Heat generating module and heat generating device

Abstract

To provide a heating cell having high durability and capable of stably heating, a heating module with high output which is equipped with the heating cell, and a small-sized and compact heating device with high thermal efficiency and high durability.SOLUTION: On an outer peripheral surface of a cylindrical supporting body configured by a porous metal sintered body, a porous ceramic sintered body or a Vycor type porous glass, a multilayer film is formed to configure a heating cell. The plurality of heating cells and rod heaters are bundled and integrated to configure heating module M. Furthermore, a heating device 5 is equipped with a storage container 6 that stores the heating module M, a supply line L1 that supplies hydrogen and a heat medium to the storage container 6, a discharge line L2 that discharges the hydrogen and the heat medium in the storage container 6, and a permeation hydrogen recovery line L3 that returns permeation hydrogen permeating the multilayer of each heating cell of the heating module M and discharged from the supporting body to the supply line L1 to recover.SELECTED DRAWING: Figure 11

Description

[Technical Field]

[0001] The present invention relates to a heat generating cell that generates heat by hydrogen permeation, a heat generating module including a plurality of such heat generating cells, and a heat generating device including such a heat generating module. [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] 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, the heat generating element can be constructed from a support and a multilayer film supported on the support, so that 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, or 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 hydrogen into the heating element 105 and a second flow path 107 for receiving hydrogen that has permeated through the heating element 105 are disposed on both sides of the heating element 105, and the heating element 105 and the first and second flow paths 106, 107 are stacked at high density to make the heating device 101 small, compact, and high-power with high heating efficiency. In the heating device 101 configured in this way, 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, since the heating element 105 is made of a very thin flat plate made of a hydrogen-absorbing metal or a hydrogen-absorbing alloy, it bends and deforms into an arc-shaped curved surface so as to bulge toward the second flow path side 107 where the pressure is lower, as shown in Figure 16. This bending deformation generates large stress, which may cause the multilayer film to peel off from the support of the heating element 105, reducing the durability of the heating element 105 and preventing the heating element 105 from generating heat stably.

[0009] The present invention has been made in view of the above problems, and aims to provide a heating cell that is highly durable and capable of stably generating heat, a high-output heating module including the same, and a heating device that is small and compact yet has high heating efficiency and durability. [Means for solving the problem]

[0010] In order to achieve the above object, the heating cell of the present invention is constructed by forming a multilayer film that generates heat by allowing hydrogen to pass through the outer surface of a cylindrical support made of a porous metal sintered body, a porous ceramic sintered body, or a Vycor-type porous glass.

[0011] The heat generating module according to the present invention includes a plurality of the heat generating cells, and is configured by bundling the plurality of heat generating cells and a rod-shaped heater together to form an integrated unit.

[0012] Furthermore, the heat generating device according to the present invention is a heat generating device equipped with the heat generating module, and includes a containment vessel for storing the heat generating module, a supply line for supplying hydrogen and a heat medium to the containment vessel, a discharge line for discharging the hydrogen and the heat medium from the containment vessel, and a permeated hydrogen recovery line for returning permeated hydrogen that has permeated through the multilayer film of each heat generating cell of the heat generating module and is discharged from the support to the supply line and recovering it. [Effects of the Invention]

[0013] The heating cell according to the present invention is constructed by forming a multilayer film on the outer peripheral surface of a highly rigid cylindrical support, so that it does not easily deform even when subjected to external forces, and the multilayer film formed on the outer peripheral surface of the support does not peel off. This ensures stable heat generation and enhanced durability. The heating cell generates heat when hydrogen permeates the multilayer film, and the permeated high-temperature hydrogen (permeated hydrogen) passes through the inside of the support and is discharged to the outside.

[0014] Furthermore, the heat generating module according to the present invention is constructed by bundling and integrating a plurality of heat generating cells and rod-shaped heaters, thereby increasing the amount of heat generated and achieving higher output, and also improving the durability of the heat generating module.

[0015] Furthermore, in the heat generating device according to the present invention, the high-temperature heat medium that has recovered the heat generated in the heat generating modules housed in the containment vessel is supplied to, for example, a heat utilization device via a discharge line and used to drive the heat utilization device, and the heat medium that has been used to drive the heat utilization device and whose temperature has decreased is returned to the containment vessel via a supply line and used to recover the heat generated in the heat generating modules.

[0016] In addition, the hydrogen (permeated hydrogen) that has permeated through each heat-generating cell of the heat-generating module and is used to generate heat in the heat-generating cell is discharged from the containment vessel and returned to the supply line via the permeated hydrogen recovery line, where it merges with the hydrogen and heat medium flowing through the supply line and is supplied back to the containment vessel to be used to generate heat in the heat-generating module and to recover the heat generated in the heat-generating module. [Brief explanation of the drawings]

[0017] [Figure 1] 1 is a perspective view of a heat generating cell according to the present invention. [Figure 2] FIG. 2 is an enlarged cross-sectional view taken along the line AA in FIG. [Figure 3] 3 is an enlarged detailed view of part B in FIG. 2, showing the layer structure of the heating element of the heating cell according to the present invention. [Figure 4] 3 is a schematic diagram illustrating the mechanism of excess heat generation in the heating element of the heating cell according to the present invention. FIG. [Figure 5] FIG. 1 is a cross-sectional view showing a first modified example of the configuration of a heat generating element provided in a heat generating cell according to the present invention. [Figure 6] FIG. 10 is a cross-sectional view showing a second modified example of the configuration of the heat generating element provided in the heat generating cell according to the present invention. [Figure 7A] FIG. 1 is a diagram showing the relationship between the pore size and stress of the support of the heat generating cell according to the present invention. [Figure 7B]FIG. 1 is a diagram showing the relationship between the pore size and stress of the support of the heat generating cell according to the present invention. [Figure 8A] FIG. 1 is a diagram showing the relationship between the porosity and compressive strength of the support of the heating cell according to the present invention. [Figure 8B] FIG. 1 is a diagram showing the relationship between the porosity and compressive strength of the support of the heating cell according to the present invention. [Figure 9] 1 is a diagram showing the relationship between the inner diameter and the wall thickness of the support of the heat generating cell according to the present invention, with the differential pressure as a parameter. [Figure 10] 1 is a perspective view of a heat generating module according to the present invention; [Figure 11] 1 is a block diagram showing a configuration of a heat generating device according to the present invention; [Figure 12] 1 is a block diagram showing the configuration of a heat utilization system including a heat generating device according to the present invention. [Figure 13] 1 is an explanatory diagram illustrating an ammonia production plant equipped with a heat generating device according to the present invention. [Figure 14] FIG. 1 is a block diagram showing the configuration of a heat generating device of an ammonia production plant. [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. DETAILED DESCRIPTION OF THE INVENTION

[0018] Hereinafter, an embodiment of the present invention will be described with reference to the accompanying drawings.

