8a and the wall portions 8b are made of, for example, stainless steel. The flat plate portions 8a are formed in a quadrangular shape in a plan view and are arranged above and below in the Z-axis direction. The wall portions 8b are provided on two opposing edge portions of the four sides of the flat plate portion 8a. In FIG. 3, the wall portions 8b are provided on the left and right edge portions of the four sides of the flat plate portion 8a in the Y-axis direction. A heat medium inlet 8c is provided on the right side surface (the surface on the right side in the X-axis direction) of the third flow path 8, and a heat medium recovery port 8d is provided on the left side surface (the surface on the left side in the X-axis direction) of the third flow path 8. The heat medium inlet 8c is connected to a branch pipe 31e (see FIG. 1) of the heat medium circulation line L2, which will be described later. The heat medium recovery port 8d is connected to a branch pipe 31f (see FIG. 1) of the heat medium circulation line L2, which will be described later. The third flow path 8 constitutes a part of the heat medium circulation line L2.

[0034] The electric heater 9 is provided between two facing first flow paths 6 of two stacked laminated structures 4, i.e., between the first flow path 6 at the bottom of the upper laminated structure 4 and the first flow path 6 at the top of the lower laminated structure 4 (see FIG. 2). The electric heater 9 heats the heating element 5 to a temperature at which it can generate heat (for example, 50°C to 1500°C) via the first flow path 6. In this embodiment, the electric heater 9 is provided in the center of the heating module M in the vertical direction, so that the temperature of the entire heating module M is efficiently increased.

[0035] As shown in FIG. 4 , the electric heater 9 is configured by attaching a heating wire 9b, repeatedly bent in a rectangular wave pattern, to both sides of a rectangular, flat base 9a made of a metal or high-heat-resistant alloy, such as molybdenum or nickel, that has a high heat resistance, or a ceramic, such as alumina or silicon carbide, that is highly heat-resistant and non-reactive with hydrogen. If the base 9a is made of a conductive material, such as a metal, the heating wire 9b is attached to the base 9a via an insulating ceramic. Here, the heating wire 9b is made of molybdenum or tungsten, which has high electrical resistance. By attaching the heating wire 9b in a rectangular wave pattern, repeatedly bent at right angles, as described above, the heating area of ​​the electric heater 9 is increased, thereby increasing the amount of heat generated. In this embodiment, the electric heater 9 is configured by attaching the heating wire 9b to both sides of the base 9a. However, the heating wire 9b may be attached to only one side of the base 9a. Although not shown in Fig. 4, a temperature sensor 11 (see Fig. 1) is provided on the base 9a of the electric heater 9, and a power source 10 (see Fig. 1) is electrically connected to the heating wire 9b. In the electric heater 9, a thin ribbon-shaped planar heater may be used instead of the heating wire 9b.

[0036] The characteristic configuration of the heat generating device 1 according to this embodiment will now be described with reference to FIGS.

[0037] Figure 5 is an enlarged detailed view of part A in Figure 1, and Figure 6 is a cross-sectional view along line BB in Figure 5. In the following, only the characteristic configuration of one (upper) laminated structure 4 will be shown and described, but since the characteristic configuration of the other (lower) laminated structure 4 is similar, it will not be shown or described here.

[0038] As shown in FIG. 5, in the laminated structure 4, on the surface (the lower surface in FIG. 5) of the first partition wall (the partition wall that partitions the first flow path 6 and the second flow path 7) 24 that forms the second flow path 7 between the heating element 5 and the heating element 5, a support 25 for receiving the deformed heating element 5 is provided so as to project toward the heating element 5. Here, in the present embodiment, as shown in FIG. 6, the support 25 is configured by assembling a plurality of metal plates in a lattice shape, and the protruding length L (see FIG. 5) is set to be smaller than the height H of the second flow path 7 (L < H). Therefore, when the heating device 1 is not operating (when the heating element 5 is not bent and deformed), the tip of the support 25 does not contact the heating element 5, and a gap δ shown in the figure is formed between the two.

[0039] The support 25 may be integrally provided on the first partition wall 24, or a support 25 separate from the first partition wall 24 may be attached to the first partition wall 24. Here, any metal with high heat resistance, pressure resistance, and thermal conductivity can be used for the support 25, but in the present embodiment, nickel (Ni) is used. Further, as the support 25, a plurality of metal pins or the like can be used in addition to the plate, but when the support 25 is configured by a metal plate as in the present embodiment, as will be described later, hydrogen (permeated hydrogen) that passes through the heating element 5 and flows into the second flow path 7 is formed in each metal plate so as not to obstruct the flow. As shown in FIGS. 5 and 6, it is necessary to form holes 25a for hydrogen (permeated hydrogen) to pass through. Note that a notch may be formed in each metal plate instead of the hole 25a.

[0040] In the laminated structure 4, as shown in FIG. 5 , the second partition wall 26, which forms the third flow path 8 between itself and the first partition wall 24, is disposed parallel to the first partition wall 24. A plurality of metal heat dissipation members 27, such as heat dissipation pins or heat dissipation fins, are provided on the surface of the first partition wall 24 facing the second partition wall 26 (the upper surface in FIG. 5 ) and protrude at equal intervals in the heat medium flow direction (the left-right direction in FIG. 5 ). The tips of each heat dissipation member 27 are in contact with the second partition wall 26. In this embodiment, stainless steel (SUS) is used for the first partition wall 24 and the second partition wall 26. Similarly to the support 25, any metal having high heat resistance, pressure resistance, and thermal conductivity may be used for the heat dissipation member 27. However, in this embodiment, nickel (Ni) is used. Similarly to the support 25, each heat dissipation member 27 may have a hole or a notch formed therein for the heat medium to pass through.

[0041] In addition, in this embodiment, the plurality of heat dissipation members 27 are integrally provided on the first partition wall 24 so as to protrude therefrom, but the heat dissipation members 27 may be formed separately from the first partition wall 24 and attached to the first partition wall 24. In this embodiment, the heat dissipation members 27 are provided on the first partition wall 24, but the heat dissipation members 27 may be provided on the second partition wall 26 side, and the tips of the heat dissipation members 27 may be in contact with the first partition wall 24.

[0042] In this embodiment, as shown in Figure 5, the tips of the multiple supports 25 that protrude integrally from the first partition 24 are not in contact with the heating element 5 when the heating device 1 is not in operation (when the heating element 5 is not flexibly deformed), and a gap δ is formed between them.However, as shown in Figure 7, the tips of the multiple supports 25 may be in contact with the heating element 5 when the heating device 1 is not in operation.

[0043] <Heating element configuration and heat generation mechanism> Next, the configuration of the heat generating element 5 will be described below with reference to FIG.

