Hydrogen heating devices for blast furnaces, hydrogen heating methods for blast furnaces, and blast furnace operation methods

Abstract

This invention provides a novel hydrogen heating device, hydrogen heating method, and blast furnace operation method for blast furnaces that can suppress CO2 production even when using hydrogen-based gases as reducing gases. The hydrogen heating device 11 for a blast furnace includes: a sealed container 15 into which hydrogen-based gas is introduced; a heating element 14 disposed inside the sealed container 15, which generates heat by absorbing and releasing hydrogen; and a temperature regulating unit that regulates the temperature of the heating element 14. The heating element 14 has one or more laminates 14a formed by a support 61 and a multilayer film 62. The support 61 is formed by at least one of a porous material, a hydrogen permeable membrane, and a proton conductor. The multilayer film 62 is supported by the support 61. The multilayer film 62 has: a first layer formed by a hydrogen-absorbing metal or a hydrogen-absorbing alloy, with a thickness of less than 1000 nm; and a second layer formed by a hydrogen-absorbing metal, hydrogen-absorbing alloy, or ceramic different from the first layer, with a thickness of less than 1000 nm. The hydrogen-based gas is heated to a specified temperature by heating with the heating element 14.

Description

Technical Field

[0001] This invention relates to a hydrogen heating device for a blast furnace, a hydrogen heating method for a blast furnace, and a blast furnace operation method. Prior Technology

[0002] Generally, in an integrated ironmaking plant equipped with blast furnaces, converters, rolling mills, and energy supply equipment for supplying energy to these facilities, coal (coke) is used as the main energy source. Most of the coal is consumed in the ironmaking process (blast furnace, coke oven, sintering machine), and the waste heat from by-product gases generated in the ironmaking process is effectively used as an energy source for various equipment within the ironmaking plant.

[0003] On the other hand, given the environmental problems facing the Earth, there is a need to curb CO2 production. Of the CO2 produced throughout the ironmaking plant, the amount generated during the iron-making process accounts for the majority, especially from the blast furnace. Therefore, research is underway to improve reduction efficiency through measures such as enhancing the reducibility of raw materials used in the blast furnace and optimizing the distribution of the top charge, thereby operating with a low reducing agent ratio. Specifically, this involves reducing the reducing agent (coke) and partially or completely replacing it with hydrogen-based gases containing hydrogen.

[0004] The coke reduction reaction using coke in the previous ironmaking process (the reaction that oxidizes C to CO2 and reduces Fe2O3 to Fe) is an exothermic reaction. The above reduction reaction is characterized by its spontaneous occurrence.

[0005] On the other hand, hydrogen reduction (the reaction of oxidizing H₂ to H₂O and reducing Fe₂O₃ to Fe) using hydrogen instead of coke is an endothermic reaction. Because it is endothermic, the reduction rate is lower. Furthermore, if the reduction efficiency of the blast furnace is increased, the calorific value of the gas discharged from the blast furnace decreases. Therefore, when the energy supply to the various equipment in the ironmaking plant is lower than the demand, energy must be supplied from external sources.

[0006] Non-Patent Literature 1 describes a temperature drop of approximately 200-600°C inside the blast furnace caused by the introduction of hydrogen during the ironmaking process. Since the reaction occurs directly below the iron ore inlet, the temperature drop near the inlet is particularly noticeable.

[0007] Furthermore, Patent Document 1 describes the following: in order to maintain the calorific value of the blast furnace in the ironmaking process where hydrogen reduction occurs, the amount of hydrogen gas injected is determined based on the previously obtained action line.

[0008] Furthermore, Patent Document 2 describes a method in which heated hydrogen gas is used as the reducing gas instead of coke in the iron-making process. By using heated hydrogen gas in the iron-making process, the amount of hydrogen gas injected can be increased, thereby improving the reduction efficiency. [Previous Technical Documents] [Patent Literature]

[0009] [Patent Document 1] Japanese Patent Application Publication No. 2020-66753 [Patent Document 2] Japanese Patent Application Publication No. 2017-172026 [Non-patent literature]

[0010] [Non-Patent Literature 1] Iron and Steel Vol. 100 (2014) No. 2, pp. 143-147 Summary of the Invention

[0011] [The problem the invention aims to solve]

[0012] As described in Patent Document 2 above, when heated hydrogen-based gases are used as reducing gases in the iron-making process, direct heating of these gases poses a fire hazard due to the low ignition point of hydrogen (around 500°C). Therefore, indirect heating has been studied. Generally, the heat transfer efficiency of indirect heating is reduced; therefore, indirect heating consumes more energy than direct heating when heating hydrogen-based gases. Furthermore, since a large amount of hydrogen is consumed, a large amount of hydrogen-based gas must be heated, requiring a significant amount of energy. Thus, if some or all of the reducing agent is replaced with hydrogen-based gases to suppress CO2 production, heating the hydrogen-based gases will consume a large amount of energy, resulting in difficulty in suppressing CO2 production.

[0013] Therefore, the object of the present invention is to provide a novel hydrogen heating device, hydrogen heating method and blast furnace operation method for blast furnaces that can suppress the generation of CO2 even when using hydrogen-based gases as reducing gases. [Technical means to solve the problem]

[0014] The hydrogen heating device for blast furnace of the present invention heats and supplies hydrogen-containing gas to the blast furnace, and comprises: a sealed container into which the hydrogen-containing gas is introduced; a heating element disposed inside the sealed container, which generates heat by the absorption and release of the hydrogen; and a temperature regulating unit that regulates the temperature of the heating element; the heating element has one or more laminates formed by a support and a multilayer film, wherein the support is formed of at least one of a porous material, a hydrogen permeable membrane, and a proton conductor, and the multilayer film is supported by the support; the multilayer film comprises: a first layer formed of a hydrogen-absorbing metal or a hydrogen-absorbing alloy, and having a thickness of less than 1000 nm; and a second layer formed of a hydrogen-absorbing metal, hydrogen-absorbing alloy, or ceramic different from the first layer, and having a thickness of less than 1000 nm; the hydrogen-containing gas is heated to a predetermined temperature by the heating of the heating element.

[0015] The blast furnace hydrogen heating method of the present invention heats and supplies hydrogen-containing gas to the blast furnace, and includes: an introduction step, which introduces the hydrogen-containing gas into a sealed container; a temperature adjustment step, which adjusts the temperature of a heating element disposed inside the sealed container by a temperature adjustment unit; and a heat generation step, which generates heat from the heating element by the absorption and release of hydrogen in the heating element; the heating element has one or more laminates formed by a support and a multilayer film, the support being formed by at least one of a porous material, a hydrogen permeable membrane, and a proton conductor, and the multilayer film being supported by the support; the multilayer film has: a first layer formed by a hydrogen-absorbing metal or a hydrogen-absorbing alloy, and a thickness of less than 1000 nm; and a second layer formed by a hydrogen-absorbing metal, hydrogen-absorbing alloy, or ceramic different from the first layer, and a thickness of less than 1000 nm; the hydrogen-containing gas is heated to a predetermined temperature by heating with the heating element.

[0016] The blast furnace operation method of the present invention includes the step of blowing hydrogen gas as a reducing gas into the interior of the blast furnace from the tuyeres, wherein the hydrogen gas system is hydrogen gas heated by the hydrogen heating device for the blast furnace. [Effects of the Invention]

[0017] According to the present invention, hydrogen-based gases can be heated without consuming a large amount of energy, and therefore, the amount of CO2 produced can be suppressed accordingly. Therefore, by using hydrogen-based gases heated in this manner as reducing gases in a blast furnace, the amount of CO2 produced can be suppressed even when using hydrogen-based gases as reducing gases. Simple Explanation of the Diagram

[0018] Figure 1 is a schematic diagram of a hydrogen heating device for a blast furnace according to the first embodiment. Figure 2 is a cross-sectional view showing the structure of the heating element. Figure 3 is a cross-sectional view showing the structure of a laminate with a first layer and a second layer. Figure 4 is an explanatory diagram illustrating the generation of excess heat. Figure 5 is an explanatory diagram illustrating the function of the hydrogen heating device for blast furnaces. Figure 6 is a cross-sectional view showing the structure of the heating element in the first variation of the stacked body having multiple stacked bodies. Figure 7 is an explanatory diagram illustrating the heating element of the first variation example. Figure 8 is an explanatory diagram used to illustrate the heating element of the second variation having multiple films on both sides. Figure 9 is an explanatory diagram used to illustrate the heating element of the third variation having a first layer, a second layer, and a third layer. Figure 10 is an explanatory diagram used to illustrate the heating element of the fourth variation having a first layer, a second layer, a third layer, and a fourth layer. Figure 11 is a graph showing the relationship between the thickness ratio of each layer of a multilayer film and excess heat. Figure 12 is a graph showing the relationship between the number of layers in a multilayer film and excess heat. Figure 13 is a graph showing the relationship between the material of the multilayer film and the excess heat. Figure 14 is a cross-sectional view of a heating element formed into a bottomed cylindrical shape. Figure 15 is a schematic diagram of the hydrogen heating device for a blast furnace in the fifth variation. Figure 16 is a cross-sectional view of a heating element having a columnar support. Figure 17 is a schematic diagram of the hydrogen heating device for the blast furnace in the sixth variation. Figure 18 is a schematic diagram of the hydrogen heating device for a blast furnace in the seventh variation. Figure 19 is a schematic diagram of the hydrogen heating device for a blast furnace in the 8th variation. Figure 20 is an explanatory diagram used to illustrate a nozzle section having a plurality of injection ports. Figure 21 is a cross-sectional view of a cylindrical heating element with openings at both ends. Figure 22 is a schematic diagram of the hydrogen heating device for the blast furnace in the 9th variation. Figure 23 is a schematic diagram of the hydrogen heating device for a blast furnace in the 10th variation. Figure 24 is an explanatory diagram illustrating the first mode of the hydrogen pressure control unit. Figure 25 is an explanatory diagram illustrating the second mode of the hydrogen pressure control unit. Figure 26 is a schematic diagram of the hydrogen heating device for a blast furnace according to the 11th variation. Figure 27 is an explanatory diagram used to illustrate the function of the hydrogen heating device for the blast furnace in the 11th variation. Figure 28 is a cross-sectional view of the hydrogen heating device for a blast furnace in the 12th variation. Figure 29 is a graph showing the relationship between hydrogen permeation, hydrogen supply pressure, and sample temperature in the reference experiment. Figure 30 is a graph showing the relationship between sample temperature and input power in the reference experiment. Figure 31 is a graph showing the relationship between the temperature of the heating element and the excess heat in Experiment Example 26. Figure 32 is a graph showing the relationship between the temperature of the heating element and the excess heat in Experiment Example 27. Figure 33 is a schematic diagram of the hydrogen heating device for a blast furnace according to the second embodiment. Figure 34 is a schematic diagram of the hydrogen heating device for a blast furnace according to the third embodiment. Figure 35 is an exploded perspective view of the heating structure. Implementation

[0019] [First Implementation] As shown in Figure 1, the blast furnace equipment 10 includes a blast furnace hydrogen heating device 11 and a blast furnace 12. During blast furnace operation, the blast furnace equipment 10 heats hydrogen-based gases containing hydrogen using the heat generated in the heating element 14 of the blast furnace hydrogen heating device 11. The heated hydrogen-based gases are then supplied as reducing gases from the blast furnace hydrogen heating device 11 to the blast furnace 12 and blown into the interior of the blast furnace 12 through the tuyeres.