[0019] [Heat generating cell] The configuration of the heat generating cell according to the present invention will be described below with reference to FIGS.

[0020] FIG. 1 is a perspective view of a heat generating cell according to the present invention, and FIG. 2 is an enlarged cross-sectional view taken along line AA in FIG. 1. The heat generating cell 1 shown in the figure is constructed by forming a multilayer film 1B, which generates heat by allowing hydrogen to pass through, on the outer surface of a cylindrical (round pipe-shaped) support 1A made of porous sintered metal, porous ceramic, or Vycor-type porous glass. The porous sintered metal, porous ceramic, or Vycor-type porous glass that constitutes the support 1A has numerous pores large enough to allow hydrogen to pass through. The porous sintered metal or porous ceramic is made of a material that does not inhibit the exothermic reaction between hydrogen and the multilayer film 1B. Specifically, the porous sintered metal is made of, for example, Ti, SUS, or Mo, and the porous ceramic is made of, for example, Al2O3, MgO, CaO, ZrO2, SiO2, SiC, or TiO2.

[0021] In this embodiment, a cylindrical (round pipe) support is used as the support 1A, but a polygonal (square pipe) support may also be used. The support 1A may be any support as long as the portion of the entire support 1A on which the multilayer film 1B is to be formed is made of a porous metal sintered body, a porous ceramic sintered body, or a Vycor-type porous glass. The portion of the entire support 1A on which the multilayer film 1B is not to be formed does not need to be porous.

[0022] Incidentally, hydrogen includes hydrogen-based gases containing isotopes of hydrogen, and either deuterium gas or proton gas is used as the hydrogen-based gas. Proton gas includes a mixture of naturally occurring protons and deuterium, i.e., a mixture in which the proportion of protons is 99.985% and the proportion of deuterium is 0.015%. In the following description, gases including hydrogen-based gases will be collectively referred to as "hydrogen."

[0023] Here, the structure of the multilayer film 1B will be described with reference to FIG.

[0024] <Multilayer film structure> In this embodiment, the multilayer film 1B formed on the outer peripheral surface of the support 1A includes a first layer 11 made of a hydrogen-absorbing metal or a hydrogen-absorbing alloy and a second layer 12 made of a different hydrogen-absorbing metal, alloy, or ceramic from the first layer 11. A dissimilar-substance interface 13 is formed between the first layer 11 and the second layer 12. In the example shown in FIG. 3, the multilayer film 1B is formed on the outer peripheral surface of the support 1A by alternately stacking five first layers 11 and five second layers 12 in this order, resulting in a total of 10 layers. The number of first layers 11 and second layers 12 is optional. Unlike the example shown in FIG. 3, the multilayer film may also be formed by alternately stacking multiple first layers 11 and multiple second layers 12 in this order on the outer peripheral surface of the support 1A. Furthermore, the multilayer film 1B may have at least one first layer 11 and one second layer 12, and may have at least one dissimilar-substance interface 13 formed between the first layer 11 and the second layer 12.

[0025] Here, the first layer 11 is made of any of Ni, Pd, Cu, Mn, Cr, Fe, Mg, Co, and alloys thereof. Here, the alloy making up the first layer 11 is preferably made of two or more of Ni, Pd, Cu, Mn, Cr, Fe, Mg, and Co. The alloy making up the first layer 11 may also be made of Ni, Pd, Cu, Mn, Cr, Fe, Mg, or Co to which an additive has been added.

[0026] The second layer 12 is made of any of Ni, Pd, Cu, Mn, Cr, Fe, Mg, Co, alloys thereof, or SiC. The alloy making up the second layer 12 is preferably made of two or more of Ni, Pd, Cu, Mn, Cr, Fe, Mg, and Co. The alloy making up the second layer 12 may also be made of Ni, Pd, Cu, Mn, Cr, Fe, Mg, or Co to which an additive has been added.

[0027] As a combination of the first layer 11 and the second layer 12, when the types of elements are expressed as "first layer-second layer," the combinations of Pd-Ni, Ni-Cu, Ni-Cr, Ni-Fe, Ni-Mg, and Ni-Co are preferable. When the second layer 52 is made of ceramics, the combination of Ni-SiC is preferable.

[0028] Here, the mechanism of heat generation (excess heat generation) when hydrogen permeates the heat generating cell 1 will be described with reference to FIG.

[0029] Figure 4 is a schematic diagram illustrating the mechanism of excess heat generation in a heat generating cell. The dissimilar material interface 13 formed between the first layer 11 and the second layer 12 of the multilayer film 1B of the heat generating cell 1 allows hydrogen atoms to pass through. When hydrogen is supplied to the heat generating cell 1 from its outer peripheral surface, the first layer 11 and the second layer 12, which have a face-centered cubic structure, i.e., the multilayer film 1B, absorbs hydrogen. Here, even if the supply of hydrogen is stopped, the heat generating cell 1 maintains the state in which hydrogen is absorbed by the multilayer film 1B.

[0030] When heating of the heat generating cell 1 is started by a heater (not shown), as shown in Fig. 4, hydrogen atoms in the metal lattice of the first layer 11 permeate the dissimilar material interface 13 and move into the metal lattice of the second layer 12, releasing the hydrogen occluded in the multilayer film 1B. This hydrogen undergoes quantum diffusion while hopping within the multilayer film 1B. It is known that hydrogen is light and undergoes quantum diffusion while hopping between sites occupied by hydrogen (octohedral or tetrahedral sites) in certain materials A and B. Therefore, when the heat generating cell 1 is heated by the heater, hydrogen permeates the dissimilar material interface 13 by quantum diffusion, or hydrogen permeates the dissimilar material interface 13 by diffusion, causing the heat generating cell 1 to generate heat in an amount greater than the amount of heat generated by the heater as excess heat.