[0044] FIG. 8 is a cross-sectional view showing the structure of the heating element 5. As shown in the figure, the heating element 5 has a support 5A and a multilayer film 5B, and the support 5A is made of a hydrogen storage metal, a hydrogen storage alloy, or a proton dielectric. Here, examples of hydrogen storage metals include Ni, Pd, V, Nb, Ta, and Ti. Examples of hydrogen storage alloys include LaNi5, CaCu5, MgZn2, ZrNi2, ZrCr2, TiFe, TiCo, Mg2Ni, and Mg2Cu. Examples of proton dielectrics include BaCeO3-based (e.g., Ba(Ce 0.95 Y 0.05 )O 3-6 ), SrCeO3 system (e.g., Sr(Ce 0.95 Y 0.05 )O 3-6 ), CaZrO3 system (e.g., Ca(Zr 0.95 Y 0.05 )O 3ーα ), SrZrO3 system (e.g., Sr(Zr 0.9 Y 0.1 )O 3ーα ), βAl2O3, βGa2O3, etc. are used.

[0045] The support 5A may be made of a porous body or a hydrogen-permeable membrane. The porous body has a large number of pores large enough to allow hydrogen-based gases to pass through. The porous body is made of a material such as a metal, non-metal, or ceramic. The porous body is preferably made of a material that does not inhibit the exothermic reaction between hydrogen and the multilayer film 5B. The hydrogen-permeable membrane is made of a material that allows hydrogen to pass through. The material of the hydrogen-permeable membrane is preferably a hydrogen-storing metal or a hydrogen-storing alloy. The hydrogen-permeable membrane may also have a mesh-like sheet.

[0046] The multilayer film 5B is formed on the support 5A. In this embodiment, the multilayer film 5B is formed on one surface of the support 5A (the left end surface and the right end surface in FIG. 8). In FIG. 8, only the multilayer film 5B formed on one surface of the support 5A (the left end surface in FIG. 8) is shown, and the multilayer film 5B formed on the other surface of the support 5A (the right end surface in FIG. 8) is not shown. Note that the multilayer film 5B is not limited to being formed on both surfaces of the support 5A, and may be formed on only one surface of the support 5A or only the other surface of the support 5A.

[0047] The multilayer film 5B includes a first layer 51 made of a hydrogen storage metal or a hydrogen storage alloy, and a second layer 52 made of a different hydrogen storage metal, hydrogen storage alloy, or ceramic from the first layer 51, with a dissimilar material interface 53 formed between the first layer 51 and the second layer 52. In the example shown in FIG. 8, the multilayer film 5B is formed as a film structure of ten layers in total, with five first layers 51 and five second layers 52 alternately stacked in this order on one surface (the left end surface in FIG. 8) of the support 5A. The numbers of first layers 51 and second layers 52 are arbitrary, and unlike the example shown in FIG. 8, the multilayer film may be formed by alternately stacking a plurality of second layers 52 and first layers 51 in this order on one surface (the left end surface in FIG. 8) of the support 5A. Furthermore, the multilayer film 5B may have at least one first layer 51 and one second layer 52, and may have at least one interface 53 between the first layer 51 and the second layer 52.

[0048] The first layer 51 is made of, for example, Ni, Pd, Cu, Mn, Cr, Fe, Mg, Co, or an alloy thereof. Here, the alloy making up the first layer 51 is preferably made of two or more of Ni, Pd, Cu, Mn, Cr, Fe, Mg, and Co. The alloy making up the first layer 51 may also be made of Ni, Pd, Cu, Mn, Cr, Fe, Mg, or Co to which an additive has been added.

[0049] The second layer 52 is made of, for example, Ni, Pd, Cu, Mn, Cr, Fe, Mg, Co, alloys thereof, or SiC. Here, the alloy making up the second layer 52 is preferably made of two or more of Ni, Pd, Cu, Mn, Cr, Fe, Mg, and Co. The alloy making up the second layer 52 may also be made of Ni, Pd, Cu, Mn, Cr, Fe, Mg, or Co to which an additive has been added.

[0050] As a combination of the first layer 51 and the second layer 52, when the types of elements are expressed as "first layer-second layer," combinations of Pd-Ni, Ni-Cu, Ni-Cr, Ni-Fe, Ni-Mg, and Ni-Co are preferable. If the second layer 52 is made of ceramic, the combination of Ni-SiC is desirable.

[0051] The thicknesses of the first layer 51 and the second layer 52 constituting the multilayer film 5B of the heating element 5 are preferably each less than 1000 nm. When the thicknesses of the first layer 51 and the second layer 52 are each less than 1000 nm, the first layer 51 and the second layer 52 can maintain a nanostructure that does not exhibit bulk properties. Incidentally, when the thicknesses of the first layer 51 and the second layer 52 are each 1000 nm or more, hydrogen is less likely to permeate the multilayer film 5B. The thicknesses of the first layer 51 and the second layer 52 are preferably less than 500 nm. When the thicknesses of the first layer 51 and the second layer 52 are each less than 500 nm, the first layer 51 and the second layer 52 can maintain a nanostructure that does not exhibit any bulk properties. As shown in FIG. 8, the heating element 5 is configured so that hydrogen permeates the multilayer film 5B while hopping. That is, the heterogeneous material interface 53 formed between the first layer 51 and the second layer 52 allows hydrogen to permeate. In FIG. 8, the manner in which hydrogen hops and permeates through the multilayer film 5B is indicated by dashed arrows.

[0052] Here, the mechanism of heat generation (excess heat generation) when hydrogen permeates the heating element 5 will be described with reference to FIG.

[0053] FIG. 9 is a schematic diagram illustrating the mechanism of excess heat generation in the heating element 5. FIG. 9 shows that the first layer 51 and the second layer 52 of the multilayer film 5B of the heating element 5 are composed of a hydrogen-storing metal having a face-centered cubic structure, and hydrogen in the metal lattice of the first layer 51 permeates the interface 53 between different materials and moves into the metal lattice of the second layer 52. When hydrogen is supplied to the heating element 5, the support 5A and the multilayer film 5B absorb the hydrogen. Here, even if the supply of hydrogen is stopped, the heating element 5 maintains the state in which hydrogen is absorbed by the support 5A and the multilayer film 5B.

[0054] When heating of the heating element 5 by the electric heater 9 begins, the hydrogen absorbed in the support 5A and the multilayer film 5B is released. It is known that hydrogen is light and undergoes quantum diffusion while hopping between sites (octohedral or tetrahedral sites) occupied by hydrogen in a certain substance A and a certain substance B. In the heating element 5, hydrogen permeates the interface 53 of different substances by quantum diffusion, or hydrogen permeates the interface 53 of different substances by diffusion, generating excess heat in an amount greater than the amount of heat generated by the electric heater 9.

[0055] In this embodiment, the first flow path 6, the heating element 5, and the second flow path 7 are stacked in this order so that one surface (front surface) of the heating element 5 faces the first flow path 6 and the other surface (back surface) of the heating element 5 faces the second flow path 7. Therefore, the first flow path 6 is pressurized by the introduction of a hydrogen-based gas, and the second flow path 7 is depressurized by the recovery of the permeated gas. As a result, the hydrogen pressure in the first flow path 6 (referred to as the "hydrogen partial pressure") becomes higher than the hydrogen partial pressure in the second flow path 7, and a hydrogen pressure difference (referred to as the "hydrogen partial pressure difference") occurs on both sides of the heating element 5.