[0020] For example, there are no particular limitations on the blast furnace 12, and the blast furnace described in Patent Document 1 or Patent Document 2 can be used. For example, it is configured such that iron-based raw materials are inserted into the blast furnace from the top of the blast furnace, and heated hydrogen-based gas is blown in as a reducing gas along with hot air from the tuyeres provided in the blast furnace.

[0021] The hydrogen heating device 11 for a blast furnace includes a heating element 14, a sealed container 15, a temperature regulating unit 16, a hydrogen flow line 17 having an inlet line 29 and an outlet line 30, and a control unit 18. The heating element 14 is housed in the sealed container 15 and is heated by the heater 16b of the temperature regulating unit 16. The heating element 14 generates heat above the heating temperature of the heater 16b (hereinafter referred to as excess heat) by absorbing and releasing hydrogen. The heating element 14 heats the passing hydrogen gas to a temperature, for example, between 50°C and 1000°C by generating excess heat. In this example, the heating element 14 is formed as a plate having a front and a back. The detailed configuration of the heating element 14 will be described below using other drawings.

[0022] The sealed container 15 is a hollow container that houses the heating element 14. The sealed container 15 is made of, for example, stainless steel. In this example, the sealed container 15 has a shape that is parallel to the direction orthogonal to the front or back of the heating element 14 in the longitudinal direction. A mounting portion 20 for mounting the heating element 14 is provided inside the sealed container 15.

[0023] The sealed container 15 has a first chamber 21 and a second chamber 22 separated by a heating element 14. The first chamber 21 is formed by the front side, which is one side of the heating element 14, and the inner surface of the sealed container 15. The first chamber 21 has an inlet 23 connected to the inlet pipe 29 of the hydrogen flow line 17. Hydrogen gas flowing along the hydrogen flow line 17 is introduced into the first chamber 21 through the inlet 23. The second chamber 22 is formed by the back side, which is the other side of the heating element 14, and the inner surface of the sealed container 15. The second chamber 22 has an outlet 24 connected to the outlet pipe 30 of the hydrogen flow line 17. The hydrogen gas in the second chamber 22 is supplied to the blast furnace 12 from the second chamber 22 through the outlet pipe 30 connected to the outlet 24.

[0024] Chamber 1, 21, is pressurized by the introduction of hydrogen-based gas. Chamber 22 is depressurized by the removal of hydrogen-based gas. Therefore, the hydrogen pressure in Chamber 1, 21, is higher than the hydrogen pressure in Chamber 22. The hydrogen pressure in Chamber 1, 21, is set to, for example, 100 kPa. The hydrogen pressure in Chamber 22, 21, is set to, for example, 1 × 10⁻⁴ Pa or less. Chamber 22 can also be in a vacuum state. Thus, the hydrogen pressures in Chamber 1, 21, and Chamber 22 are different. Therefore, the interior of the sealed container 15 becomes a state where a pressure difference is generated on both sides of the heating element 14.

[0025] If a pressure difference is generated across the heating element 14, hydrogen molecules contained in the hydrogen-based gas are adsorbed on the side of the heating element 14 positioned on the high-pressure side (front side), and these hydrogen molecules dissociate into two hydrogen atoms. The dissociated hydrogen atoms then permeate into the interior of the heating element 14. That is, hydrogen is absorbed into the heating element 14. The hydrogen atoms diffuse and pass through the interior of the heating element 14. On the other side of the heating element 14 positioned on the low-pressure side (back side), the hydrogen atoms that have passed through the heating element 14 re-bond into hydrogen molecules and are released. That is, hydrogen is released from the heating element 14.

[0026] Thus, the heating element 14 allows hydrogen to permeate from the high-pressure side to the low-pressure side. "Permeation" refers to hydrogen being absorbed on one side of the heating element and released from the other side. The heating element 14 generates heat by absorbing hydrogen and also by releasing hydrogen, as will be described in detail below. Therefore, the heating element 14 generates heat through hydrogen permeation. Furthermore, in the following description, regarding the heating element, "hydrogen permeation" may sometimes be written as "hydrogen-based gas permeation".

[0027] A pressure sensor (not shown) for detecting the pressure inside chamber 1 21 is installed inside chamber 1 21. A pressure sensor (not shown) for detecting the pressure inside chamber 22 is installed inside chamber 22. Each pressure sensor installed in chamber 1 21 and chamber 22 is electrically connected to control unit 18 and outputs a signal corresponding to the detected pressure to control unit 18.

[0028] The temperature regulating unit 16 regulates the temperature of the heating element 14 to maintain it at a suitable temperature for heating. The suitable temperature for heating the heating element 14 is, for example, in the range of 50°C to 1000°C. The temperature regulating unit 16 includes a temperature sensor 16a and a heater 16b. The temperature sensor 16a detects the temperature of the heating element 14. The temperature sensor 16a, for example, is a thermocouple and is installed in the mounting section 20 of the sealed container 15. The temperature sensor 16a is electrically connected to the control unit 18 and outputs a signal corresponding to the detected temperature to the control unit 18.

[0029] Heater 16b heats heating element 14. Heater 16b is, for example, a resistance heating type electric heating wire wound around the outer periphery of the sealed container 15. Heater 16b is electrically connected to power source 26 and heats up by receiving power from power source 26. Heater 16b can also be an electric furnace arranged to cover the outer periphery of the sealed container 15.

[0030] The hydrogen flow line 17 is located outside the sealed container 15, allowing hydrogen-containing gas to be introduced from the outside of the sealed container 15 into the inside, and allowing heated hydrogen gas to be discharged from the inside of the sealed container 15 to the outside. In addition to the inlet line 29 and the outlet line 30, the hydrogen flow line 17 also includes a hydrogen tank 28 and a filter 31. Although not illustrated in Figure 1, the blast furnace hydrogen heating device 11 includes a supply line for supplying hydrogen gas to the hydrogen tank 28 and an exhaust line for discharging hydrogen gas from the hydrogen flow line 17. For example, when the blast furnace hydrogen heating device 11 starts operating, hydrogen gas is supplied to the hydrogen tank 28 from the supply line, and when the blast furnace hydrogen heating device 11 stops operating, the hydrogen gas from the hydrogen flow line 17 is discharged to the exhaust line.

[0031] Hydrogen tank 28 stores hydrogen-based gases. The hydrogen-based gas system comprises gases containing isotopes of hydrogen. As hydrogen-based gases, at least one of deuterium and protium can be used. Protium comprises a mixture of naturally occurring protium and deuterium, i.e., a mixture with an abundance ratio of 99.985% for protium and 0.015% for deuterium.

[0032] The inlet line 29 connects the hydrogen tank 28 to the inlet 23 of the first chamber 21, introducing hydrogen gas from the hydrogen tank 28 into the first chamber 21. The inlet line 29 has a pressure regulating valve 32. The pressure regulating valve 32 reduces the pressure of the hydrogen gas supplied from the hydrogen tank 28 to a specified pressure. The pressure regulating valve 32 is electrically connected to the control unit 18. The inlet line 29 also has a pump 33. The pump 33 introduces hydrogen gas from the hydrogen tank 28 into the first chamber 21. For example, a metal telescopic pump can be used as the pump 33. The pump 33 is electrically connected to the control unit 18.

[0033] The outlet pipeline 30 connects the outlet 24 of the second chamber 22 to the blast furnace 12, and supplies the hydrogen gas that passes from the first chamber 21 to the second chamber 22 via the heating element 14 to the blast furnace 12.

[0034] The filter 31 installed in the inlet pipe 29 is used to remove impurities contained in the hydrogen gas. Here, the amount of hydrogen passing through the heating element 14 (hereinafter referred to as hydrogen permeation) is determined by the temperature of the heating element 14, the pressure difference between the two sides of the heating element 14, and the condition of the front side of the heating element 14. When the hydrogen gas contains impurities, sometimes the impurities will adhere to the front side of the heating element 14, resulting in a deterioration of the condition of the front side of the heating element 14. When impurities adhere to the front side of the heating element 14, the adsorption and dissociation of hydrogen molecules on the front side of the heating element 14 are hindered, thereby reducing the hydrogen permeation.

[0035] As impurities that hinder the adsorption and dissociation of hydrogen molecules on the front side of the heating element 14, consider, for example, water (including water vapor), hydrocarbons (methane, ethane, methanol, ethanol, etc.), C, S, and Si. Water is considered to be released from the inner wall of the sealed container 15 or obtained by the reduction of oxide films contained in components disposed inside the sealed container 15 by hydrogen. Hydrocarbons, C, S, and Si are considered to be released from various components disposed inside the sealed container 15. Therefore, the filter 31 removes at least water (including water vapor), hydrocarbons, C, S, and Si as impurities. By removing impurities contained in the hydrogen-based gas, the filter 31 suppresses the reduction in the amount of hydrogen permeating into the heating element 14.

[0036] The control unit 18 controls the operation of various parts of the hydrogen heating device 11 for the blast furnace. The control unit 18 mainly includes, for example, a central processing unit (CPU), read-only memory (ROM), or random access memory (RAM). The CPU performs various calculations using programs or data stored in the memory.

[0037] The control unit 18 is electrically connected to the temperature sensor 16a, the power supply 26, the pressure regulating valve 32, and the pump 33. The control unit 18 controls the output of excess heat generated in the heating element 14 by adjusting the input power of the heater 16b and the pressure of the sealed container 15.

[0038] The control unit 18 functions as an output control unit that controls the output of the heater 16b based on the temperature detected by the temperature sensor 16a. The control unit 18 regulates the input power to the heater 16b by controlling the power supply 26, thereby maintaining the heating element 14 at a suitable temperature for heating.

[0039] The control unit 18 controls the pressure regulating valve 32 and the pump 33 based on the pressure detected by each pressure sensor (not shown) installed in the first chamber 21 and the second chamber 22, thereby adjusting the pressure difference of hydrogen generated between the first chamber 21 and the second chamber 22.