[0031] In the heat generating cell 1, a hydrogen-based gas containing hydrogen is supplied to the outer peripheral surface of the multilayer film 1B, and the gas inside the support 1A is discharged and reduced in pressure. As a result, the hydrogen pressure outside the heat generating cell 1 (referred to as the "hydrogen partial pressure") becomes higher than the hydrogen partial pressure inside, and a hydrogen pressure difference (referred to as the "hydrogen partial pressure difference") occurs between the inside and outside of the heat generating cell 1.

[0032] As described above, when a difference in hydrogen partial pressure occurs between the inside and outside of the heat generation cell 1, hydrogen molecules contained in the hydrogen-based gas supplied to the outer peripheral surface of the heat generation cell 1 are adsorbed onto the outer peripheral surface of the multilayer film 1B, dissociate into two hydrogen atoms, and the dissociated hydrogen atoms penetrate into the interior of the multilayer film 1B. In other words, hydrogen is absorbed into the heat generation cell 1. The hydrogen atoms that penetrate into the interior of the multilayer film 1B permeate the interface 13 of different materials by quantum diffusion, or permeate the interface 13 of different materials by diffusion. At the inner peripheral surface (the surface in contact with the support 1A) on the low-pressure side of the multilayer film 1B, the hydrogen atoms that permeate the multilayer film 1B recombine to form hydrogen molecules, which are released to the outside of the multilayer film 1B. In other words, hydrogen is released from the heat generation cell 1.

[0033] As described above, the heat generating cell 1 generates excess heat by allowing hydrogen to permeate from the outside to the inside. By maintaining a state in which the outside of the heat generating cell 1 is at a higher pressure than the inside, it is possible to maintain a state in which hydrogen is simultaneously absorbed on the outer peripheral surface of the heat generating cell 1 and released from the inner peripheral surface of the heat generating cell 1. Note that "simultaneous" does not necessarily mean completely simultaneously, but rather means within a short period of time that can be considered substantially simultaneous. By simultaneously absorbing and releasing hydrogen, hydrogen continuously permeates the heat generating cell 1, and excess heat is efficiently generated from the heat generating cell 1.

[0034] The thicknesses of the first layer 11 and the second layer 12 constituting the multilayer film of the heating cell 1 are preferably each less than 1000 nm. When the thicknesses of the first layer 11 and the second layer 12 are each less than 1000 nm, the first layer 11 and the second layer 12 can maintain a nanostructure that does not exhibit bulk properties. Incidentally, when the thicknesses of the first layer 11 and the second layer 12 are each 1000 nm or more, hydrogen becomes less likely to permeate the multilayer film 1B. The thicknesses of the first layer 11 and the second layer 12 are preferably each less than 500 nm. When the thicknesses of the first layer 11 and the second layer 12 are each less than 500 nm, the first layer 11 and the second layer 12 can maintain a nanostructure that does not exhibit any bulk properties.

[0035] <Production method of heating cell> Here, an example of a method for manufacturing the heat generating cell 1 will be described.

[0036] The heat generating cell 1 is manufactured by preparing a cylindrical (round pipe-shaped) support 1A, rotating the support 1A around its axis, and using a vapor deposition device to vaporize a hydrogen storage metal or alloy to become the first layer 11 and the second layer 12, and then forming the first layer 11 and the second layer 12 alternately on the outer circumferential surface of the support 1A through aggregation and adsorption of the hydrogen storage metal or alloy in the vapor state. In this case, it is preferable to form the first layer 11 and the second layer 12 successively in a vacuum state, which allows a dissimilar material interface 13 to be formed between the first layer 11 and the second layer 12 without forming a native oxide film.

[0037] The deposition device used is a physical deposition device that deposits a hydrogen-storing metal or alloy by a physical method, and examples of such physical deposition devices include a sputtering device, a vacuum deposition device, and a CVD (Chemical Vapor Deposition) device. Alternatively, the first layer 11 and the second layer 12 may be alternately formed on the surface of the support 1A by depositing a hydrogen-storing metal or alloy by electroplating. Alternatively, the first layer 11 and the second layer 12 may be alternately formed on the surface of the support 1A by using a thermal spraying method, an inkjet method, or the like.

[0038] 5 and 6 show first and second modifications of the multilayer film structure of the heat generating cell 1. Fig. 5 and Fig. 6 are cross-sectional views showing the layer structures of multilayer films 60B and 70B according to the first and second modifications.

[0039] <Another form of multilayer film layer structure 1> In the present embodiment described above, the multilayer film 1B of the heat generating cell 1 is formed by alternately stacking five first layers 11 and five second layers 12 as shown in Fig. 3, but in the heat generating cell 60 shown in Fig. 5, the multilayer film 60B further has a third layer 63 in addition to the first layer 61 and the second layer 62. Here, the third layer 63 is formed of a hydrogen storage metal, hydrogen storage alloy, or ceramic different from the first layer 61 and the second layer 62, and its thickness is preferably less than 1000 nm.

[0040] In the heat generating cell 60 shown in FIG. 5, a first layer 61, a second layer 62, a first layer 61, and a third layer 63 are laminated in this order on the surface of a support 60A. In this heat generating cell 60, a dissimilar material interface 64 formed between the first layer 61 and the second layer 62 and a dissimilar material interface 65 formed between the first layer 61 and the third layer 63 allow hydrogen atoms to pass through. Note that the first layer 61, the second layer 62, and the third layer 63 may also be laminated on the surface of the support 60A in the order of the first layer 61, the third layer 63, the first layer 61, and the second layer 62. In other words, the multilayer film 60B has a laminated structure in which the first layer 61 is provided between the second layer 62 and the third layer 63. Note that the multilayer film 60B may have at least one third layer 63.

[0041] 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.

[0042] In particular, it is desirable that the third layer 63 be made of any one of CaO, Y2O3, TiC, LaB6, SrO, and BaO. A heat generating cell 60 having a third layer 63 made of any one of CaO, Y2O3, TiC, LaB6, SrO, and BaO can store more hydrogen, and the amount of hydrogen that permeates the interfaces 64 and 65 between different materials can be increased, resulting in a higher output of excess heat.