[0056] As described above, when a difference in hydrogen partial pressure occurs on both sides of the heating element 5, a hydrogen molecule contained in the hydrogen-based gas introduced into the first flow path 6 is adsorbed to one surface (front surface) of the heating element 5, the hydrogen molecule dissociates into two hydrogen atoms, and the dissociated hydrogen atoms penetrate into the heating element 5. In other words, hydrogen is absorbed into the heating element 5. The hydrogen atoms that penetrate into the heating element 5 permeate the interface 53 of different materials by quantum diffusion, or permeate the interface 53 of different materials by diffusion. On the other surface (rear surface) arranged on the low-pressure side of the heating element 5, the hydrogen atoms that permeated the heating element 5 recombine to form hydrogen molecules, which are released into the second flow path 7. In other words, hydrogen is released from the heating element 5.

[0057] As described above, the heating element 5 generates excess heat by allowing hydrogen to permeate from the first flow path 6 on the high-pressure side to the second flow path 7 on the low-pressure side. By maintaining a state in which the first flow path 6 is at a higher pressure than the second flow path 7, it is possible to maintain a state in which hydrogen is simultaneously absorbed on the surface of the heating element 5 and released from the back surface of the heating element 5. Note that "simultaneous" does not necessarily mean completely simultaneously, but rather means within a short period of time that can be considered to be substantially simultaneous. By simultaneously absorbing and releasing hydrogen, hydrogen continuously permeates the heating element 5, and excess heat is efficiently generated from the heating element 5.

[0058] <Method of manufacturing the heating element> Here, an example of a method for manufacturing the heat generating element 5 will be described.

[0059] Heating element 5 is manufactured by preparing plate-shaped support 5A, using a vapor deposition apparatus to vaporize a hydrogen-storing metal or alloy to be first layer 51 and second layer 52, and depositing this vapor-phase hydrogen-storing metal or alloy on the surface of support 5A to alternately form first layer 51 and second layer 52. In this case, first layer 51 and second layer 52 are preferably deposited successively in a vacuum, which allows only a dissimilar material interface 53 to be formed between first layer 51 and second layer 52 without forming a native oxide film. A Ni plate, for example, is used as support 5A.

[0060] The deposition apparatus may be a physical deposition apparatus that physically deposits a hydrogen storage metal or alloy on the surface of the support 5A, or a chemical deposition apparatus that chemically deposits a hydrogen storage metal or alloy on the surface of the support 5A. Examples of the physical deposition apparatus include a sputtering apparatus and a vacuum deposition apparatus. Examples of the chemical deposition apparatus include an ALD (Atomic Layer Deposition) apparatus. Alternatively, the first layer 51 and the second layer 52 may be alternately formed on the surface of the support 5A by a thermal spraying method, a spin coating method, a spray coating method, a dipping method, an electroplating method, or the like.

[0061] As shown in Fig. 8, the heating element 5 according to this embodiment has a multilayer film 5B formed by alternately laminating first layers 51 and second layers 52 on a support 5A, but the configuration of the heating element 5 is not limited to this. Modifications 1 and 2 of the configuration of the heating element 5 will now be described with reference to Figs. 10 and 11, respectively. Fig. 10 is a cross-sectional view showing the configuration of a heating element 60 according to modification 1, and Fig. 11 is a cross-sectional view showing the configuration of a heating element 70 according to modification 2.

[0062] <Modification 1 of Heating Element> As shown in Fig. 10, the heating element 60 has a support 60A and a multilayer film 60B. Here, the configuration of the support 60A is the same as the configuration of the support 5A of the heating element 5 shown in Fig. 8, so a description of this support 60A will be omitted.

[0063] Multilayer film 60B is formed on support 60A. In addition to first layer 61 and second layer 62, multilayer film 60B further includes a third layer 63 made of a hydrogen storage metal, hydrogen storage alloy, or ceramic different from those of first layer 61 and second layer 62. The configuration of first layer 61 is the same as that of first layer 51 of heating element 5 shown in FIG. 7 , and the configuration of second layer 62 is the same as that of second layer 52 of heating element 5, so a description of first layer 61 and second layer 62 will be omitted.

[0064] A dissimilar material interface 64 is formed between the first layer 61 and the second layer 62. A dissimilar material interface 65 is formed between the first layer 61 and the third layer 63. The dissimilar material interface 64 and the dissimilar material interface 65 allow hydrogen to permeate, similar to the dissimilar material interface 53 of the heating element 5. In the heating element 60, excess heat is generated when hydrogen permeates the dissimilar material interface 64 and the dissimilar material interface 65 or when hydrogen diffuses at the dissimilar material interface 64 and the dissimilar material interface 65.

[0065] The multilayer film 60B is formed on the support 60A as a multilayer film structure in which a first layer 61 is provided between a second layer 62 and a third layer 63. In the example shown in FIG. 10, the multilayer film 60B is formed by alternately stacking the first layer 61, the second layer 62, the first layer 61, and the third layer 63 in this order on one surface (the upper end surface in FIG. 10) of the support 60A. The multilayer film 60B may be formed in a film structure different from that shown in FIG. 10, i.e., by alternately stacking the first layer 61, the third layer 63, the first layer 61, and the second layer 62 in this order on one surface (the upper end surface in FIG. 10) of the support 60A. The multilayer film 60B is not limited to being formed on one surface (the upper end surface in FIG. 10) of the support 60A, but may also be formed on the other surface (the lower end surface in FIG. 10) of the support 60A or on both surfaces (the upper and lower end surfaces in FIG. 10) of the support 60A. The number of first layers 61, second layers 62, and third layers 63 is arbitrary. The multilayer film 60B only needs to have one or more third layers 63.

[0066] Here, the third layer 63 is made of Ni, Pd, Cu, Cr, Fe, Mg, Co, or an alloy thereof, or SiC, CaO, YO, TiC, LaB, SrO, or BaO. The alloy making up the third layer 63 is preferably made of two or more of Ni, Pd, Cu, Cr, Fe, Mg, and Co. However, the alloy making up the third layer 63 may also be made of Ni, Pd, Cu, Cr, Fe, Mg, or Co to which an additive element has been added.

[0067] In particular, it is desirable that the third layer 63 be made of any one of CaO, Y2O3, TiC, LaB6, SrO, and BaO. A heating element 60 having a third layer 63 made of any one of CaO, Y2O3, TiC, LaB6, SrO, and BaO has an increased hydrogen storage capacity and an increased amount of hydrogen permeating through the dissimilar material interfaces 64 and 65, thereby increasing the excess heat generated by the heating element 60 and achieving higher output.

[0068] The thickness of the third layer 63 is preferably less than 1000 nm. When the thickness of the third layer 63 is less than 1000 nm, the third layer 63 can maintain a nanostructure without exhibiting bulk properties. In particular, the third layer 63 made of any of CaO, YO, TiC, LaB, SrO, and BaO is preferably 10 nm or less in thickness. When the thickness of the third layer 63 is 10 nm or less, the multilayer film 60B can easily allow hydrogen to permeate.