[0040] The control unit 18 performs a hydrogen absorption step of absorbing hydrogen into the heating element 14 and a hydrogen release step of releasing hydrogen from the heating element 14. In this embodiment, the control unit 18 performs the hydrogen absorption step and the hydrogen release step simultaneously by creating a hydrogen pressure difference between the first chamber 21 and the second chamber 22. The control unit 18 introduces hydrogen into the first chamber 21 through the inlet line 29 and discharges the hydrogen gas in the second chamber 22 to the outlet line 30, thereby making the pressure in the first chamber 21 higher than that in the second chamber 22, thus maintaining the state of simultaneous hydrogen absorption on the front side of the heating element 14 and hydrogen release on the back side of the heating element 14.

[0041] In this invention, "simultaneously" refers to a time period that is completely simultaneous or short enough to be considered substantially simultaneous. By simultaneously performing the hydrogen absorption and hydrogen release steps, hydrogen continuously passes through the heating element 14, thus efficiently generating excess heat in the heating element 14. Furthermore, the control unit 18 can also alternately and repeatedly perform the hydrogen absorption and hydrogen release steps. That is, the control unit 18 can first perform the hydrogen absorption step to absorb hydrogen in the heating element 14, and then perform the hydrogen release step to release the hydrogen absorbed in the heating element 14. By alternately and repeatedly performing the hydrogen absorption and hydrogen release steps in this way, excess heat can also be generated from the heating element 14.

[0042] The hydrogen heating device 11 for blast furnaces generates excess heat by creating a hydrogen pressure difference between the first chamber 21 and the second chamber 22, which are separated by a heating element 14. As the hydrogen gas passes through the heating element 14, it is heated by this excess heat. The thicker the heating element 14 and the longer the distance before passing through it, the longer the hydrogen gas is heated by the excess heat generated in the heating element 14, and consequently, the higher its temperature when passing through the heating element 14 and exiting into the second chamber 22. The hydrogen gas is heated to a specified temperature by the heating element 14.

[0043] Next, the detailed structure of the heating element 14 will be described using Figures 2 and 3. As shown in Figure 2, the heating element 14 has a laminate 14a comprising a support 61 and a multilayer film 62.

[0044] Here, for example, hydrogen gas at around 25°C passes through the heating element 14, thereby heating the hydrogen gas and making it a hydrogen gas at a temperature of 50°C to 1000°C, preferably 600°C to 1000°C, after passing through the heating element 14. Furthermore, in this embodiment, Figure 2 shows the hydrogen gas passing through the support 61 at the left end of the paper towards the multilayer film 62 at the right end of the paper. However, the present invention is not limited to this, and the hydrogen gas can also pass through the multilayer film 62 at the right end of the paper towards the support 61 at the left end of the paper.

[0045] The support 61 is formed from at least one of a porous body, a hydrogen-permeable membrane, and a proton conductor. In this example, the support 61 is formed as a plate having a front and a back side. The porous body has pores of a size capable of allowing hydrogen gases to pass through. The porous body is formed, for example, from a metal, a non-metal, or a ceramic. Preferably, the porous body is formed from a material that does not impede the reaction (hereinafter referred to as the exothermic reaction) between the hydrogen gases and the multilayer membrane 62. The hydrogen-permeable membrane is formed, for example, from a hydrogen-absorbing metal or a hydrogen-absorbing alloy. As a hydrogen-absorbing metal, Ni, Pd, V, Nb, Ta, Ti, etc. can be used. As a hydrogen-absorbing alloy, LaNi 5, CaCu 5, MgZn 2, ZrNi 2, ZrCr 2, TiFe, TiCo, Mg 2Ni, Mg 2Cu, etc. can be used. The hydrogen-permeable membrane includes sheets with a mesh structure. As proton conductors, BaCeO3 series (e.g., Ba(Ce 0.95Y 0.05)O 3-6), SrCeO3 series (e.g., Sr(Ce 0.95Y 0.05)O 3-6), CaZrO3 series (e.g., CaZr 0.95Y 0.05O 3- α), SrZrO3 series (e.g., SrZr 0.9Y 0.1O 3- α), βAl 2O 3, βGa 2O 3, etc., can be used.

[0046] As shown in Figure 3, a multilayer film 62 is disposed on a support 61. The multilayer film 62 is formed by a first layer 71 and a second layer 72. The first layer 71 is formed by a hydrogen-absorbing metal or a hydrogen-absorbing alloy, and the second layer 72 is formed by a hydrogen-absorbing metal, hydrogen-absorbing alloy, or ceramic different from the first layer 71. A dissimilar material interface 73 is formed between the support 61 and the first layer 71 and the second layer 72. In Figure 3, the multilayer film 62 is formed by sequentially and alternately depositing the first layer 71 and the second layer 72 on one side (e.g., the front side) of the support 61. The first layer 71 and the second layer 72 are each set to 5 layers. Furthermore, the number of layers of the first layer 71 and the second layer 72 can be appropriately changed. The multilayer film 62 can also be obtained by sequentially and alternately depositing the second layer 72 and the first layer 71 on the front side of the support 61. The multilayer film 62 has one or more first layers 71 and one or more second layers 72, and the heterogeneous material interface 73 is formed at least once.

[0047] The first layer 71 is formed, for example, from any alloy of Ni, Pd, Cu, Mn, Cr, Fe, Mg, Co, etc. Preferably, the alloy forming the first layer 71 is an alloy containing two or more of Ni, Pd, Cu, Mn, Cr, Fe, Mg, and Co. Alternatively, an alloy obtained by adding additive elements to Ni, Pd, Cu, Mn, Cr, Fe, Mg, or Co can be used as the alloy forming the first layer 71.

[0048] The second layer 72 is formed, for example, from any one of Ni, Pd, Cu, Mn, Cr, Fe, Mg, Co, their alloys, or SiC. Preferably, the alloy forming the second layer 72 is an alloy containing two or more of Ni, Pd, Cu, Mn, Cr, Fe, Mg, and Co. Alternatively, an alloy obtained by adding additive elements to Ni, Pd, Cu, Mn, Cr, Fe, Mg, or Co can also be used as the alloy forming the second layer 72.

[0049] When the combination of layer 1 71 and layer 2 72 is represented as "layer 1 71 - layer 2 72 (layer 2 72 - layer 1 71)", the preferred elements are Pd-Ni, Ni-Cu, Ni-Cr, Ni-Fe, Ni-Mg, and Ni-Co. When layer 2 72 is ceramic, "layer 1 71 - layer 2 72" is preferably Ni-SiC.

[0050] As shown in Figure 4, the heterogeneous material interface 73 allows hydrogen atoms to pass through. Figure 4 is a schematic diagram illustrating the following: in the first layer 71 and the second layer 72 formed by a face-centered cubic hydrogen-absorbing metal, hydrogen atoms in the metal lattice of the first layer 71 move through the heterogeneous material interface 73 to the metal lattice of the second layer 72. Hydrogen is known to be relatively light, and it undergoes quantum diffusion by jumping between the positions (octahedral or tetrahedral) occupied by hydrogen in substances A and B. Therefore, the hydrogen absorbed in the heating element 14 undergoes quantum diffusion by jumping within the multilayer film 62. In the heating element 14, hydrogen passes through the first layer 71, the heterogeneous material interface 73, and the second layer 72 via quantum diffusion.

[0051] The thickness of layer 1 71 and layer 2 72 is preferably less than 1000 nm each. If the thickness of layer 1 71 and layer 2 72 is greater than 1000 nm, hydrogen will have difficulty passing through the multilayer film 62. Furthermore, by ensuring that the thickness of layer 1 71 and layer 2 72 is less than 1000 nm, a nanostructure that does not exhibit bulk characteristics can be maintained. More preferably, the thickness of layer 1 71 and layer 2 72 is less than 500 nm. By ensuring that the thickness of layer 1 71 and layer 2 72 is less than 500 nm, a nanostructure that does not exhibit bulk characteristics at all can be maintained.

[0052] Next, an example of a method for manufacturing the heating element 14 will be described. In this case, a plate-shaped support 61 is prepared, and a vapor deposition apparatus is used to deposit the hydrogen-absorbing metal or hydrogen-absorbing alloy, which becomes the first layer 71 or the second layer 72, in a gaseous state. The first layer 71 and the second layer 72 are alternately film-formed on the front side of the support 61 by condensation or adsorption. In this way, a laminate 14a with multiple films 62 on the front side of the support 61 is formed. Furthermore, the first layer 71 and the second layer 72 are preferably formed continuously in a vacuum state. In this way, no natural oxide film is formed between the first layer 71 and the second layer 72, but only a dissimilar material interface 73 is formed. As the vapor deposition apparatus, a physical vapor deposition apparatus that uses physical methods to vapor deposit the hydrogen-absorbing metal or hydrogen-absorbing alloy can be used. As a physical vapor deposition apparatus, a sputtering apparatus, a vacuum vapor deposition apparatus, or a CVD (Chemical Vapor Deposition) apparatus is preferred. Alternatively, hydrogen-absorbing metal or hydrogen-absorbing alloy can be deposited onto the front surface of the support 61 by electroplating to alternately form the first layer 71 and the second layer 72 in a film-like manner.

[0053] As shown in Figure 5, in the heating element 14, for example, the support 61 of the laminate 14a located at one end is disposed on the first chamber 21 side (high pressure side), and the multilayer film 62 of the laminate 14a located at the other end is disposed on the second chamber 22 side (low pressure side). Hydrogen introduced into the first chamber 21 by the pressure difference between the first chamber 21 and the second chamber 22 passes through the interior of the heating element 14 in the order of the support 61 and the multilayer film 62, and moves to the second chamber 22. The heating element 14 generates excess heat when hydrogen passes through the multilayer film 62, i.e., by the absorption of hydrogen in the multilayer film 62 and the release of hydrogen from the multilayer film 62. Alternatively, the heating element 14 may also have the support 61 disposed on the second chamber 22 side (low pressure side) and the multilayer film 62 disposed on the first chamber 21 side (high pressure side).

[0054] The heating element 14 heats the passing hydrogen-based gas using the excess heat it generates. Since the heating element 14 uses hydrogen to generate heat, it does not produce greenhouse gases such as carbon dioxide, making it a clean heat source. Furthermore, the hydrogen used can be generated from water, making it inexpensive. Moreover, the heating process of the heating element 14 is different from nuclear fission reactions and does not involve a chain reaction, thus it is considered safe. Therefore, the hydrogen heating device 11 for the blast furnace uses this heating element 14 as a heat source to heat the hydrogen-based gas, thereby enabling the hydrogen-based gas heated using an inexpensive, clean, and safe heat source to be supplied to the blast furnace 12 as a reducing gas.