[0043] The third layer 63, which is made of any of CaO, YO, TiC, LaB, SrO, and BaO, preferably has a thickness of 10 nm or less. This allows hydrogen atoms to easily pass through the multilayer film 60B. The third layer 63, which is made of any of CaO, YO, TiC, LaB, SrO, and BaO, may be formed in the shape of islands rather than as 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.

[0044] 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.

[0045] <Modification 2 of the Layer Structure of the Multilayer Film> 6, the multilayer film 70B of the heat generating cell 70 according to this embodiment further includes a fourth layer 74 in addition to the first layer 71, the second layer 72, and the third layer 73. The fourth layer 74 is made of a hydrogen storage metal, a hydrogen storage alloy, or a ceramic different from the first layer 71, the second layer 72, and the third layer 73, and its thickness is preferably less than 1000 nm.

[0046] 6, 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 laminated in this order on the surface of support 70A. Note that 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 also be laminated in this order on the surface of support 70A. That is, multilayer film 70B has a laminate structure in which the second layer 72, the third layer 73, and the fourth layer 74 are laminated in any order, and the first layer 71 is provided between each of the second layer 72, the third layer 73, and the fourth layer 74. Here, a dissimilar material interface 75 formed between the first layer 71 and the second layer 72, a dissimilar material interface 76 formed between the first layer 71 and the third layer 73, and a dissimilar material interface 77 formed between the first layer 71 and the fourth layer 74 allow hydrogen atoms to pass through. The multilayer film 70B may have at least one fourth layer 74.

[0047] The fourth layer 74 is made of Ni, Pd, Cu, Cr, Fe, Mg, Co, or an alloy thereof, or SiC, Y2O3, TiC, LaB6, 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.

[0048] In particular, the fourth layer 74 is preferably made of any one of CaO, Y2O3, TiC, LaB6, SrO, and BaO. Here, in a heating cell 70 having a 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 dissimilar material interfaces 75, 76, and 77 also increases, thereby increasing the output of excess heat generated by the heating cell 70. Furthermore, the thickness of the fourth layer 74 made of any one of CaO, Y2O3, TiC, LaB6, SrO, and BaO is preferably 10 nm or less to allow easy permeation of hydrogen atoms.

[0049] Furthermore, the fourth layer 74, which is made of any of CaO, YO, TiC, LaB, SrO, and BaO, may be formed in the shape of islands rather than as a complete film. Furthermore, it is desirable that the first layer 71 and the fourth layer 74 are successively formed in a vacuum, and by doing so, only a dissimilar material interface 77 is formed between the first layer 71 and the fourth layer 74 without forming a native oxide film.

[0050] 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.

[0051] As described above, the heat generating cell 1 shown in Fig. 1 according to this embodiment is constructed by forming the multilayer film 1B on the outer peripheral surface of the highly rigid cylindrical (round pipe-shaped) support 1A. Therefore, it is not easily deformed even when subjected to external forces, and the multilayer film 1B formed on the outer peripheral surface of the support 1A does not peel off. This ensures stable heat generation by the heat generating cell 1 and enhanced durability. The heat generating cell 1 generates heat by allowing hydrogen to permeate the multilayer film 1B, and the permeated high-temperature hydrogen (permeated hydrogen) passes through the inside of the support 1A and is discharged from above the support 1A to the outside.

[0052] The heat generating cell 1 is not limited to being composed of a support 1A and a multilayer film 1B, but may further include a pedestal made of a hydrogen storage metal, a hydrogen storage alloy, or a proton dielectric. A heat generating cell with a pedestal can be constructed, for example, by forming a pedestal on the outer peripheral surface of the support 1A and then forming a multilayer film 1B on the outer peripheral surface of the pedestal. The multilayer film 1B is not limited to being formed only on the outer peripheral surface of the pedestal, but may also be formed only on the inner peripheral surface of the pedestal, i.e., between the support 1A and the pedestal. The multilayer film 1B may also be formed on both the inner and outer peripheral surfaces of the pedestal. Multiple pedestals and multilayer films 1B may be alternately stacked on the support 1A. Examples of hydrogen storage metals used for the pedestal include Ni, Pd, V, Nb, Ta, and Ti. Examples of hydrogen storage alloys used for the pedestal include LaNi5, CaCu5, MgZn2, ZrNi2, ZrCr2, TiFe, TiCo, Mg2Ni, and Mg2Cu. The proton dielectric used for the base is, for example, a BaCeO3 system (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. The base may be made of a porous body or a hydrogen-permeable membrane. The porous body has a large number of holes large enough to allow hydrogen-based gases to pass through. The porous body is made of materials such as metals, non-metals, and ceramics. The porous body is preferably made of a material that does not inhibit the exothermic reaction between hydrogen and the multilayer film 1B. 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. Hydrogen-permeable membranes also include those having a mesh-like sheet.

[0053] <Considerations regarding the support> When the heat generating cell 1 is used only for heat generation, for example, the relationship between the pore diameter (the inner diameter of the numerous holes formed in the support 1A) [nm] and the stress [MPa] at a temperature of 900°C for a support 1A having a multilayer film 1B made of a 100 nm thick Ni film formed on its outer surface is shown in Figure 7A. Here, since the allowable tensile stress of Ni at a temperature of 900°C is 13 MPa, Figure 7A shows that in order to keep the stress of the support 1A at 13 MPa or less, the pore diameter must be kept at 160 nm or less.

[0054] Furthermore, when the heat generating cell 1 is operated by high-pressure chemistry, for example, Figure 7B shows the relationship between pore diameter [nm] and stress [MPa] at a temperature of 500°C for a support 1A having a multilayer film 1B made of a 100-nm-thick Ni film formed on its outer surface. Here, since the allowable tensile stress of Ni at a temperature of 500°C is 28 MPa, Figure 7B shows that in order to keep the stress of the support 1A below 28 MPa, the pore diameter must be kept below 230 nm. Considering the progress of chemical reactions within the pores, the pore diameter must be 2 nm or larger. Therefore, the pore diameter in this case is set within the range of 2 to 230 nm.

[0055] When the heat generating cell 1 is used solely for heat generation, the relationship between the porosity (p) and compressive strength [MPa] is shown in Figure 8A when the support 1A made of a porous ceramic sintered body is subjected to a differential pressure of 0.1 MPa at a temperature of 900°C. As is clear from Figure 8A, the compressive strength of the support 1A decreases rapidly in a hyperbolic manner as the porosity (p) increases. For example, if the compressive strength of the support 1A is set to 5 to 175 MPa, the porosity (p) should be set to 0.1 to 0.6.