[0069] The third layer 63, which is made of any of CaO, YO, TiC, LaB, SrO, and BaO, preferably has a total thickness of 10 nm or less. This allows the multilayer film 60B to be formed in an island shape rather than a complete film. The first layer 61 and the third layer 63 are preferably formed successively in a vacuum. This allows only a heterogeneous material interface 65 to be formed between the first layer 61 and the third layer 63, without forming a native oxide film.

[0070] The combinations of the first layer 61, the second layer 62 and the third layer 63, when the types of elements are displayed as "first layer-third layer-second layer", are Pd-CaO-Ni, Pd-Y2O3-Ni, Pd-TiC-Ni, Pd-LaB6-Ni, Ni-CaO-Cu, Ni-Y2O3-Cu, Ni-TiC-Cu, Ni-LaB6-Cu, Ni-Co-Cu, Ni-CaO-Cr, Ni-Y2O3-Cr, Ni-TiC-Cr, Ni-LaB6-Cr, N i-CaO-Fe, Ni-Y2O3-Fe, Ni-TiC-Fe, Ni-LaB6-Fe, Ni-Cr-Fe, Ni-CaO-Mg, Ni-Y2O3-Mg, Ni-TiC-Mg, Ni-LaB6-Mg, Ni-Ca Desirably, it is any one of O-Co, Ni-Y2O3-Co, Ni-TiC-Co, Ni-LaB6-Co, Ni-CaO-SiC, Ni-Y2O3-SiC, Ni-TiC-SiC, and Ni-LaB6-SiC.

[0071] <Modification 2 of Heating Element> As shown in Figure 11, the multilayer film 70B of the heating element 70 in this modified example has a support 70A and a multilayer film 70B, but since the configuration of the support 70A is the same as the configuration of the support 5A of the heating element 5 shown in Figure 8, a description of the support 70A will be omitted.

[0072] Multilayer film 70B is formed on support 70A, and in addition to first layer 71, second layer 72, and third layer 73, further includes a fourth layer 74 made of a hydrogen storage metal, hydrogen storage alloy, or ceramic different from those of first layer 71, second layer 72, and third layer 73. The configurations of first layer 71, second layer 72, and third layer 73 are the same as those of first layer 61, second layer 62, and third layer 63 of heating element 60 shown in Fig. 10, and therefore a description of first layer 71, second layer 72, and third layer 73 will be omitted.

[0073] A dissimilar material interface 75 is formed between the first layer 71 and the second layer 72, and a dissimilar material interface 76 is formed between the first layer 71 and the third layer 73. Furthermore, a dissimilar material interface 77 is formed between the first layer 71 and the fourth layer 74. These dissimilar material interfaces 75, 76, and 77 allow hydrogen to permeate, similar to the dissimilar material interface 53 of the heating element 5. In the heating element 70, excess heat is generated when hydrogen permeates the dissimilar material interfaces 75, 76, and 77 by quantum diffusion, or when hydrogen diffuses at the dissimilar material interfaces 75, 76, and 77.

[0074] In FIG. 11 , a first layer 71, a second layer 72, a first layer 71, a third layer 73, a first layer 71, and a fourth layer 74 are stacked in this order on the surface of the support 70A. Alternatively, the first layer 71, the fourth layer 74, the first layer 71, the third layer 73, the first layer 71, and the second layer 72 may be stacked in this order on the surface of the support 70A. That is, the multilayer film 70B has a stacked structure in which the second layer 72, the third layer 73, and the fourth layer 74 are stacked in any order, with the first layer 71 provided between each of the second layer 72, the third layer 73, and the fourth layer 74. The heterogeneous material interface 75 formed between the first layer 71 and the fourth layer 74 allows hydrogen atoms to pass through. The multilayer film 70B may have at least one fourth layer 74.

[0075] The fourth layer 74 is made of Ni, Pd, Cu, Cr, Fe, Mg, Co, or an alloy thereof, or SiC, CaO, YO, TiC, LaB, SrO, or BaO. The alloy constituting the fourth layer 74 is preferably made of two or more of Ni, Pd, Cu, Cr, Fe, Mg, and Co. The alloy constituting the fourth layer 74 may also be made of Ni, Pd, Cu, Cr, Fe, Mg, or Co to which an additive element has been added.

[0076] In particular, the fourth layer 74 is preferably made of any one of CaO, Y2O3, TiC, LaB6, SrO, and BaO. Here, in the heating element 70 having the fourth layer 74 made of any one of CaO, Y2O3, TiC, LaB6, SrO, and BaO, the amount of hydrogen absorbed increases, and the amount of hydrogen permeating the interfaces 75, 76, and 77 of different materials increases, so that the output of excess heat generated by the heating element 70 is increased.

[0077] The thickness of the fourth layer 74 is preferably less than 1000 nm. When the thickness of the fourth layer 74 is less than 1000 nm, the fourth layer 74 can maintain a nanostructure without exhibiting bulk properties. In particular, the fourth layer 74 made of any of CaO, YO, TiC, LaB, SrO, and BaO is preferably 10 nm or less in thickness to allow easy permeation of hydrogen atoms. When the thickness of the fourth layer 74 is 10 nm or less, the multilayer film 70B allows easy permeation of hydrogen.

[0078] Furthermore, the fourth layer 74, which is made of any of CaO, YO, TiC, LaB, SrO, and BaO, may be formed in an island shape rather than as a complete film. Furthermore, the first layer 71 and the fourth layer 74 are preferably formed successively in a vacuum, so that only a dissimilar material interface 75 is formed between the first layer 71 and the fourth layer 74 without forming a native oxide film.

[0079] Desirable combinations of the first layer 71, second layer 72, third layer 73, and fourth layer 74 are Ni-CaO-Cr-Fe, Ni-Y2O3-Cr-Fe, Ni-TiC-Cr-Fe, and Ni-LaB6-Cr-Fe, when the types of elements are expressed as "first layer-fourth layer-third layer-second layer." The configuration of the multilayer film 70B, such as the thickness ratio of each layer, the number of layers, and the materials, can be set appropriately and arbitrarily depending on the heating temperature.

[0080] (Effect of the heating device) Next, the operation of the heat generating device 1 configured as above will be described.

[0081] When the circulation pump 14 is driven by a control signal from the control unit 2, hydrogen (hydrogen-based gas) discharged from the circulation pump 14 is introduced into each of the first flow paths 6 formed in each of the laminate structures 4 of the heat generating module M through the inlet pipe 12 of the hydrogen supply line L1 and four branch pipes 15 branching off from the inlet pipe 12. Note that as the hydrogen (hydrogen-based gas) flows through the inlet pipe 12, pressure fluctuations are suppressed by the buffer tank 17, and the pressure is reduced to a predetermined value by the pressure regulating valve 18.

[0082] Furthermore, the electric heater 9 provided in the heat generating module M generates heat using power supplied from the power source 10, and heats the heat generating element 5 to a predetermined temperature (for example, 50°C to 1500°C) via the hydrogen in the first flow path 6. As described above, the temperature of the heat generating element 5 is adjusted to an appropriate value by the control unit 2 controlling the output of the power source 10 based on the temperature detected by the temperature sensor 11. Here, since the electric heater 9 is interposed between the two laminated structures 4 in the heat generating module M, specifically between the first flow paths 6 facing each other of the two laminated structures 4, the heat of the electric heater 9 is not dissipated to the surroundings by heat radiation from the sealed container 3. Therefore, the heat generating element 5 is efficiently heated to an appropriate temperature, and its power consumption is kept low.