[0055] The hydrogen heating device 11 for blast furnaces in this embodiment can heat hydrogen-based gases without consuming a large amount of energy, and therefore, the amount of CO2 produced can be suppressed accordingly. Therefore, the hydrogen heating device 11 for blast furnaces uses hydrogen-based gases heated in this way as reducing gases in the blast furnace 12 during blast furnace operation, and even when hydrogen-based gases are used as reducing gases in the blast furnace 12, the amount of CO2 produced can be suppressed.

[0056] This invention is not limited to the first embodiment described above, and appropriate modifications can be made without departing from the spirit of this invention. Hereinafter, variations of the first embodiment will be described. In the drawings and descriptions of the variations, the same or equivalent constituent elements and components as those in the first embodiment are labeled with the same symbols. Descriptions that are repeated in the first embodiment are appropriately omitted, and key structural differences from the first embodiment are explained.

[0057] [Example of the first variation] As shown in Figure 6, the heating element 19 is composed of a plurality of laminated bodies 14a, including a support 61 and a multilayer film 62. Furthermore, the thickness of the heating element 19 through which hydrogen gas passes is adjusted by changing the number of laminated bodies 14a. Specifically, the more laminated bodies 14a there are, the thicker the heating element 19 becomes, and the longer the distance the hydrogen gas travels before passing through the heating element 19. Therefore, the more laminated bodies 14a there are, the higher the temperature of the hydrogen gas after passing through the heating element 19. On the other hand, the fewer laminated bodies 14a there are, the thinner the heating element 19 becomes, and the shorter the distance the hydrogen gas travels before passing through the heating element 19. Therefore, the fewer laminated bodies 14a there are, the lower the temperature of the hydrogen gas after passing through the heating element 19.

[0058] When setting the number of layers of the laminate 14a, it is ideal to predetermine the correspondence between the temperature of the hydrogen gas after passing through the heating element 19 and the number of layers of the laminate 14a based on past operating experience, and then determine the number of layers of the laminate 14a based on this correspondence so that the hydrogen gas reaches the desired temperature.

[0059] The heating element 19 is constructed by depositing a support 61 of a second laminate 14a on the multilayer film 62 of the first laminate 14a, and a support 61 of a third laminate 14a on the multilayer film 62 of the second laminate 14a, and so on, with a plurality of laminates 14a deposited sequentially. Thus, the heating element 19 shown in FIG. 6 is configured such that, from left to right, the support 61 and the multilayer film 62 are alternately arranged in the order of support 61, multilayer film 62, support 61, and multilayer film 62. Furthermore, in this embodiment, the illustration shows hydrogen gas permeating from the support 61 at the left end of the paper towards the multilayer film 62 at the right end of the paper; however, the invention is not limited to this, and hydrogen gas may also permeate from the multilayer film 62 at the right end of the paper towards the support 61 at the left end of the paper.

[0060] A plurality of laminates 14a can be prepared, and the back side of the support 61 of another laminate 14a can be overlapped with the front side of the multilayer film 62 of a laminate 14a, so that a predetermined number of laminates 14a are laminated, thereby manufacturing a heating element 19. Alternatively, after forming a laminate 14a, a new support 61 can be laminated on the front side of the multilayer film 62 of the laminate 14a, and a vapor deposition apparatus can be used to alternately form a first layer 71 and a second layer 72 on the front side of the new support 61, thereby sequentially forming a new laminate 14a on the front side of a laminate 14a.

[0061] As shown in Figure 7, in the heating element 19, for example, the support 61 of the laminate 14a located at one end is disposed on the first chamber 21 side (high pressure side), and the multilayer membrane 62 of the laminate 14a located at the other end is disposed on the second chamber 22 side (low pressure side). Hydrogen introduced into the first chamber 21 by the pressure difference between the first chamber 21 and the second chamber 22 passes through the interior of the heating element 19 in the order of support 61, multilayer membrane 62, support 61, multilayer membrane 62… and moves to the second chamber 22. The heating element 19 generates excess heat when hydrogen passes through each multilayer membrane 62, i.e., by the absorption of hydrogen in each multilayer membrane 62 and the release of hydrogen from the multilayer membrane 62. Alternatively, the heating element 19 may also have the support 61 disposed on the second chamber 22 side (low pressure side) and the multilayer membrane 62 disposed on the first chamber 21 side (high pressure side).

[0062] [Second Variation Example] As shown in Figure 8, the hydrogen heating device 11 for the blast furnace can also use a heating element 74, which has multiple layers of film 62 disposed on the back side of the support 61 of the laminate 14a disposed at one end, and multiple layers of film 62 disposed on both sides of the support 61. The heating element 74 passes through the multiple layers of film 62, support 61, multiple layers of film 62, support 61, multiple layers of film 62... in sequence, and generates excess heat by the absorption and release of hydrogen in each multiple layer of film 62. By using the heating element 74, high output of excess heat can be achieved.

[0063] [Example of the third variation] The hydrogen heating device 11 for the blast furnace can also include a heating element 75 as shown in FIG. 9 instead of the heating element 14. In the heating element 75 shown in FIG. 9, the multilayer film 62 of the laminate has a first layer 71 and a second layer 72, and further has a third layer 77. The third layer 77 is formed of a hydrogen-absorbing metal, hydrogen-absorbing alloy, or ceramic that is different from the first layer 71 and the second layer 72. The thickness of the third layer 77 is preferably less than 1000 nm. In FIG. 9, the first layer 71, the second layer 72, and the third layer 77 are laminated on the front side of the support 61 in the order of the first layer 71, the second layer 72, the first layer 71, and the third layer 77. Furthermore, the first layer 71, the second layer 72, and the third layer 77 can also be laminated on the front side of the support 61 in the order of the first layer 71, the third layer 77, the first layer 71, and the second layer 72. That is, the multilayer film 62 is configured with a first layer 71 disposed between the second layer 72 and the third layer 77. The multilayer film 62 only needs to have one or more third layers 77. The dissimilar material interface 78 formed between the first layer 71 and the third layer 77, like the dissimilar material interface 73, allows hydrogen atoms to pass through.

[0064] The third layer 77 is formed, for example, from any one of Ni, Pd, Cu, Cr, Fe, Mg, Co, alloys thereof, SiC, CaO, Y₂O₃, TiC, LaB₆, SrO, and BaO. Preferably, the alloy forming the third layer 77 is an alloy containing two or more of Ni, Pd, Cu, Cr, Fe, Mg, and Co. Alternatively, an alloy obtained by adding additive elements to Ni, Pd, Cu, Cr, Fe, Mg, and Co can also be used as the alloy forming the third layer 77.

[0065] In particular, the third layer 77 is preferably formed from any one of CaO, Y₂O₃, TiC, LaB₆, SrO, and BaO. The heating element 75 having a third layer 77 formed from any one of CaO, Y₂O₃, TiC, LaB₆, SrO, and BaO increases the amount of hydrogen absorbed and the amount of hydrogen passing through the heterogeneous material interfaces 73 and 78, thus achieving high output of excess heat. The third layer 77 formed from any one of CaO, Y₂O₃, TiC, LaB₆, SrO, and BaO preferably has a thickness of 10 nm or less. This allows hydrogen atoms to easily permeate through the multilayer film 62. The third layer 77 formed from any one of CaO, Y₂O₃, TiC, LaB₆, SrO, and BaO may also not be formed as a complete film, but rather as an island distribution. Furthermore, the first layer 71 and the third layer 77 are preferably formed as a continuous film under vacuum conditions. In this way, no natural oxide film is formed between the first layer 71 and the third layer 77, but only a heterogeneous material interface 78 is formed.

[0066] When the elements are represented as "Layer 1 71 - Layer 3 77 - Layer 2 72" as a combination of Layer 1 71, Layer 2 72, and Layer 3 77, the preferred combinations 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, Ni-CaO-Fe, Ni-Y₂O₃-Fe, Ni-TiC-Fe, Ni-LaB₆-Fe, Ni-Cr-Fe, Ni-CaO-Mg, Ni-Y₂O₃-Mg, Ni-TiC-Mg, and Ni-LaB₆-Fe. 6-Mg, Ni-CaO-Co, Ni-Y 2O 3-Co, Ni-TiC-Co, Ni-LaB 6-Co, Ni-CaO-SiC, Ni-Y 2O 3-SiC, Ni-TiC-SiC, Ni-LaB 6-SiC.

[0067] [Example of the 4th variation] The hydrogen heating device 11 for blast furnaces includes a heating element 80, as shown in FIG. 10, instead of the heating element 14. In the heating element 80 shown in FIG. 10, the multilayer film 62 of the laminated body has a first layer 71, a second layer 72, and a third layer 77, and further includes a fourth layer 82. The fourth layer 82 is formed of a hydrogen-absorbing metal, hydrogen-absorbing alloy, or ceramic, which is different from the first layer 71, the second layer 72, and the third layer 77. The thickness of the fourth layer 82 is preferably less than 1000 nm. In FIG. 10, the first layer 71, the second layer 72, the third layer 77, and the fourth layer 82 are deposited on the front side of the support 61 in the order of first layer 71, second layer 72, first layer 71, third layer 77, first layer 71, and fourth layer 82. Furthermore, the first layer 71, the second layer 72, the third layer 77, and the fourth layer 82 can also be deposited on the front side of the support 61 in the order of the first layer 71, the fourth layer 82, the first layer 71, the third layer 77, the first layer 71, and the second layer 72. That is, the multilayer film 62 is configured such that the second layer 72, the third layer 77, and the fourth layer 82 are deposited in any order, and the first layer 71 is disposed between each of the second layer 72, the third layer 77, and the fourth layer 82. The multilayer film 62 only needs to have one or more fourth layers 82. The heterogeneous material interface 83 formed between the first layer 71 and the fourth layer 82, like the heterogeneous material interfaces 73 and 78, allows hydrogen atoms to pass through.

[0068] The fourth layer 82 is formed, for example, from any one of Ni, Pd, Cu, Cr, Fe, Mg, Co, alloys thereof, SiC, CaO, Y₂O₃, TiC, LaB₆, SrO, and BaO. Preferably, the alloy forming the fourth layer 82 is an alloy containing two or more of Ni, Pd, Cu, Cr, Fe, Mg, and Co. Alternatively, an alloy obtained by adding additive elements to Ni, Pd, Cu, Cr, Fe, Mg, and Co can also be used as the alloy forming the fourth layer 82.

[0069] In particular, the fourth layer 82 is preferably formed from any one of CaO, Y₂O₃, TiC, LaB₆, SrO, and BaO. The heating element 80 having a fourth layer 82 formed from any one of CaO, Y₂O₃, TiC, LaB₆, SrO, and BaO increases the amount of hydrogen absorbed and the amount of hydrogen passing through the heterogeneous material interfaces 73, 78, and 83, thus achieving high output of excess heat. The fourth layer 82 formed from any one of CaO, Y₂O₃, TiC, LaB₆, SrO, and BaO preferably has a thickness of 10 nm or less. This allows hydrogen atoms to easily permeate through the multilayer film 62. The fourth layer 82 formed from any one of CaO, Y₂O₃, TiC, LaB₆, SrO, and BaO may also not be formed as a complete film, but rather as an island distribution. Furthermore, the first layer 71 and the fourth layer 82 are preferably formed as a continuous film under vacuum conditions. In this way, no natural oxide film is formed between the first layer 71 and the fourth layer 82, but only a heterogeneous material interface 83 is formed.