[0056] Furthermore, when the heat generating cell 1 is operated by high-pressure chemistry, the relationship between porosity (p) and compressive strength [MPa] when the support 1A made of porous glass is subjected to a differential pressure of 1 to 10 MPa at a temperature of 500°C is shown in Figure 8B. As is clear from Figure 8B, the compressive strength of the support 1A decreases rapidly in a hyperbolic manner as the porosity (p) increases.

[0057] Next, Figure 9 shows the relationship between the wall thickness [mm] and inner diameter [mm] required when the support 1A of the heat generating cell 1 is subjected to differential pressures of 1 MPa, 3 MPa, 5 MPa, and 10 MPa. As is clear from Figure 9, the greater the differential pressure to which the support 1A is subjected, the greater the wall thickness required for the support 1A, and conversely, the smaller the inner diameter. For example, when the support 1A is subjected to a differential pressure of 10 MPa, the support 1A needs to have a wall thickness of 5 nm or more. When the support 1A is subjected to a differential pressure of 5 MPa, the wall thickness of the support 1A may be less than 2 mm. It can also be seen that when the support 1A is subjected to differential pressures of 3 MPa and 1 MPa, the wall thickness of the support 1A may be less than 1 mm.

[0058] [Heat generating module] Next, the heat generating module according to the present invention will be described below with reference to FIG.

[0059] 10 is a perspective view of a heat generating module according to the present invention, and the illustrated heat generating module M is configured as a single unit by bundling together a plurality of heat generating cells 1 and a plurality of round rod-shaped heaters 2 shown in FIG. 1 and standing them upright, and connecting these heat generating cells 1 and heaters 2 together with upper and lower disk-shaped support brackets 3 and 4. In this heat generating module M, a plurality of heaters 2 are regularly and orderly arranged, surrounded by a plurality of heat generating cells 1.

[0060] The heat generating module M configured as described above is composed of a large number of heat generating cells 1 densely packed together, so that it generates a large amount of heat, has high output, and is highly durable. The number of heat generating cells 1 and heaters 2 that make up the heat generating module M can be set as desired depending on the heat generating amount (output) required for the heat generating module M.

[0061] [Heat generating device] Next, the heating device 5 according to the present invention will be described below with reference to FIG.

[0062] 11 is a block diagram showing the configuration of a heat generating device 5 according to the present invention, and the illustrated heat generating device 5 includes a containment vessel 6 that stores the heat generating module M shown in FIG. 10, a temperature adjustment unit T that adjusts the temperature of the heat generating module M, a supply line L1 that supplies hydrogen and a heat medium to the containment vessel 6, a discharge line L2 that discharges the hydrogen and heat medium from the containment vessel 6, and a permeated hydrogen recovery line L3 that returns permeated hydrogen that has permeated through the multilayer film 1B (see FIG. 3) of each heat generating cell 1 of the heat generating module M and is discharged from the support 1A to the supply line L1 and is recovered. Note that the heat medium preferably has excellent thermal conductivity and is chemically stable, and examples of the heat medium that can be used include rare gases such as helium gas and argon gas, hydrogen gas, nitrogen gas, water vapor, air, carbon dioxide, and gases that form hydrides.

[0063] Here, the temperature adjusting section T, the supply line L1, the discharge line L2, and the permeated hydrogen recovery line L3 will be described below.

[0064] (Temperature adjustment part) The temperature adjustment unit T adjusts the temperature of the heat generation module M to maintain the heat generation module M at an optimum temperature for heat generation (for example, 50°C to 1500°C), and includes a heater 2 (see FIG. 10), a power supply 7 that supplies power to the heater 2, a temperature sensor 8 such as a thermocouple that detects the temperature of the heater 2, and a control unit 9 that controls the output of the power supply 7 based on the temperature detected by the temperature sensor 8. The control unit 9 includes a CPU (Central Processing Unit), and storage units such as a ROM (Read Only Memory) and RAM (Random Access Memory), and the CPU performs various arithmetic operations using programs and data stored in the ROM and RAM.

[0065] (supply line) The supply line L1 supplies low-temperature hydrogen and a heat transfer medium from the supply pipe 10 into the containment vessel 6. The supply pipe 10 extends from the discharge side of the circulation pump 14, and its end is inserted into the containment vessel 6 and opens at the top of the containment vessel 6.

[0066] Meanwhile, a recovery pipe 15 extending from a heat utilization device 30 (see FIG. 12) is connected to the suction side of the circulation pump 14, and a supply pipe 10 extending from the discharge side of the circulation pump 14 is provided with a buffer tank 16, an electric pressure regulating valve (pressure reducing valve) 17, and a filter 18. The circulation pump 14 and the pressure regulating valve 17 are electrically connected to the control unit 9, and the operations of the circulation pump 14 and the pressure regulating valve 17 are controlled by control signals output from the control unit 9. The circulation pump 14 may be, for example, a metal bellows pump.

[0067] The buffer tank 16 stores hydrogen and the heat transfer medium and absorbs fluctuations in the flow rates of these hydrogen and the heat transfer medium. The pressure regulating valve 17 receives a control signal from the control unit 9 and adjusts its opening, thereby regulating the pressure of the hydrogen and the heat transfer medium supplied from the buffer tank 16.

[0068] The filter 18 is used to remove impurities contained in the hydrogen and the heat medium. The amount of hydrogen that permeates each heat generating cell 1 of the heat generating module M (hydrogen permeation amount) depends on the temperature of the heat generating cell 1, the pressure difference between the inside and outside of the heat generating cell 1, and the surface condition of the outer circumferential surface of the heat generating cell 1. If impurities are contained in the hydrogen, the impurities may adhere to the outer circumferential surface of the heat generating cell 1, deteriorating the surface condition of the heat generating cell 1. If the surface condition of the heat generating cell 1 deteriorates, the adsorption and dissociation of hydrogen molecules on the outer circumferential surface of the multilayer film 1B of the heat generating cell 1 is hindered, resulting in a problem of a reduced hydrogen permeation amount. Possible substances that hinder the adsorption and dissociation of hydrogen molecules on the outer circumferential surface of the multilayer film 1B of the heat generating cell 1 include, for example, water (including water vapor), hydrocarbons (methane, ethane, methanol, ethanol, etc.), C, S, and Si.