[0083] Incidentally, hydrogen introduced into each first flow path 6 of the heating module M permeates the heating element 5 and flows into the second flow path 7 as described above, and this hydrogen permeates the heating element 5, causing the heating element 5 to generate heat. The mechanism by which this heating element 5 generates heat has been described above (see FIG. 9 ). A hydrogen molecule is adsorbed on one surface (front surface) of each heating element 5, and this hydrogen molecule dissociates into two hydrogen atoms, and the dissociated hydrogen atoms enter the interior of the heating element 5. That is, hydrogen is absorbed into the heating element 5, and the hydrogen atoms pass through the interior of the heating element 5 while diffusing. Furthermore, on the other surface (rear surface) of the heating element 5, the hydrogen atoms that have passed through the heating element 5 recombine and are released as hydrogen molecules. That is, hydrogen is released from the heating element 5. The heating element 5 generates heat by absorbing hydrogen, and also by releasing hydrogen.

[0084] As described above, the hydrogen (permeated hydrogen) that has permeated (passed through) each heating element 5 of the heating module M and is used to generate heat in the heating elements 5 flows out into each branch pipe 16, joins together in the recovery pipe 13, and is then sucked into the circulation pump 14 and recovered. Similar operations are repeated, causing the hydrogen to circulate through the hydrogen circulation line L1 and, in the process, to be used to generate heat in each heating element 5 of the heating module M. In this way, in this embodiment, hydrogen is continuously circulated through the hydrogen circulation line L1 that forms a closed loop, eliminating the need for hydrogen replenishment, which is economical. Furthermore, the high-temperature hydrogen (permeated hydrogen) that has passed through the heating elements 5 prevents each heating element 5 from being supercooled, thereby accelerating the heat generation of each heating element 5.

[0085] As shown in FIG. 1, the first flow path 6 into which hydrogen is introduced is connected to the discharge side of the circulation pump 14 via a branch pipe 15 and an inlet pipe 12, and the second flow path 7 into which permeated hydrogen flows is connected to the suction side of the circulation pump 14 via a branch pipe 16 and a recovery pipe 13. Therefore, the pressure in the first flow path 6 is higher than the pressure in the second flow path 7, and a pressure difference occurs between the first flow path 6 and the second flow path 7.

[0086] Here, the heating element 5 is very thin and therefore easily deformed, and as mentioned above, due to the pressure difference between the first flow path 6 and the second flow path 7, the heating element 5 is bent and deformed in an arc-shaped curve so as to bulge toward the second flow path 7 side (upward in Figure 12) where the pressure is lower, as shown in Figure 12 (see Figure 16).

[0087] In the heating device 1 according to this embodiment, as shown in FIGS. 5 and 6, a plurality of supports 25 are provided on the surface of the first partition wall 24 facing the heating element 5, protruding toward the heating element 5. As a result, the deflected heating element 5 comes into contact with the supports 25 and is supported by the supports 25, as shown schematically in FIG. 12. This prevents further deformation of the heating element 5, and the supports 25 keep the deflection of the heating element 5 small. In other words, the maximum deflection of the heating element 5 is kept to δ (gap). As a result, peeling of the multilayer film 5B from the support 5A (see FIG. 8) due to deformation of the heating element 5 is prevented, improving the durability of the heating element 5. Furthermore, the heating action of the heating element 5 is not hindered by deformation, and the heating element 5 can stably generate heat, resulting in high heat generation efficiency and heat exchange efficiency.

[0088] Furthermore, in the heat generating device 1 according to this embodiment, in each stacked structure 4 constituting the heat generating module M, the third flow path 8 is disposed adjacent to the second flow path 7, and therefore the heat medium flowing through the third flow path 8 is efficiently heated by heat exchange with the permeated hydrogen (permeated gas) flowing through the second flow path 7. That is, the second flow path 7 and the third flow path 8 function as a heat exchanger, and heat generated in the heat generating element 5 is efficiently recovered to the heat medium via the permeated hydrogen (permeated gas). Some of the heat generated in the heat generating element 5 is transferred from the permeated hydrogen (permeated gas) through the first partition wall 24 to the multiple heat dissipation members 27, and the heat medium is efficiently heated by heat dissipation from these heat dissipation members 27. That is, the multiple heat dissipation members 27 increase the heat transfer area of ​​the first partition wall 24, thereby improving the heat exchange efficiency between the heat generating element 5 and the permeated hydrogen (permeated gas), and the heat generated in the heat generating element 5 is more efficiently recovered by the heat medium.

[0089] Furthermore, a portion of the heat generated in the heating element 5 is conducted to the first partition 24 via the support 25 that contacts and supports the heating element 5, and this heat is conducted from the first partition 24 to the heat dissipation member 27 and used to heat the heat medium, so that the heat generated in the heating element 5 is recovered more effectively by the heat medium.

[0090] (Calculation results of heat transfer and their considerations) Table 1 shows the results of calculations of the temperature and heat transfer amount (radiant heat amount, conductive heat amount, and their total) of the first partition wall 24 and the second partition wall 26 for cases where no supports 25 were provided and where supports 25 arranged in a lattice pattern were provided. Tables 2 and 3 show the physical property data of nickel used in the supports 25 and heat dissipation member 27 and the physical property data of stainless steel (SUS) used in the first partition wall 24 and the second partition wall 26, respectively. These physical property data were used to calculate the temperature and heat transfer amount. As shown in FIG. 5, plates arranged in a lattice pattern were used as supports 25. The number of supports 25, the number of lattice sections, and the section size were changed as shown in Table 1, resulting in Case 0, Case 1, Case 2, and Case 3, respectively. The height of the supports 25 was 1 mm, and the thickness was 0.1 mm.

[0091] Case 0 shown in Table 1 is the case where there is no support, Case 1 is the case where the number of supports 25 is 2, the number of lattice divisions is 4, and the lattice division size is 10.5 mm, Case 2 is the case where the number of supports 25 is 6, the number of lattice divisions is 16, and the lattice division size is 5.25 mm, and Case 3 is the case where the number of supports 25 is 14, the number of lattice divisions is 64, and the lattice division size is 2.625 mm.

[0092] [Table 1]

[0093] [Table 2]

[0094] [Table 3]

[0095] The results shown in Table 1 show that the greater the number of supports 25, the greater the amount of heat transferred to the first partition wall 24 and the second partition wall 26. For example, in Case 0, where there are no supports, the temperature of the second partition wall 26 is 768.4°C, whereas in Case 3, where there are 14 supports 25 (divided into 64), the temperature of the second partition wall 26 is 894.8°C, which is more than 120°C higher than in Case 0, where there are no supports.