[0070] When the combination of layer 1 71, layer 2 72, layer 3 77 and layer 4 82 represents the types of elements as "layer 1 71-layer 4 82-layer 3 77-layer 2 72", it is preferred to be Ni-CaO-Cr-Fe, Ni-Y 2O 3-Cr-Fe, Ni-TiC-Cr-Fe, or Ni-LaB 6-Cr-Fe.

[0071] Furthermore, as a heating element, it can also be configured by mixing any two or more of the following: the stacked body 14a of the heating element 14 shown in FIG. 3, the stacked body of the heating element 75 shown in FIG. 9, and the stacked body of the heating element 80 shown in FIG. 10, and stacking multiple stacked bodies alternately or in any order. The configuration of the multilayer film 62, such as the ratio of the thickness of each layer, the number of layers, and the material, can also be appropriately changed according to the operating temperature. Hereinafter, the "relationship between the thickness ratio of each layer of the multilayer film and excess heat", the "relationship between the number of layers of the multilayer film and excess heat", and the "relationship between the material of the multilayer film and excess heat" will be explained, and then an example of the configuration of the multilayer film 62 corresponding to the temperature will be explained.

[0072] The relationships between the thickness ratio of each layer in a multilayer film and excess heat, the number of layers in a multilayer film and excess heat, and the material of the multilayer film and excess heat were investigated using an experimental hydrogen heating device for a blast furnace (not shown). The investigation focused on whether an experimentally prepared heating element containing a single multilayer film would generate excess heat. The experimental hydrogen heating device for a blast furnace includes a sealed container, two heating elements disposed inside the sealed container, and heaters for heating each heating element. The heating elements are plate-shaped. The heaters are plate-shaped ceramic heaters with built-in thermocouples. The heaters are positioned between the two heating elements. The sealed container is connected to a hydrogen gas supply path and an exhaust path. The hydrogen gas supply path connects a storage tank containing hydrogen gas to the sealed container. An adjustment valve is installed in the hydrogen gas supply path to adjust the amount of hydrogen gas supplied from the storage tank to the sealed container. The exhaust path is connected to a dry pump used for vacuuming the interior of the sealed container. Adjusting valves for regulating the gas flow rate are installed in the exhaust path.

[0073] The experimental hydrogen heating device for the blast furnace generates excess heat from the self-heating element by alternately performing hydrogen absorption and release steps. Specifically, the device absorbs hydrogen into the heating element through a hydrogen absorption step, and then releases the absorbed hydrogen through a hydrogen release step. During the hydrogen absorption step, hydrogen gas is supplied to the sealed container. During the hydrogen release step, vacuum exhaust and heating of the heating element are performed inside the sealed container.

[0074] The relationship between the thickness ratio of each layer of the multilayer film and excess heat will be explained. First, focusing on a laminate 14a, a heat-generating element 14 is used, which has a Ni-containing support 61 and a multilayer film 62 formed by a first layer 71 containing Cu and a second layer 72 containing Ni. The relationship between the thickness ratio of the first layer 71 to the second layer 72 and excess heat is investigated. Hereinafter, the thickness ratio of each layer of the multilayer film 62 will be described as Ni:Cu.

[0075] Eight types of heating elements 14, excluding Ni:Cu, were fabricated under the same conditions to form a multilayer film 62, designated as Experimental Examples 1 to 8. Furthermore, the multilayer film 62 was only disposed on the front side of the support 61. The Ni:Cu ratios of the heating elements 14 in Experimental Examples 1 to 8 were 7:1, 14:1, 4.33:1, 3:1, 5:1, 8:1, 6:1, and 6.5:1. In each heating element 14 of Experimental Examples 1 to 8, the multilayer film 62 was composed of repeated layers of a first layer 71 and a second layer 72. The number of layers of the multilayer film 62 (hereinafter referred to as the number of layers of the multilayer film) in each heating element 14 of Experimental Examples 1 to 8 was set to 5. The overall thickness of the multilayer film 62 in each heating element 14 of Experimental Examples 1 to 8 was set to be approximately the same.

[0076] The heating element 14 of Examples 1-8 was placed inside the sealed container of the hydrogen heating device for the experimental blast furnace, and the hydrogen absorption and release steps were repeated alternately. Protium gas (manufactured by Numata Oxygen Co., Ltd., grade II, purity 99.999 vol% or higher) was used as the hydrogen-based gas. In the hydrogen absorption step, the hydrogen-based gas was supplied to the inside of the sealed container at approximately 50 Pa. The time for hydrogen absorption in the heating element 14 was set to approximately 64 hours. Furthermore, before the hydrogen absorption step, the inside of the sealed container was preheated at 200°C or higher for approximately 36 hours using a heater to remove water and other substances adhering to the surface of the heating element 14.

[0077] In the hydrogen release step, the hydrogen storage step is interrupted, and the input power to the heater is set to 9 W, 18 W, and 27 W. Furthermore, the temperature of the heating element 14 during each hydrogen release step is measured using a thermocouple built into the heater. The results are shown in Figure 11. Figure 11 is a graph obtained by fitting the measured data using a prescribed method. In Figure 11, the horizontal axis represents the heater temperature, and the vertical axis represents the excess heat power. The heater temperature is the temperature of the heating element 14 under the prescribed input power. In Figure 11, Experiment 1 is described as "Ni:Cu=7:1", Experiment 2 as "Ni:Cu=14:1", Experiment 3 as "Ni:Cu=4.33:1", Experiment 4 as "Ni:Cu=3:1", Experiment 5 as "Ni:Cu=5:1", Experiment 6 as "Ni:Cu=8:1", Experiment 7 as "Ni:Cu=6:1", and Experiment 8 as "Ni:Cu=6.5:1".

[0078] As shown in Figure 11, excess heat is generated in all heating elements 14 in Experiments 1-8. Therefore, it can be confirmed that hydrogen gas can be heated when it passes through a heating element 14 containing one stacked body 14a. Furthermore, if a heating element 14 is formed by stacking multiple such stacked bodies 14a, the time required to heat the hydrogen gas is correspondingly longer because the distance between the stacked bodies 14a that generate excess heat is extended, thereby increasing the temperature of the hydrogen gas. Therefore, it is known that by changing the number of stacked bodies 14a in the heating element 14, the temperature of the hydrogen gas after passing through the heating element 14 can be adjusted.

[0079] Comparing the heating elements 14 of Experiments 1-8 at heater temperatures above 700°C, it is evident that Experiment 1 generates the greatest excess heat. Comparing the heating element 14 of Experiments 1, 2, 4-8 with that of Experiment 3, it is clear that excess heat is generated over a wide range of heater temperatures, from 300°C to 1000°C. It is also evident that for the heating elements 14 of Experiments 1, 3-8, where the Ni:Cu ratio of the multilayer film 62 is 3:1 to 8:1, the excess heat increases with increasing heater temperature. It is also evident that the excess heat of the heating element 14 of Experiment 2, where the Ni:Cu ratio of the multilayer film 62 is 14:1, decreases when the heater temperature is above 800°C. It is believed that this non-simply increasing excess heat relative to the Ni:Cu ratio is caused by the quantum effect of hydrogen in the multilayer film 62.

[0080] Next, the relationship between the number of layers in a multilayer film and excess heat will be explained. Using a heating element 14 containing one stack 14a, the relationship between the number of layers in a multilayer film 62 and excess heat will be investigated. The stack 14a is composed of a support 61 containing Ni and a multilayer film 62. The multilayer film 62 is formed by a first layer 71 containing Cu and a second layer 72 containing Ni.

[0081] The heating element 14 of Experimental Example 1 and eight other heating elements 14 (each having a single multilayer film 14a) manufactured under the same conditions except for the number of layers in the multilayer film 62 were prepared and designated as Experimental Examples 9 to 16. The number of layers in the multilayer film 62 of each heating element 14 in Experimental Examples 1, 9 to 16 are 5, 3, 7, 6, 8, 9, 12, 4, and 2, respectively.

[0082] The heating elements 14 of Examples 1, 9-16 were placed inside the sealed container of the hydrogen heating device for the experimental blast furnace. The hydrogen heating device for the experimental blast furnace was the same as the device used to investigate the relationship between the thickness ratio of each layer of the multilayer film and excess heat. In the hydrogen heating device for the experimental blast furnace, the temperature of the heating element 14 during the hydrogen release step was measured using the same method as for the relationship between the thickness ratio of each layer of the multilayer film and excess heat. The results are shown in Figure 12. Figure 12 is a graph obtained by fitting the measured data using a prescribed method. In Figure 12, the horizontal axis represents the heater temperature, and the vertical axis represents the electricity for excess heat. In Figure 12, based on the thickness of each layer, Experiment 1 is described as "Ni 0.875Cu 0.1255 layer", Experiment 9 as "Ni 0.875Cu 0.1253 layer", Experiment 10 as "Ni 0.875Cu 0.1257 layer", Experiment 11 as "Ni 0.875Cu 0.1256 layer", Experiment 12 as "Ni 0.875Cu 0.1258 layer", Experiment 13 as "Ni 0.875Cu 0.1259 layer", Experiment 14 as "Ni 0.875Cu 0.12512 layer", Experiment 15 as "Ni 0.875Cu 0.1254 layer", and Experiment 16 as "Ni 0.875Cu 0.1254 layer". "0.1252 layers".

[0083] As confirmed by Figure 12, excess heat was generated in all heating elements 14 of Experiments 1, 9-16. Comparing the heating elements 14 of Experiments 1, 9-16 at heater temperatures above 840°C, it was found that the excess heat was greatest in Experiment 11, where the number of layers in the multilayer film 62 was 6, and smallest in Experiment 12, where the number of layers in the multilayer film 62 was 8. It is believed that the reason why the excess heat did not simply increase relative to the number of layers in the multilayer film 62 is that the wave behavior of hydrogen in the multilayer film 62 has a wavelength on the nanometer scale, which interferes with the multilayer film 62.

[0084] Next, the relationship between the material of the multilayer film and excess heat will be explained. Using a heating element 75 containing a multilayer film 62, the relationship between the type of material forming the third layer 77 and excess heat will be investigated. The multilayer film 62 is formed by a first layer 71 containing Ni, a second layer 72 containing Cu, and a third layer 77 containing a hydrogen-absorbing metal, hydrogen-absorbing alloy, or ceramic that is different from the first layer 71 and the second layer 72.