[0069] The filter 18 removes impurities contained in the hydrogen and heat medium, such as water (including water vapor), hydrocarbons, C, S, and Si, thereby suppressing a decrease in the amount of hydrogen permeated through the heat generating cell 1.

[0070] (Discharge line) The discharge line L2 discharges the hydrogen that has not permeated through each heat generating cell 1 of the heat generating module M housed within the containment vessel 6 (non-permeated hydrogen) and the heat medium from a discharge pipe 19 extending from the bottom of the containment vessel 6 to the outside of the containment vessel 6. The non-permeated hydrogen and the heat medium are heated by the heat generating module M to a high temperature. A hydrogen separator 22 for separating the hydrogen and the heat medium is provided in the discharge pipe 19, and the hydrogen separated by this hydrogen separator 22 is returned to the recovery pipe 15 through a hydrogen pipe 23. The heat medium from which hydrogen has been separated and removed in the hydrogen separator 22 is transported to a heat utilization device 30 (see FIG. 12), and the heat recovered by this heat medium is supplied to the heat utilization device 30.

[0071] (Permeation hydrogen recovery line) The permeated hydrogen recovery line L3 is a line that returns hydrogen (permeated hydrogen) that has permeated through each heat generation cell 1 of the heat generation module M contained in the containment vessel 6 and has been used to generate heat in the heat generation cell 1 to the recovery pipe 15, and is configured by connecting a permeated hydrogen recovery pipe 21 that extends upward from a junction header 20 connected to the upper end of the cylindrical support body 1A of each heat generation cell 1, penetrating the top of the containment vessel 6, to the recovery pipe 15. The lower end of each heat generation cell 1 of the heat generation module M is sealed or connected to a junction header (not shown), so that a difference in hydrogen partial pressure occurs inside and outside each heat generation cell 1.

[0072] (Effect of the heating device) Next, the operation of the heating device 5 configured as above will be described.

[0073] When the circulation pump 14 is driven by a control signal from the control unit 9, the hydrogen and heat transfer medium discharged from the circulation pump 14 are introduced into the upper part of the containment vessel 6 through the supply piping 10 of the supply line L1. Note that as the hydrogen and heat transfer medium flow through the supply piping 10, pressure fluctuations are suppressed by the buffer tank 16, and the pressure is reduced to a predetermined value by the pressure regulating valve 17.

[0074] Furthermore, the heaters 2 (see FIG. 10) provided in the heat generating module M generate heat using power supplied from the power source 7, and heat each heat generating cell 1 to a predetermined temperature (for example, 50°C to 1500°C). As described above, the temperature of the heat generating cell 1 is adjusted to an appropriate value by the control unit 9 controlling the output of the power source 7 based on the temperature detected by the temperature sensor 8.

[0075] As described above, hydrogen introduced into the containment vessel 6 together with the heat medium permeates the multilayer film 1B of each heat generation cell 1 of the heat generation module M, flows upward within each support 1A, and is introduced into the junction header 20. In the heat generation device 5, hydrogen is supplied to the outside of each heat generation cell 1, and hydrogen (permeated hydrogen) inside each heat generation cell 1 is discharged, resulting in a difference in hydrogen partial pressure between the inside and outside of each heat generation cell 1. This difference in hydrogen partial pressure causes hydrogen to permeate the multilayer film 1B (see FIG. 4) of each heat generation cell 1, and each heat generation cell 1 generates heat due to this permeation of hydrogen. Specifically, a hydrogen molecule is adsorbed on the outer peripheral surface of the multilayer film 1B of each heat generation cell 1, and this hydrogen molecule dissociates into two hydrogen atoms. The dissociated hydrogen atom then penetrates (occludes) the inside of the multilayer film 1B, recombines at the inner peripheral surface of the multilayer film 1B (the surface in contact with the support 1A), and is released as a hydrogen molecule. In this way, when hydrogen atoms move from the outer peripheral surface to the inner peripheral surface of the multilayer film 1B, the hydrogen atoms pass through the dissimilar material interface 13 (see FIG. 4) by quantum diffusion, or the hydrogen atoms pass through the dissimilar material interface 13 by diffusion, thereby generating heat in each heat generating cell 1. In the heat generating device 5, hydrogen passes through each heat generating cell 1 continuously, so that excess heat can be generated efficiently.

[0076] As described above, the hydrogen (permeated hydrogen) that has permeated (passed through) each heat generation cell 1 of the heat generation module M and is used to generate heat in the heat generation cell 1 joins together in the joining header 20, then flows through the permeated hydrogen recovery pipe 21 to the recovery pipe 15, where it joins with the hydrogen and heat transfer medium flowing through the recovery pipe 15, and these hydrogen and heat transfer medium are pressurized by the circulation pump 14 and then introduced back into the containment vessel 6 through the supply pipe 10.

[0077] Furthermore, the high-temperature hydrogen (non-permeated hydrogen) heated by the heat generating module M inside the containment vessel 6 and the heat medium are discharged to the outside of the containment vessel 6 through the discharge pipe 19, and the hydrogen and the heat medium are separated by the hydrogen separator 22. As described above, the hydrogen separated in the hydrogen separator 22 is returned to the recovery pipe 15 through the hydrogen pipe 23, and the heat medium from which the hydrogen has been separated and removed is transported to the heat utilization device 30, and the heat recovered by this heat medium is supplied to the heat utilization device 30.

[0078] Thereafter, the same operations as above are repeated, and the hydrogen and heat medium circulate in the closed loop, during which the hydrogen and heat medium are used to generate heat in each heat generation cell 1 of the heat generation module M, and the heat medium that has recovered the heat generated in the heat generation module M is supplied to the heat utilization device 30, which uses this heat to drive the heat utilization device 30. The heat medium, whose temperature has been reduced by being used to drive the heat utilization device 30, is returned to the suction side of the circulation pump 14 via the recovery piping 15, and is pressurized by the circulation pump 14 together with the hydrogen returned from the hydrogen piping 23 and the permeated hydrogen flowing through the permeated hydrogen recovery piping 21, and then returned to the containment vessel 6 again via the supply piping 10, and the same operations are repeated thereafter.