[0096] Furthermore, the heat medium returned to the heat generation module M from the fourth pipe 31d of the heat medium circulation line L2 of the heat utilization system (see FIG. 14 ) described below is introduced from the fourth pipe 31d through two branch pipes 31e into each of the third flow paths 8. As it flows through each of the third flow paths 8, it is heated by heat exchange with the high-temperature permeated hydrogen flowing through the two second flow paths 7 located on both sides of the third flow path 8. That is, the heat medium is heated by absorbing heat from the high-temperature permeated gas flowing through the second flow paths 7, and the heat is transported to the heat utilization device 30 (see FIG. 14 ) and used as a heat source for the heat utilization device 30. In this case, the heat medium flowing through the third flow path 8 is effectively heated by the permeated gas flowing through the two second flow paths 7 located on both sides of the third flow path 8, thereby improving the heat recovery efficiency of the heat medium. Therefore, the heat generation module M also functions as a heat exchanger, and the heat generation device 1 including this heat generation module M has an integrated heat generation / heat exchange configuration.

[0097] That is, the heat medium heated by heat exchange with the permeate gas while flowing through each third flow path 8 of the heat generation module M passes through the branch pipe 31f from each third flow path 8 to merge with the first pipe 31a, and is supplied to the heat utilization device 30 via this first pipe 31a, which performs required work such as power generation using the heat supplied from the heat medium. Then, the heat medium whose temperature has dropped after supplying heat to the heat utilization device 30 passes through the fourth pipe 31d and branch pipe 31e and is returned to the heat generation module M, where it is heated again. Thereafter, the same action is continuously repeated, and the heat utilization device 30 is continuously driven.

[0098] As described above, the heat generating device 1 according to this embodiment comprises a laminated structure 4 formed by sequentially and symmetrically stacking, on both sides of the third flow path 8 through which the heat medium flows, the second flow path 7 for receiving hydrogen that has permeated the heat generating element 5 (permeated hydrogen), the heat generating element 5, and the first flow path 6 for introducing hydrogen into the heat generating element 5, in that order from the third flow path 8, and an electric heater 9 for heating the heat generating element 5. The laminated structure 4 is formed by stacking the heat generating element 5, the first flow path 6, the second flow path 7, and the third flow path 8 at a high density. As a result, the laminated structure 4 can generate heat efficiently, and the laminated structure 4 and the heat generating device 1 including it can be made small and compact.

[0099] Furthermore, in the laminated structure 4, the heat generated by the heating element 5 is efficiently transferred to the heat medium through heat exchange between the heat medium flowing through the third flow path 8 and hydrogen (permeable gas) flowing through the second flow paths 7 arranged on both sides of the third flow path 8, so that the heat generated in the heating element 5 can be efficiently recovered by the heat medium.

[0100] In this embodiment, the heat generating module M is constructed by stacking two laminated structures 4 in two layers, but it is also possible to stack three or more laminated structures 4 in three or more layers to form a heat generating module M with a multi-layer structure.By doing so, the heat generating module M can generate heat more efficiently and achieve higher output.

[0101] The heat generating device 1 may be configured such that, of the hydrogen introduced into each first flow path 6, hydrogen that does not permeate the heating element 5 (also referred to as "non-permeating hydrogen") is recovered using a non-permeating hydrogen recovery line (not shown), returned to the upstream side (low-pressure side) of the circulation pump 14 of the recovery pipe 13, and then introduced again into each first flow path 6 through the introduction pipe 12 and branch pipe 15 to be used to generate heat in each heating element 5.

[0102] As shown in FIG. 5 , when the tips of the supports 25 protruding from the first partition wall 24 do not contact the heating element 5 when the heating device 1 is not in operation, forming a gap δ between them, the heating element 5 curves and bulges upward as shown in FIG. 12 when the heating device 1 is in operation. In contrast, when the tips of the supports 25 contact the heating element 5 when the heating device 1 is not in operation, as shown in FIG. 7 , the heating element 5 flexes and bulges upward between adjacent supports 25 as shown in FIG. 13 . In this case, the amount of flexure between the supports 25 of the heating element 5 is kept small compared to the amount of flexure shown in FIG. 12 . This reduces the stress acting on the heating element 5, prevents plastic deformation of the heating element 5, and improves its durability. Furthermore, because the tips of all the supports 25 contact the heating element 5, heat conduction to the first partition wall 24 is promoted via these supports 25.

[0103] Here, we calculated the maximum stress acting on the portion of the nickel heating element 5 partitioned by the lattice-like support 25 (the portion restrained on all four sides by the metal plates) when the support 25 is composed of a lattice-like metal plate as shown in Figure 6. In the calculation, when the lattice spacing of the metal plates constituting the support 25 was 10 mm, the thickness was 0.1 mm, and the pressure acting on the heating element 5 was 100 KPa, the maximum stress acting on each partitioned portion of the heating element 5 was 287 MPa.

[0104] The strength (tensile strength and yield strength) of nickel, which is the material of the heating element 5, is temperature dependent, and for example, the yield stress at a temperature of 900°C is approximately 16 MPa. Therefore, the maximum stress of 287 MPa acting on each compartment of the heating element 5 exceeds the yield stress of 16 MPa of nickel at a temperature of 900°C, and there is a possibility that the heating element 5 will undergo plastic deformation.

[0105] Therefore, in order to prevent the occurrence of the above-mentioned plastic deformation, it is necessary to take into account a safety factor and reduce the stress to, for example, 12 MPa (1 / 24 of the maximum stress of 287 MPa), which is less than 3 / 4 of the yield stress of 16 MPa. Therefore, to keep the maximum stress acting on each lattice portion of the heating element 5 at 12 MPa or less, the spacing a of the supports 25 (the lattice spacing of the heating element 5) must be set to 10 mm / √24 = 1.8 mm or less.

[0106] Incidentally, when the thickness t of the heating element 5 and the pressure p acting on each lattice portion are constant, the maximum stress acting on each lattice portion of the heating element 5 is proportional to the square of the spacing a (lattice spacing) of the supports 25. Furthermore, the lower the operating temperature of the heating element 5, the greater the yield stress, so the spacing a of the supports 25 can be increased. Furthermore, when the pressure difference acting on the heating element 5 is small, the stress acting on the heating element 5 also decreases proportionally, so the spacing a of the supports 25 can also be increased.

[0107] If the above relationship is expressed as an approximation equation with temperature T, the spacing a of the supports 25 is a<0.866t{(177-0.183T) / (0.287p)} 0.5 It is desirable to satisfy the following.

[0108] [Heat utilization system] Next, a heat utilization system for utilizing the heat generated in the heat generating device 1 according to the present invention will be described below with reference to FIG.

[0109] The heat utilization system shown in Fig. 12 includes the heat generation device 1 according to the present invention and a heat utilization device 30. Here, the heat utilization device 30 is a device that generates electricity using a heat medium heated by heat generated in the heat generation device 1 as a heat source, and includes a heat medium circulation line L2, a gas turbine 32, a steam generator 33, a steam turbine 34, a Stirling engine 35, and a thermoelectric conversion unit 36. Below, the heat medium circulation line L2, the gas turbine 32, the steam generator 33, the steam turbine 34, the Stirling engine 35, and the thermoelectric conversion unit 36 ​​will be described respectively below.