[0085] Nine types of heating elements 75, excluding the type of material used to form the third layer 77, were fabricated under the same conditions to form a multilayer film 62, and these were designated as Experimental Examples 17-25. In each of the heating elements 75 in Experimental Examples 17-25, the types of materials used to form the third layer 77 were CaO, SiC, Y₂O₃, TiC, Co, LaB₆, ZrC, TiB₂, and CaO / ZrO.

[0086] Each heating element 75 from Examples 17-25 was placed inside the sealed container of the hydrogen heating device for the experimental blast furnace. The hydrogen heating device for the experimental blast furnace was the same as the device used to investigate the relationship between the thickness ratio of each layer of the multilayer film and excess heat. In the hydrogen heating device for the experimental blast furnace, the temperature of the heating element 75 during the hydrogen release step was measured using the same method as for the relationship between the thickness ratio of each layer of the multilayer film and excess heat. The results are shown in Figure 13. Figure 13 is a graph obtained by fitting the measured data using a prescribed method. In Figure 13, the horizontal axis represents the heater temperature, and the vertical axis represents the electricity for excess heat. In Figure 13, based on the thickness of each layer, Experimental Example 17 is described as "Ni 0.793CaO 0.113Cu 0.094", Experimental Example 18 is described as "Ni 0.793SiC 0.113Cu 0.094", Experimental Example 19 is described as "Ni 0.793Y₂O₃ 0.113Cu 0.094", Experimental Example 20 is described as "Ni 0.793TiC 0.113Cu 0.094", Experimental Example 21 is described as "Ni 0.793Co 0.113Cu 0.094", Experimental Example 22 is described as "Ni 0.793LaB₆ 0.113Cu 0.094", and Experimental Example 23 is described as "Ni 0.793ZrC 0.113Cu". 0.094”, Experiment 24 is described as “Ni 0.793TiB 20.113Cu 0.094”, and Experiment 25 is described as “Ni 0.793CaOZrO 0.113Cu 0.094”.

[0087] Figure 13 confirms that excess heat is generated in all heating elements 75 in Experiments 17-25. Therefore, it can be confirmed that hydrogen gas can be heated when it passes through a heating element 75 containing a single stacked volume. Furthermore, it is known that if a heating element 75 is composed of multiple such stacked volume layers, the distance between the stacked volumes that generate excess heat is increased, thus the heating time for the hydrogen gas is correspondingly longer, thereby increasing the temperature of the hydrogen gas. Therefore, it is known that by changing the number of stacked volume layers in the heating element 75, the temperature of the hydrogen gas ultimately passing through the heating element 75 can be adjusted.

[0088] Furthermore, in particular, compared with other experimental examples 18, 19, 21, and 23-25, the materials forming the third layer 77 (CaO in Example 17, TiC in Example 20, and LaB6 in Example 22) show that the excess heat increases approximately linearly over a wide range of heater temperatures between 400°C and 1000°C. The materials forming the third layer 77 in Examples 17, 20, and 22 have lower work functions compared to the materials in other experimental examples 18, 19, 21, and 23-25. Therefore, it is preferable to use materials with lower work functions for forming the third layer 77. Based on these results, the electron density within the multilayer film 62 may contribute to the exothermic reaction.

[0089] An example of the configuration of the multilayer film 62 corresponding to the temperature of the heating element 14 will be described. Considering the aforementioned relationship between the thickness ratio of each layer of the multilayer film and excess heat for the heating element 14, when the temperature of the heating element 14 is low (e.g., in the range of 50°C to 500°C), it is preferable that the thickness ratio of each layer of the multilayer film 62 is in the range of 2:1 to 5:1. When the temperature of the heating element 14 is medium (e.g., in the range of 500°C to 800°C), it is preferable that the thickness ratio of each layer of the multilayer film 62 is in the range of 5:1 to 6:1. When the temperature of the heating element 14 is high (e.g., in the range of 800°C to 1000°C), it is preferable that the thickness ratio of each layer of the multilayer film 62 is in the range of 6:1 to 12:1.

[0090] If we consider the above-mentioned "relationship between the number of layers of the multilayer film and the excess heat", then when the temperature of the heating element 14 is any of low temperature, medium temperature and high temperature, it is preferable that the first layer 71 of the multilayer film 62 is in the range of 2 to 18 layers, and the second layer 72 is in the range of 2 to 18 layers.

[0091] If we consider the aforementioned relationship between the materials of the multilayer film and excess heat for the heating element 75, then when the temperature of the heating element 75 is low, it is preferable that the first layer 71 is Ni, the second layer 72 is Cu, and the third layer 77 is Y₂O₃. When the temperature of the heating element 75 is medium, it is preferable that the first layer 71 is Ni, the second layer 72 is Cu, and the third layer 77 is TiC. When the temperature of the heating element 75 is high, it is preferable that the first layer 71 is Ni, the second layer 72 is Cu, and the third layer 77 is CaO or LaB₆.

[0092] [5th ​​Variation Example] Figure 14 is a cross-sectional view of a bottomed cylindrical heating element 90 that is open at one end and closed at the other. The heating element 90 has a plurality of laminated bodies 90a having a support 91 and a multilayer film 92. In this case, the multilayer film 92 is formed on the outer peripheral surface and outer bottom surface of the bottomed cylindrical support 91, which is open at one end and closed at the other. The multilayer film 92 is also formed as a bottomed cylindrical shape with one end open and closed at the other.

[0093] The heating element 90 has the following configuration: a support 91 for the outer layer of the multilayer film 92 of the inner layer 90a is disposed along the outer peripheral surface and the outer bottom surface of the outer layer 90a. The support 91 and multilayer film 92 are alternately deposited from the inner surface to the outer surface in the order of support 91, multilayer film 92, support 91, and multilayer film 92. In this manner, a plurality of bottomed cylindrical layers 90a are deposited in the heating element 90. The number of layers of these layers 90a is set so that the hydrogen gas that has passed through the heating element 90 is heated to a predetermined temperature.

[0094] Each support 91 is formed from at least one of a porous material, a hydrogen-permeable membrane, and a proton conductor. Furthermore, each multilayer film 92 has: a first layer (not shown), formed of a hydrogen-absorbing metal or hydrogen-absorbing alloy, with a thickness of less than 1000 nm; and a second layer (not shown), formed of a hydrogen-absorbing metal, hydrogen-absorbing alloy, or ceramic different from the first layer, with a thickness of less than 1000 nm. Moreover, in Figure 14, the heating element 90 is formed as a bottomed cylindrical shape, but it can also be formed as a bottomed corner cylinder.

[0095] Next, an example of a method for manufacturing the heating element 90 will be described. The heating element 90 is prepared to be formed as a bottomed cylindrical support 91, and a multilayer film 92 is formed on the support 91 using a wet film formation method. In this example, the multilayer film 92 is formed on the outer surface of the support 91. This forms the innermost bottomed cylindrical laminate 90a. Then, another support 91 is prepared to be formed as a sheet, and a multilayer film 92 is formed on the outer surface of the sheet-like support 91 using a wet film formation method, thereby forming a new bottomed cylindrical sheet-like laminate 90a. Then, the other sheet-like laminates 90a are repeatedly overlapped on the outer surface of the innermost laminate 90a, thereby manufacturing a heating element 90 obtained by stacking multiple laminates 90a. Furthermore, a multilayer film 92 can be formed on the outer surface of the innermost bottomed cylindrical support 91, and then a sheet-like support 91 can be formed on the outer peripheral surface and bottom surface of the multilayer film 92, and a multilayer film 92 can be formed again on the outer peripheral surface and bottom surface of the support 91, etc., in sequence forming the support 91 and the multilayer film 92.

[0096] Furthermore, as a wet film formation method, spin coating, spraying, and dipping methods can be used. Also, the multilayer film 92 can be formed using ALD (Atomic Layer Deposition) or a sputtering apparatus equipped with a spin mechanism that rotates the support 91, forming the multilayer film 92 on the support 91 while it is being rotated. Furthermore, the multilayer film 92 can also be disposed on the innermost surface of the support 91, with the multilayer film 92 disposed on both sides of the support 91 located at the innermost periphery.

[0097] As shown in Figure 15, the blast furnace equipment 95 includes a hydrogen heating device 96 for the blast furnace and a blast furnace 12. The hydrogen heating device 96 differs from the hydrogen heating device 11 for the blast furnace described above in that it has a heating element 90 instead of a heating element 14. The heating element 90 is mounted in a sealed container 15 using a mounting pipe 97. Although omitted in Figure 15, the hydrogen heating device 96 includes a temperature sensor for detecting the temperature of the heating element 90, a power supply for inputting power to the heater 16b, and a control unit that controls the output of the heater 16b based on the temperature detected by the temperature sensor. The temperature sensor is, for example, provided on the outer surface of the heating element 90.

[0098] The mounting tube 97 is made of, for example, stainless steel. The mounting tube 97 passes through the sealed container 15, with one end disposed on the outer surface of the sealed container 15 and the other end disposed inside the sealed container 15. One end of the mounting tube 97 is connected to the inlet line 29 of the hydrogen flow line 17. A heating element 90 is provided at the other end of the mounting tube 97.

[0099] In the fifth variation, the first chamber 21 is formed from the inner surface of the heating element 90. The second chamber 22 is formed from the inner surface of the sealed container 15 and the outer surface of the heating element 90. Therefore, the heating element 90 has a support 91 disposed on the first chamber 21 side (high pressure side) and a multilayer membrane 92 disposed on the second chamber 22 side (low pressure side) (see Figure 14). Hydrogen introduced into the first chamber 21 by the pressure difference generated between the first chamber 21 and the second chamber 22 passes through the interior of the heating element 90 in the order of support 91, multilayer membrane 92, support 91, multilayer membrane 92, ... and moves to the second chamber 22. That is, hydrogen passes from the inner surface of the heating element 90 to the outer surface through a plurality of stacked bodies 90a in a predetermined number. In this way, each stacked body 90a of the heating element 90 generates excess heat when hydrogen is released from the multilayer membrane 92. Therefore, the hydrogen heating device 96 for blast furnace has the same effect as the hydrogen heating device 11 for blast furnace described in the above embodiment.

[0100] Furthermore, the hydrogen heating device 96 for the blast furnace can also include a heating element 98 as shown in FIG. 16 instead of the heating element 90. The heating element 98 differs from the heating element 90 in that the innermost laminate 90b has a columnar support 91a. The support 91a is formed, similarly to the support 61, from at least one of a porous material, a hydrogen-permeable membrane, and a proton conductor. The support 91a allows hydrogen gas to pass through and improves the mechanical strength of the heating element 98. Furthermore, in FIG. 16, the support 91a is formed as a cylinder, but it can also be formed as a prismatic shape. Also, in the fifth variation above, a configuration with multiple laminates 90a is shown, but a configuration with only one laminate 90a is also possible.