[0079] [Heat utilization system] Next, a heat utilization system for utilizing the heat generated in the heat generating device 5 according to the present invention will be described below with reference to FIG.

[0080] The heat utilization system shown in Fig. 12 includes a heat generation device 5 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 5 as a heat source, and includes a gas turbine 32, a steam generator 33, a steam turbine 34, a Stirling engine 35, and a thermoelectric conversion unit 36. Below, the gas turbine 32, the steam generator 33, the steam turbine 34, the Stirling engine 35, and the thermoelectric conversion unit 36 ​​will each be described.

[0081] The discharge pipe 19 extending from the bottom of the containment vessel 6 of the heat generating device 5 is connected to the inlet side of the gas turbine 32, the gas turbine 32 and the steam generator 33 are connected by a pipe 31a, and the steam generator 33 and the Stirling engine 35 are connected by a pipe 31b. A recovery pipe 15 extends from the Stirling engine 35 and is connected to the suction side of the circulation pump 14 through a thermoelectric conversion unit 36. A circulation pump 37 and a flow control valve 38 are provided midway along the discharge pipe 19. 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.

[0082] (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.

[0083] (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 pipe 31a 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 also 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.

[0084] (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.

[0085] 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.

[0086] 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 pipe 31b and the recovery pipe 15, and functions to circulate the heat medium from the pipe 31b to the recovery pipe 15. When the heat medium flows from the pipe 31b 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.

[0087] 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.

[0088] 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.

[0089] 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.

[0090] (Thermoelectric conversion part) The thermoelectric converter 36 converts the heat of the heat medium flowing through the recovery pipe 15 into electricity by utilizing the Seebeck effect, and converts, for example, the heat of the heat medium at 300° C. or less into electricity. The thermoelectric converter 36 is formed in a cylindrical shape and is disposed so as to cover the outer periphery of the recovery pipe 15.

[0091] The thermoelectric conversion unit 36 ​​includes a thermoelectric conversion module 36a provided on its inner surface and a cooling unit 36b provided on its outer surface. The thermoelectric conversion module 36a includes a heat receiving substrate facing the recovery pipe 15, a heat receiving electrode provided on the heat receiving substrate, a heat dissipation substrate facing the cooling unit 36b, a heat dissipation 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 includes p-type thermoelectric elements and n-type thermoelectric elements arranged alternately, with adjacent p-type and n-type thermoelectric elements electrically connected by a heat receiving electrode and a heat dissipation electrode.

[0092] 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.

[0093] (Thermal utilization system action) Next, the operation of the heat utilization system configured as above will be described.

[0094] In the heat generation device 5 according to the present invention, as described above, the heat generated by hydrogen permeating through each heat generation cell 1 of the heat generation module M housed in the containment vessel 6 is imparted to the heat medium introduced into the containment vessel 6, heating the heat medium to a predetermined temperature. When the circulation pump 37 provided in the exhaust pipe 19 is driven, the heat recovered by the heat medium is supplied to the gas turbine 32, the steam turbine 34, the Stirling engine 35, and the thermoelectric converter 36, which are sequentially driven to generate 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 8 (see FIG. 11 ). That is, when the temperature of the heat generation module M detected by the temperature sensor 8 exceeds an appropriate upper temperature limit, the flow control valve 38 increases the circulating flow rate of the heat medium to suppress a temperature rise in the heat generation module M. Conversely, when the temperature of the heat generation module M detected by the temperature sensor 8 is below an appropriate lower temperature limit, the flow control valve 38 reduces the circulating flow rate of the heat medium to suppress a temperature drop in the heat generation module M.

[0095] Thus, the high-temperature (for example, 600°C to 1500°C) heat medium heated by the heat generating module M of the heat generating device 5 and discharged from the containment vessel 6 to the discharge pipe 19 is introduced into the gas turbine 32 and compressed by the compressor 32a of this gas turbine 32. Then, the compressed heat medium flows through the turbine 32b while expanding, thereby rotating the turbine 32b and rotating the generator 40 connected to the output shaft of the turbine 32b, thereby generating the required amount of 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.

[0096] The heat transfer medium discharged from the gas turbine 32 to the pipe 31a 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 rotated by the steam, and the rotation of the steam turbine 34 also rotates the generator 50, thereby generating required electricity. That is, part of the heat of the heat transfer 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 driving the steam turbine 34 is cooled in a condenser (not shown) and returned to the boiler water. This boiler water then flows from the feedwater pipe 33d to the heat exchange pipe 33b of the steam generator 33. During this process, the boiler water is heated by the heat transfer medium flowing through the internal pipe 33a and becomes steam.

[0097] 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 pipe 31b 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.

[0098] As described above, the heat medium used to drive the Stirling engine 35 is supplied to the thermoelectric converter 36 via the recovery pipe 15, 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.

[0099] The heat medium, whose temperature has been reduced after being used to generate electricity in the thermoelectric conversion section 36, is returned to the suction side of the circulation pump 14 through the recovery pipe 15, and the same process is then continuously repeated, with the heat generated in the heat generating module M being recovered by the heat medium and the thermal energy being converted into electrical energy.

[0100] 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.

[0101] 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 5 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.

[0102] The heat generating device 5 can be applied to an ammonia production plant that synthesizes ammonia by the Haber-Bosch process.

[0103] 13 is an explanatory diagram illustrating an ammonia production plant 90 equipped with heat generation devices 94, 98 according to the present invention. The ammonia production plant 90 includes a reforming section 91, a CO conversion section 92, a CO2 removal section 93, a heat generation device 94, a compression section 95, a synthesis section 96, a cooling section 97, and a heat generation device 98.

[0104] The reforming unit 91 performs primary reforming, in which water vapor (H2O) is added to natural gas (CH4) to produce carbon monoxide (CO) and hydrogen (H2), and secondary reforming, in which air containing nitrogen (N2) corresponding to the amount of hydrogen produced is added to the CH4 remaining in the primary reforming to produce carbon dioxide (CO2) and water vapor (H2O).

[0105] The CO conversion section 92 generates CO2 and H2 from CO and H2O by carrying out a two-stage conversion reaction using an Fe-Cr based catalyst and a Cu-Zn based catalyst.