[0110] (heat medium circulation line) The heat medium circulation line L2 forms a closed loop that circulates the heat medium among the heat generation module M of the heat generation device 1, the gas turbine 32, the steam generator 33, the steam turbine 34, the Stirling engine 35, and the thermoelectric converter 36. Specifically, the heat medium circulation line L2 includes a first pipe 31a extending from the outlet side of the third flow path 8 of the heat generation module M and connected to the gas turbine 32, a second pipe 31b connecting the gas turbine 32 and the steam generator 33, a third pipe 31c connecting the steam generator 33 and the Stirling engine 35, and a fourth pipe 31d extending from the Stirling engine 35 and connected to the inlet side of the third flow path 8 of the heat generation module M. A circulation pump 37 and a flow control valve 38 are provided midway along the first pipe 31a. A metal bellows pump or the like is used as the circulation pump 37, and a variable leak valve or the like is used as the flow control valve 38.

[0111] (Gas Turbine) The gas turbine 32 includes a compressor 32a and a turbine 32b that are connected by a common shaft, and a generator 40 is connected to the output shaft of the turbine 32b.

[0112] (Steam generator) The steam generator 33 generates high-pressure steam for driving the steam turbine 34, and includes an internal pipe 33a connected to the second pipe 31b and a heat exchange pipe 33b facing the internal pipe 33a. The heat exchange pipe 33b is connected to the inlet side of the steam turbine 34 via a steam pipe 33c, and is connected to the outlet side of the steam turbine 34 via a feedwater pipe 33d. Although not shown, a condenser and a feedwater pump are provided in the feedwater pipe 33d. A generator 50 is connected to the output shaft of the steam turbine 34.

[0113] (Stirling engine) The Stirling engine 35 includes a cylinder 35a, a displacer piston 35b, a power piston 35c, a flow path 35d, and a crank portion 35e. The interior of the cylinder 35a is divided by the displacer piston 35b into an expansion space S1 and a compression space S2, and a working fluid is sealed in the expansion space S1 and the compression space S2. While helium gas, hydrogen-based gas, air, or the like can be used as the working fluid, helium gas is used in this embodiment.

[0114] Furthermore, flow path 35d is provided outside cylinder 35a and connects expansion space S1 and compression space S2. Flow path 35d functions to circulate working fluid between expansion space S1 and compression space S2 and includes high-temperature section 35f, low-temperature section 35g, and regenerator 35h. The working fluid in expansion space S1 passes through high-temperature section 35f, regenerator 35h, and low-temperature section 35g in this order before flowing into compression space S2. The working fluid in compression space S2 passes through low-temperature section 35g, regenerator 35h, and high-temperature section 35f in this order before flowing into expansion space S1.

[0115] The high-temperature section 35f is a heat exchanger for heating the working fluid, and a heat transfer tube 35i is provided outside the high-temperature section 35f. The heat transfer tube 35i connects the third pipe 31c and the fourth pipe 31d, and functions to circulate the heat medium from the third pipe 31c to the fourth pipe 31d. When the heat medium flows from the third pipe 31c to the heat transfer tube 35i, the heat of the heat medium is transferred to the high-temperature section 35f, and the working fluid passing through the high-temperature section 35f is heated.

[0116] The low-temperature section 35g is a heat exchanger for cooling the working fluid, and a cooling pipe 35j is provided outside the low-temperature section 35g. The cooling pipe 35j is connected to a cooling medium supply unit (not shown) that supplies a cooling medium such as water, and passes the cooling medium supplied from the cooling medium supply unit. When the cooling medium flows through the cooling pipe 35j, the working fluid passing through the low-temperature section 35g is cooled by the cooling medium removing heat from the cooling medium.

[0117] The regenerator 35h is a heat exchanger for storing heat and is provided between the high-temperature section 35f and the low-temperature section 35g. When the working fluid moves from the expansion space S1 to the compression space S2, the regenerator 35h receives and stores heat from the working fluid that has passed through the high-temperature section 35f. When the working fluid moves from the compression space S2 to the expansion space S1, the regenerator 35h provides the stored heat to the working fluid that has passed through the low-temperature section 35g, thereby heating the working fluid.

[0118] The crank section 35e is provided at the other end of the cylinder 35a and includes a crankshaft rotatably supported in a crankcase (not shown), a rod connected to the displacer piston 35b, a rod connected to the power piston 35c, and connecting members connecting each rod to the crankshaft, and serves to convert the reciprocating linear motion of the displacer piston 35b and the power piston 35c into rotational motion. A generator 80 is connected to the crankshaft of the Stirling engine 35.

[0119] (Thermoelectric conversion part) The thermoelectric converter 36 converts the heat of the heat medium flowing through the fourth pipe 31d into electric power by utilizing the Seebeck effect, and converts, for example, the heat of the heat medium at 300° C. or less into electric power. The thermoelectric converter 36 is formed in a cylindrical shape and is disposed so as to cover the outer periphery of the fourth pipe 31d.

[0120] The thermoelectric conversion unit 36 ​​includes a thermoelectric conversion module 36a provided on the inner surface and a cooling unit 36b provided on the outer surface. Here, the thermoelectric conversion module 36a includes a heat receiving substrate facing the fourth pipe 31d, a heat receiving-side electrode provided on the heat receiving substrate, a heat dissipation substrate facing the cooling unit 36b, a heat dissipation-side electrode provided on the heat dissipation substrate, p-type thermoelectric elements formed of p-type semiconductors, and n-type thermoelectric elements formed of n-type semiconductors. In this embodiment, the thermoelectric conversion module 36a has p-type thermoelectric elements and n-type thermoelectric elements arranged alternately, and adjacent p-type thermoelectric elements and n-type thermoelectric elements are electrically connected by a heat receiving-side electrode and a heat dissipation-side electrode.

[0121] In addition, the thermoelectric conversion module 36a has leads electrically connected to the p-type thermoelectric element arranged at one end and the n-type thermoelectric element arranged at the other end via heat-dissipation electrodes. Here, the cooling unit 36b is formed, for example, by a pipe through which cooling water flows, and the thermoelectric conversion unit 36 ​​generates power according to the temperature difference occurring between its inner and outer surfaces.

[0122] (Thermal utilization system action) Next, the operation of the heat utilization system configured as above will be described.

[0123] In the heat generation device 1 according to the present invention, as described above, heat generated by hydrogen permeating each heating element 5 of the heat generation module M is imparted to the heat medium flowing through the third flow path 8, thereby heating the heat medium to a predetermined temperature. When the circulation pump 37 provided in the first pipe 31a of the heat utilization device 30 is driven, the heated heat medium circulates through the third flow path 8, the first pipe 31a, the second pipe 31b, the third pipe 31c, and the fourth pipe 31d of the heat generation module M, which form a closed loop. The gas turbine 32, the steam turbine 34, the Stirling engine 35, and the thermoelectric converter 36 are sequentially driven by the heat supplied from the heat medium, thereby generating the required amount of electricity. At this time, the flow control valve 38 controls the flow rate of the heat medium based on the temperature detected by the temperature sensor 11 (see FIG. 1 ). That is, when the temperature of the heating element 5 detected by the temperature sensor 11 exceeds an appropriate upper limit temperature, the flow control valve 38 increases the circulating flow rate of the heat medium to suppress a rise in the temperature of the heating element 5. Conversely, when the temperature of the heating element 5 detected by the temperature sensor 11 is below the appropriate lower limit temperature, the flow control valve 38 reduces the circulating flow rate of the heat medium to prevent the temperature of the heating element 5 from dropping.