[0101] [Sixth variation example] As shown in Figure 17, the blast furnace equipment 115 includes a hydrogen heating device 121 for the blast furnace and a blast furnace 12. The hydrogen heating device 121 differs from the hydrogen heating device 11 for the blast furnace described in the above embodiment in that it has a sealed container 123 instead of a sealed container 15. The sealed container 123 is a hollow container that houses the heating element 14. The sealed container 123 is covered by insulation material 51. An installation pipe 125 for mounting the heating element 14 is provided in the sealed container 123.

[0102] The mounting tube 125 is made of, for example, stainless steel. The mounting tube 125 passes through the sealed container 123, with one end disposed outside the sealed container 123 and the other end disposed inside the sealed container 123. In this example, one end of the mounting tube 125 is disposed within the insulation material 51. One end of the mounting tube 125 is connected to the inlet line 29 of the hydrogen flow line 17. A heating element 14 is provided at the other end of the mounting tube 125. A heater 16b with a temperature regulating section (not shown) is wound around the outer periphery of the mounting tube 125.

[0103] The sealed container 123 has a first chamber 126 and a second chamber 127 separated by an installation tube 125 and a heating element 14. The first chamber 126 is formed by the front surface of the heating element 14 and the inner surface of the installation tube 125. The first chamber 126 has an inlet 23 connected to an inlet line 29. The second chamber 127 is formed by the inner surface of the sealed container 123, the back surface of the heating element 14, and the outer surface of the installation tube 125. The second chamber 127 has an outlet 24 connected to an outlet line 30. In Figure 17, the outlet 24 is located approximately at the center along the length of the sealed container 123. The first chamber 126 is pressurized by introducing hydrogen gas. The second chamber 127 is depressurized by discharging hydrogen gas. Therefore, the hydrogen pressure in the first chamber 126 is higher than the hydrogen pressure in the second chamber 127. The hydrogen pressures in the first chamber 126 and the second chamber 127 are different. Therefore, the interior of the sealed container 123 becomes a state in which a pressure difference is generated on both sides of the heating element 14.

[0104] The heated hydrogen gas system flowing along the outlet pipeline 30 is transported from the tuyeres of the blast furnace 12 to the interior of the blast furnace 12 via the outlet pipeline 30 in the same manner as in the above embodiment, and is used as a reducing gas in the blast furnace 12.

[0105] As described above, the hydrogen heating device 121 for blast furnaces utilizes the heat generated in each layer 14a of the heating element 14 within the sealed container 123 to heat the hydrogen gas from the first chamber 126 inside the mounting tube 125 to the second chamber 127. In this way, even with the hydrogen heating device 121 for blast furnaces, the temperature of the hydrogen gas can be raised to a predetermined temperature by presetting the number of layers 14a of the heating element 14 to a predetermined number. Therefore, it has the same operating effect as the hydrogen heating device 11 for blast furnaces described above.

[0106] [Seventh Variation Example] As shown in Figure 18, the blast furnace equipment 145 includes a hydrogen heating device 146 for the blast furnace and a blast furnace 12. The hydrogen heating device 146 for the blast furnace has a heater 137 installed in the inlet pipe 29 and a nozzle 148 disposed inside the sealed container 15. The hydrogen heating device 146 for the blast furnace differs from the hydrogen heating device 11 for the blast furnace described in the above embodiment in the placement of the heater 137 in the temperature regulating unit (not shown), and in the installation of the nozzle 148 and the non-permeable gas recovery pipe 149. The temperature regulating unit (not shown) is composed of a temperature sensor 16a, a heater 137, and a control unit 18 that serves as an output control unit.

[0107] Heater 137 is installed in inlet pipe 29 and heats heating element 14 by heating hydrogen gas flowing along inlet pipe 29. Heater 137 is electrically connected to power supply 26 and heats up by receiving power from power supply 26. Power supply 26 is controlled by control unit 18. Control unit 18 adjusts the power input to heater 137 based on the temperature detected by temperature sensor 16a, thereby maintaining heating element 14 at a suitable temperature for heating.

[0108] The hydrogen heating device 146 for blast furnaces, by having a heater 137 in the inlet pipeline 29, can deliver heated hydrogen gas to the interior of the sealed container 15, and use the heated hydrogen gas to heat the heating element 14, thereby maintaining the heating element 14 at a suitable temperature for heating. Even with this configuration, it has the same operating effect as the hydrogen heating device 11 for blast furnaces described above.

[0109] A nozzle portion 148 is disposed between the inlet 23 and the heating element 14. The nozzle portion 148 is connected to the inlet pipe 29 via the inlet 23. The nozzle portion 148 injects hydrogen gas, which has flowed along the inlet pipe 29 and has had impurities removed by the filter 31, from the injection port disposed at the nozzle tip. The distance between the nozzle tip and the front surface of the heating element 14 is, for example, 1 to 2 cm. The direction of the nozzle tip is set to be perpendicular to the front surface of the heating element 14. In this way, the nozzle portion 148 injects hydrogen gas into the entire front surface area of ​​the heating element 14. Furthermore, the distance between the nozzle tip and the front surface of the heating element 14, or the direction of the nozzle tip, is preferably set to the distance or direction at which the hydrogen gas ejected from the nozzle tip is blown to the entire front surface area of ​​the heating element 14.

[0110] The non-permeable gas recovery pipeline 149 is connected to the non-permeable gas recovery port 151 located in the first chamber 21, recovering the non-permeable gas that has not passed through the heating element 14 from the hydrogen-based gas introduced into the first chamber 21. The non-permeable gas recovery pipeline 149 is connected to the hydrogen tank 28, returning the recovered non-permeable gas to the hydrogen tank 28. The non-permeable gas recovery port 151 is arranged side by side with the inlet 23.

[0111] In the above configuration, the hydrogen gas introduced into the first chamber 21 is gradually heated by the heat of each of the stacked bodies 14a of the heating element 14. The hydrogen gas heated by the heating element 14 is discharged along the discharge pipeline 30. The hydrogen gas discharged along the discharge pipeline 30 is supplied to the blast furnace 12 via the pressure regulating valve 32.

[0112] On the other hand, the remaining hydrogen gas system introduced into chamber 21 but not passing through the heating element 14 is recovered as non-permeable gas by the non-permeable gas recovery line 149. The non-permeable gas system flows back to the hydrogen tank 28 along the non-permeable gas recovery line 149, and then flows again along the inlet line 29 as hydrogen gas introduced into chamber 21. That is, the non-permeable gas recovery line 149 connects chamber 21 and inlet line 29, recovering the non-permeable gas that did not pass through the heating element 14 from the hydrogen gas introduced into chamber 21 from inlet line 29 and sending it back to inlet line 29.

[0113] The non-permeable gas recovery line 149 includes a non-permeable gas flow control unit 152 and a circulation pump 153. The non-permeable gas flow control unit 152 has, for example, a variable leak valve as an adjustment valve. The non-permeable gas flow control unit 152 controls the flow rate of the non-permeable gas based on the temperature detected by the temperature sensor 16a. For example, when the temperature of the heating element 14 detected by the temperature sensor 16a exceeds the upper limit of the appropriate temperature range for heating the heating element 14, the non-permeable gas flow control unit 152 increases the circulation flow rate of the non-permeable gas. When the temperature of the heating element 14 detected by the temperature sensor 16a does not reach the lower limit of the appropriate temperature range for heating the heating element 14, the non-permeable gas flow control unit 152 decreases the flow rate of the non-permeable gas. In this way, the non-permeable gas flow control unit 152 maintains the heating element 14 at a suitable temperature for heating by increasing or decreasing the circulation flow rate of the non-permeable gas.

[0114] The circulation pump 153 recovers the non-permeable gas from chamber 21 through the non-permeable gas recovery port 151 and delivers it to the hydrogen tank 28. For example, a metal telescopic pump can be used as the circulation pump 153. The circulation pump 153 is electrically connected to the control unit 18.

[0115] The hydrogen heating device 146 for blast furnaces blows hydrogen gas, after impurities have been removed, directly onto the front of the heating element 14 via a nozzle portion 148. In this way, impurities on the front and periphery of the heating element 14 are dispersed, and the front of the heating element 14 is positioned in an atmosphere created by the clean hydrogen gas after impurities have been removed by the filter 31. Therefore, high output of excess heat can be achieved.

[0116] [8th Variation Example] As shown in Figure 19, the blast furnace equipment 155 includes a hydrogen heating device 156 for the blast furnace and a blast furnace 12. The hydrogen heating device 156 has a heating element 90 replacing the heating element 14, and a nozzle portion 158 is arranged inside a sealed container 15. In this example, the inlet 23 and the non-permeable gas recovery port 151 are arranged side by side relative to the mounting pipe 97.

[0117] The nozzle portion 158 is disposed between the inlet 23 and the heating element 90, with one end connected to the inlet 23 and the other end extending to the other end of the heating element 90. The nozzle portion 158 is connected to the inlet line 29 via the inlet 23.

[0118] As shown in Figure 20, a plurality of injection ports 159 are formed on the circumferential side of the cylindrical nozzle portion 158 along the axial direction of the heating element 90. Furthermore, in this embodiment, the nozzle portion 158 also has injection ports 159 formed on its bottom surface. The nozzle portion 158 injects hydrogen-based gas from the plurality of injection ports 159 into the entire area of ​​the inner surface of the heating element 90 (inner circumferential surface and inner bottom surface). The plurality of injection ports 159 are preferably arranged at equal intervals. By arranging the plurality of injection ports 159 at equal intervals, hydrogen-based gas is uniformly injected into the entire area of ​​the inner surface of the heating element 90. The number or diameter of the injection ports 159 can be appropriately varied. Furthermore, in the eighth variation described above, a configuration with a plurality of laminates 90a is shown, but a configuration with only one laminate 90a is also possible.

[0119] Furthermore, the heating element 90 is configured to have a non-permeable gas recovery line 149 connected to the non-permeable gas recovery port 151 provided in the first chamber 21, which can recover the non-permeable gas that does not pass through the heating element 14 in the hydrogen gas introduced into the first chamber 21 from the non-permeable gas recovery line 149.

[0120] Furthermore, the hydrogen heating device 156 for blast furnace sprays hydrogen gas from the nozzle 158, and the impurities on the inner surface and surrounding area of ​​the heating element 90 are blown away by the hydrogen gas. The interior of the heating element 90 is set to an atmosphere formed by fresh hydrogen gas after impurities are removed by the filter 31. Therefore, high output of excess heat can be achieved.