[0106] The CO2 removal unit 93 removes CO2 using an aqueous potassium carbonate solution. Since the remaining CO becomes a catalyst poison in the ammonia synthesis reaction in the synthesis unit 96, which will be described later, it is reacted with H2 using a nickel-based catalyst to return it to CH4. As a result, a synthesis feed gas containing H2 and N2 is obtained. The synthesis feed gas also contains CH4 and argon (Ar). The synthesis feed gas is introduced into the heat generating device 94.

[0107] As shown in FIG. 14, the heat generating device 94 includes a containment vessel 6 that stores the heat generating module M shown in FIG. 10, and a temperature adjusting unit T that adjusts the temperature of the heat generating module M. In the heat generating device 94, a portion of the hydrogen contained in the synthesis feed gas introduced from the top of the containment vessel 6 permeates through the multilayer film 1B (see FIG. 3) of each heat generating cell 1 of the heat generating module M, causing the heat generating cell 1 to generate heat. The synthesis feed gas is heated by the heat generating cell 1 and rises in temperature to a temperature (approximately 500°C) required for ammonia synthesis. The high-temperature synthesis feed gas is discharged from the bottom of the containment vessel 6 and introduced into the compression unit 95. The hydrogen that permeates the heat generating cell 1 (permeated hydrogen) may be recovered using a permeated hydrogen recovery line (not shown) and returned to the containment vessel 6.

[0108] The compression section 95 increases the pressure of the high-temperature synthesis feed gas to the pressure (approximately 30 MPa) required for ammonia synthesis. The high-temperature, high-pressure synthesis feed gas is introduced into the synthesis section 96.

[0109] The synthesis unit 96 synthesizes ammonia (NH3) by passing a high-temperature, high-pressure synthesis feed gas through a catalyst layer containing a doubly promoted iron catalyst.

[0110] The cooling unit 97 cools the gaseous NH3 to about -33°C, condenses it, and discharges it in liquid form. The unliquefied gas contains the synthetic raw materials H2 and N2, as well as Ar derived from the air. A portion of the unliquefied gas is introduced into the heat generating device 98, and the remaining portion of the unliquefied gas is discharged as purge gas. The purge gas may be used to remove sulfur from the natural gas in a desulfurization unit (not shown).

[0111] The heat generating device 98 has the same configuration as the heat generating device 94. Specifically, the heat generating device 98 includes a containment vessel 6 housing a heat generating module M shown in FIG. 10 and a temperature adjusting unit T for adjusting the temperature of the heat generating module M. In the heat generating device 98, a portion of the hydrogen contained in the unliquefied gas introduced from the top of the containment vessel 6 permeates through the multilayer membrane 1B (see FIG. 3) of each heat generating cell 1 of the heat generating module M, causing the heat generating cell 1 to generate heat. The unliquefied gas is heated by the heat generating cell 1 and raised to the temperature required for ammonia synthesis (approximately 500°C). The high-temperature unliquefied gas is discharged from the bottom of the containment vessel 6, introduced back into the compression unit 95, and pressurized to the pressure required for ammonia synthesis. The high-temperature unliquefied gas is then introduced into the synthesis unit 96 and recycled as a high-temperature, high-pressure synthesis feed gas. The hydrogen that permeates the heat generating cell 1 (permeated hydrogen) may be recovered using a permeated hydrogen recovery line (not shown) and returned to the containment vessel 6.

[0112] The ammonia production plant 90 is equipped with a heat generating device 94 that heats the synthesis feed gas from the CO2 removal section 93 and a heat generating device 98 that heats the unliquefied gas from the cooling section 97. However, instead of the heat generating devices 94 and 98, a heat generating device that heats the high-pressure synthesis feed gas from the compression section 95 may be provided. In this case, the low-temperature synthesis feed gas is introduced from the CO2 removal section 93 to the compression section 95. In the compression section 95, the pressure of the low-temperature synthesis feed gas is increased to the pressure required for ammonia synthesis. The low-temperature, high-pressure synthesis feed gas is introduced into the heat generating device. In the heat generating device, a portion of the hydrogen contained in the low-temperature, high-pressure synthesis feed gas permeates through the multilayer film 1B (see FIG. 3) of each heat generating cell 1 of the heat generating module M, causing the heat generating cell 1 to generate heat. As a result, the high-temperature, high-pressure synthesis feed gas is introduced from the heat generating device to the synthesis section 96, where ammonia is synthesized.

[0113] However, the present invention is not limited to the application of the above-described embodiments, and it goes without saying that various modifications are possible within the scope of the claims and the technical ideas described in the specification and drawings. [Explanation of symbols]

[0114] 1,60,70 Heating Cell 1A, 60A, 70A support 1B,60B,70B multilayer film 11,61,71 1st layer 12,62,72 2nd layer 5,94,98 Heating device 6. Containment vessel 63,73 3rd layer 74 4th layer Supply line L2 discharge line L3 Permeation hydrogen recovery line M Heating Module

Claims

1. a heating cell formed by forming a multilayer film that generates heat by allowing hydrogen to pass through the outer peripheral surface of a cylindrical support made of a porous metal sintered body, a porous ceramic sintered body, or a Vycor porous glass; a rod-shaped heater; A heat generating module in which a plurality of the heaters are arranged in a state where they are surrounded by a plurality of the heat generating cells, and are integrally connected with a disk-shaped support metal fitting.

2. The porous metal sintered body is made of Ti, SUS or Mo, and the porous ceramic sintered body is made of Al. ２ O ３ , MgO, CaO, ZrO ２ , SiO ２ , SiC or TiO ２ The heat generating module according to claim 1, wherein the heat generating module comprises:

3. 3. The heat generating module according to claim 1, wherein the multilayer film comprises a first layer less than 1000 nm thick formed from a hydrogen storage metal or a hydrogen storage alloy, and a second layer less than 1000 nm thick formed from a hydrogen storage metal, a hydrogen storage alloy, or a ceramic different from the first layer.

4. A heat generating device comprising the heat generating module according to any one of claims 1 to 3, a storage container for storing the heat generating module; a supply line for supplying hydrogen and a heat transfer medium to the containment vessel; a discharge line for discharging the hydrogen and the heat medium from the containment vessel; a permeated hydrogen recovery line that returns permeated hydrogen that has permeated through the multilayer membrane of each of the heat generating cells of the heat generating module and is discharged from the support to the supply line and recovers it; A heating device comprising:

Images