[0124] The high-temperature (for example, 600°C to 1500°C) heat medium that is heated by the heat generation module M of the heat generation device 1 and flows from the third flow path 8 to the first pipe 31a is introduced into the gas turbine 32 and compressed by the compressor 32a of this gas turbine 32. The compressed heat medium then expands and flows through the turbine 32b, which rotates and drives the turbine 32b, and the generator 40 connected to the output shaft of this turbine 32b is rotated and generates required electricity. That is, part of the heat of the heat medium is converted into kinetic energy of the gas turbine 32, and this kinetic energy is converted into electrical energy by the generator 40.

[0125] Then, the heat medium discharged from the gas turbine 32 to the second pipe 31b exchanges heat with boiler water flowing through the heat exchange pipe 33b while flowing through the internal pipe 33a of the steam generator 33, thereby heating the boiler water. As a result, high-temperature (300°C to 700°C) and high-pressure steam is generated in the steam generator 33, and this steam is supplied to the steam turbine 34 through the steam pipe 33c. As a result, the steam turbine 34 is rotationally driven by the steam, and the rotation of this steam turbine 34 also rotates and drives the generator 50, thereby generating the required electricity. That is, part of the heat of the heat medium is converted into kinetic energy of the steam turbine 34, and this kinetic energy is converted into electrical energy by the generator 50. The steam whose temperature has been reduced by being used to drive the steam turbine 34 is cooled in a condenser (not shown) and returned to the boiler water. This boiler water flows from the water supply pipe 33d to the heat exchange pipe 33b of the steam generator 33, and in the process, the boiler water is heated by the thermal refrigerant flowing through the internal pipe 33a and turns into steam.

[0126] Furthermore, the heat medium having a temperature of 300°C to 1000°C, which is used to generate steam while flowing through the internal pipe 33a of the steam generator 33, is supplied from the internal pipe 33a through the third pipe 31c to the Stirling engine 35, and is used to drive the Stirling engine 35 by the above-mentioned action. As a result, the crankshaft of the Stirling engine 35 is driven to rotate, and the generator 80 connected to this crankshaft is also driven to rotate, thereby generating the required amount of electricity. In other words, part of the heat of the heat medium is converted into kinetic energy of the Stirling engine 35, and this kinetic energy is converted into electrical energy by the generator 80.

[0127] As described above, the heat medium used to drive the Stirling engine 35 is supplied to the thermoelectric converter 36 via the fourth pipe 31d, and part of the heat of this heat medium is converted into electric power by the Seebeck effect as described above. That is, part of the heat of the heat medium is converted into electric energy by the thermoelectric converter 36.

[0128] Then, the heat medium, whose temperature has been reduced after being used for power generation in the thermoelectric conversion section 36, is returned to the inlet side of the third flow path 8 of the heat generation module M from the fourth piping 31d, and thereafter the same action is continuously repeated, with the heat generated in the heat generation module M being recovered by the heat medium and the thermal energy being converted into electrical energy.

[0129] In this embodiment, the gas turbine 32, the steam turbine 34, and the Stirling engine 35 are driven by the heat recovered by the heat medium, and the kinetic energy is converted into electrical energy by the generators 40, 50, and 80, and the thermal energy is directly converted into electrical energy by the thermoelectric conversion unit 36. However, the heat utilization device 30 may be configured by arbitrarily combining the gas turbine 32, the steam turbine 34, the Stirling engine 35, and the thermoelectric conversion unit 36.

[0130] Furthermore, in the above embodiment, the heat utilization device 30 that converts thermal energy into electrical energy has been described, but the heat generated by the heat generation device 1 of the present invention can be used for purposes other than power generation, such as preheating the combustion air supplied to a boiler, heating an absorption liquid that has absorbed CO2 by chemical absorption, heating raw material gas containing CO2 and H2 in a methane production plant, as well as heat pump systems, heat transport systems, and cold (refrigeration) systems.

[0131] In the heat utilization system described above, the heat generated in the heat generating device 1 is recovered by the heat medium flowing through the third flow path 8 and supplied to the heat utilization device 30. However, the third flow path 8 may not be provided and the heat may be recovered directly by the permeable gas flowing through the second flow path 7. In this case, the second partition wall 26 and the heat dissipation member 27 are not necessary, and the first partition wall 24 and the support 25 function as heat dissipation members, increasing the heat transfer area and improving the heat recovery efficiency. When such a configuration is adopted, it is desirable to introduce another heat medium into the second flow path 7, recover the permeable gas and the heat medium from the second flow path 7, separate the permeable gas and the heat medium using a hydrogen-permeable membrane or the like, return the permeable gas to the hydrogen circulation line L1, and supply the heat medium to the heat utilization device 30.

[0132] It should be noted that the present invention is not limited to the application of the above-described embodiments, and various modifications are possible within the scope of the claims and the technical ideas described in the specification and drawings. [Explanation of symbols]

[0133] 1 Heating device 5 Heating element 6 First flow path 7 Second flow path 8 Third Stream 24 First Bulkhead 25 Support 26 Second bulkhead 27 Heat dissipation material

Claims

1. The fuel cell comprises a flat heating element that generates heat by absorbing and releasing hydrogen, a first flow path through which a hydrogen-based gas containing the hydrogen is introduced and which supplies hydrogen to the heating element, and a second flow path through which a permeated gas containing hydrogen that has permeated the heating element flows, A heat generating device configured by arranging the first flow path and the second flow path on both sides of the heat generating element, a support for receiving the deformed heating element is provided on a first partition wall that forms the second flow path between the first partition wall and the heating element, and protrudes toward the heating element; a third flow path through which a heat medium flows is disposed adjacent to the second flow path, and a heat dissipation member is provided on at least one of the first and second partition walls, which form the third flow path between themselves and the first partition wall, and which protrudes toward the other partition wall and makes contact with the other partition wall.

2. The heat generating device according to claim 1 , wherein the support is made up of a plurality of metal pins or plates.

3. 3. The heat generating device according to claim 1, wherein the heat dissipating member is made up of a plurality of metal heat dissipating pins or fins.

4. A heating element having a flat shape that generates heat by absorbing and releasing hydrogen, a first flow path through which a hydrogen-based gas containing the hydrogen is introduced and which supplies hydrogen to the heating element, and a second flow path through which a permeated gas containing hydrogen that has permeated the heating element flows, A heat generating device configured by arranging the first flow path and the second flow path on both sides of the heat generating element, a support for receiving the deformed heating element is provided on a first partition wall that forms the second flow path between the first partition wall and the heating element, and protrudes toward the heating element; The support is a heat generating device configured by assembling multiple metal plates in a grid pattern.

5. A heat generating device as described in Claim 4, wherein each of the metal plates has holes formed therein for hydrogen to pass through.

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