[0121] [9th Variation Example] Figure 21 is a cross-sectional view of a cylindrical heating element 160 with openings at both ends. The heating element 160 includes a plurality of laminated bodies 160a having a support body 161 and a multilayer film 162. In this case, each laminated body 160a has a cylindrical multilayer film 162 formed on the outer peripheral surface of the cylindrical support body 161. The heating element 160 is constructed by providing the support body 161 of other laminated bodies 160a on the outer peripheral surface of the multilayer film 162 of one laminated body 160a, and by sequentially and alternately arranging the support body 161 and the multilayer film 162 from the inside to the outside in the order of support body 161, multilayer film 162, support body 161, multilayer film 162, thereby laminating a predetermined number of a plurality of laminated bodies 160a. In this way, a plurality of cylindrical stacked bodies 160a are stacked on the heating element 160, and the number of stacked bodies 160a is set so that the hydrogen gas that has passed through the heating element 160 is heated to a specified temperature.

[0122] Furthermore, the support 161 is formed from at least one of a porous material, a hydrogen-permeable membrane, and a proton conductor. The multilayer film 162 has: a first layer (not shown), which is formed from a hydrogen-absorbing metal or a hydrogen-absorbing alloy and has a thickness of less than 1000 nm; and a second layer (not shown), which is formed from a hydrogen-absorbing metal, hydrogen-absorbing alloy, or ceramic different from the first layer and has a thickness of less than 1000 nm. The manufacturing method of the heating element 160 is the same as that of the heating element 90, except that a cylindrical support 161 with openings at both ends is prepared, so the description is omitted. Furthermore, in FIG. 21, the heating element 160 is formed into a cylindrical shape with openings at both ends, but it can also be formed into a corner tube shape with openings at both ends. Also, in the above-described ninth variation, a configuration in which multiple layers of the laminate 160a are stacked is shown, but a configuration having only one laminate 160a is also possible.

[0123] As shown in Figure 22, the blast furnace equipment 165 includes a blast furnace hydrogen heating device 166 and a blast furnace 12. The difference between the blast furnace hydrogen heating device 166 and the blast furnace hydrogen heating device 156 in the eighth variation is that the heating element 90 is replaced by a heating element 160.

[0124] The heating element 160 has mounting pipes 97 at both ends. One end of the mounting pipe 97 is connected to the inlet pipe 29. The other end of the mounting pipe 97 is connected to the non-permeable gas recovery pipe 149. That is, one end of the heating element 160 is connected to the inlet pipe 29, and the other end is connected to the non-permeable gas recovery pipe 149. Therefore, the hydrogen heating device 166 for the blast furnace, like the hydrogen heating device 156 for the blast furnace in the eighth variation described above, can recover the non-permeable gas that has not permeated through the heating element 160 from the non-permeable gas recovery pipe 149 in the hydrogen gas introduced into the first chamber 21.

[0125] [10th Variation Example] In the above-described embodiments and variations, hydrogen gas is introduced into the first chamber via an inlet pipeline and discharged from the second chamber via an outlet pipeline, thereby creating a hydrogen pressure difference between the first and second chambers. However, in the tenth variation, instead of using a hydrogen flow pipeline, a hydrogen-absorbing metal or hydrogen-absorbing alloy is used, utilizing the absorption and release of hydrogen to create a hydrogen pressure difference between the first and second chambers. Hereinafter, the hydrogen heating apparatus for a blast furnace in the tenth variation will be described in terms of aspects that differ from the above-described embodiments and variations.

[0126] As shown in Figure 23, the hydrogen heating device 171 for blast furnace includes a heating element 14, a sealed container 173, a first hydrogen absorption and release section 174, a second hydrogen absorption and release section 175, a first temperature sensor 176, a second temperature sensor 177, a first heater 178, a second heater 179, a first pressure gauge 180, a second pressure gauge 181, and a hydrogen pressure control unit 182. The heating element 14 may be configured to have a single stacked body 14a (see Figure 2), or it may be configured to have a plurality of stacked bodies 14a stacked with a predetermined number of stacked layers (see Figure 6). Furthermore, the hydrogen heating device 171 for blast furnace also includes a control unit (not shown) as an output control unit. The control unit, the first temperature sensor 176, the second temperature sensor 177, the first heater 178, and the second heater 179 form a temperature regulation unit (not shown). The temperature control unit adjusts the temperature of the heating element 14 and maintains it at a suitable temperature for heating.

[0127] The sealed container 173 has a first chamber 184 and a second chamber 185 separated by a heating element 14. The first chamber 184 and the second chamber 185 have different hydrogen pressures by switching control using a hydrogen pressure control unit 182. The first chamber 184 is formed by the front side of the heating element 14 and the inner surface of the sealed container 173. The second chamber 185 is formed by the back side of the heating element 14 and the inner surface of the sealed container 173. Although not shown in FIG. 23, an inlet is provided in the sealed container 173, for example, in the first chamber 184 or the second chamber 185, and an inlet pipe for introducing hydrogen gas is connected to the inlet. Similarly, although not shown in FIG. 23, an outlet is provided in the sealed container 173, in the first chamber 184 or the second chamber 185, and an outlet pipe for discharging the hydrogen gas heated by the heating element 14 to the blast furnace is connected to the outlet.

[0128] The first hydrogen storage and release unit 174 is provided in the first chamber 184. The first hydrogen storage and release unit 174 is formed of hydrogen storage metal or hydrogen storage alloy. The first hydrogen storage and release unit 174 performs hydrogen storage and release. The hydrogen storage and release of the first hydrogen storage and release unit 174 is switched sequentially by the hydrogen pressure control unit 182 described below.

[0129] A second hydrogen storage and release unit 175 is provided in the second chamber 185. The second hydrogen storage and release unit 175 is formed of hydrogen storage metal or hydrogen storage alloy. The second hydrogen storage and release unit 175 performs hydrogen storage and release. The hydrogen storage and release of the second hydrogen storage and release unit 175 is switched sequentially by the hydrogen pressure control unit 182 described below.

[0130] A first temperature sensor 176 is disposed in the first hydrogen storage and release section 174 to detect the temperature of the first hydrogen storage and release section 174. A second temperature sensor 177 is disposed in the second hydrogen storage and release section 175 to detect the temperature of the second hydrogen storage and release section 175.

[0131] A first heater 178 is disposed at the first hydrogen absorption and release section 174 and heats the first hydrogen absorption and release section 174. The first heater 178 is electrically connected to a power source 187 and heats up by receiving power from the power source 187. A second heater 179 is disposed at the second hydrogen absorption and release section 175 and heats the second hydrogen absorption and release section 175. The second heater 179 is electrically connected to a power source 188 and heats up by receiving power from the power source 188.

[0132] The first pressure gauge 180 is installed inside the first chamber 184 to detect the hydrogen pressure in the first chamber 184. The second pressure gauge 181 is installed inside the second chamber 185 to detect the hydrogen pressure in the second chamber 185.

[0133] The hydrogen pressure control unit 182 is electrically connected to the first temperature sensor 176, the second temperature sensor 177, the first pressure gauge 180, the second pressure gauge 181, the power supply 187, and the power supply 188.

[0134] The hydrogen pressure control unit 182 controls the temperature of the first hydrogen absorption and release unit 174 based on the temperature detected by the first temperature sensor 176. The hydrogen pressure control unit 182 heats the first hydrogen absorption and release unit 174 to a predetermined temperature by turning on the power supply 187 and adjusting the input power to the first heater 178. Furthermore, the hydrogen pressure control unit 182 cools the first hydrogen absorption and release unit 174 by turning off the power supply 187. Alternatively, a cooling device (not shown) can be used to cool the first hydrogen absorption and release unit 174.

[0135] The hydrogen pressure control unit 182 controls the temperature of the second hydrogen absorption and release unit 175 based on the temperature detected by the second temperature sensor 177. The hydrogen pressure control unit 182 heats the second hydrogen absorption and release unit 175 to a predetermined temperature by turning on the power supply 188 and adjusting the input power to the second heater 179. Furthermore, the hydrogen pressure control unit 182 cools the second hydrogen absorption and release unit 175 by turning off the power supply 188. Alternatively, a cooling device (not shown) can be used to cool the second hydrogen absorption and release unit 175.

[0136] The hydrogen pressure control unit 182 has a first mode in which the hydrogen pressure in the first chamber 184 is higher than the hydrogen pressure in the second chamber 185, and a second mode in which the hydrogen pressure in the second chamber 185 is higher than the hydrogen pressure in the first chamber 184.

[0137] As shown in Figure 24, in the first mode, the hydrogen pressure control unit 182 heats the first hydrogen absorption and release unit 174 by the first heater 178 and cools the second hydrogen absorption and release unit 175. The first hydrogen absorption and release unit 174 releases hydrogen by being heated. The first chamber 184 is pressurized by releasing hydrogen from the first hydrogen absorption and release unit 174. On the other hand, the second hydrogen absorption and release unit 175 absorbs hydrogen by being cooled. The second chamber 185 is depressurized by absorbing hydrogen in the second hydrogen absorption and release unit 175. As a result, the hydrogen pressure in the first chamber 184 is higher than the hydrogen pressure in the second chamber 185. Due to the hydrogen pressure difference generated between the first chamber 184 and the second chamber 185, the hydrogen in the first chamber 184 passes through the heating element 14 and moves to the second chamber 185. The heating element 14 generates excess heat due to the hydrogen passing through.

[0138] As shown in Figure 25, in the second mode, the hydrogen pressure control unit 182 cools the first hydrogen absorption and release unit 174 and heats the second hydrogen absorption and release unit 175 by means of the second heater 179. The first hydrogen absorption and release unit 174 absorbs hydrogen by being cooled. The first chamber 184 is depressurized by hydrogen absorption in the first hydrogen absorption and release unit 174. On the other hand, the second hydrogen absorption and release unit 175 releases hydrogen by being heated. The second chamber 185 is pressurized by releasing hydrogen from the second hydrogen absorption and release unit 175. As a result, the hydrogen pressure in the second chamber 185 is higher than the hydrogen pressure in the first chamber 184. Due to the hydrogen pressure difference generated between the first chamber 184 and the second chamber 185, the hydrogen in the second chamber 185 passes through the heating element 14 and moves to the first chamber 184. The heating element 14 generates excess heat by the hydrogen passing through.

[0139] The hydrogen pressure control unit 182 performs switching control between mode 1 and mode 2. An example of the switching control will be explained. In mode 1, the hydrogen pressure control unit 182 switches to mode 2 when the pressure detected by the first pressure gauge 180 falls below a predetermined threshold. In mode 2, the hydrogen pressure control unit 182 switches to mode 1 when the pressure detected by the second pressure gauge 181 falls below a predetermined pressure. By performing switching control between mode 1 and mode 2, the hydrogen pressure control unit 182 switches the direction in which hydrogen passes through the heating element 14, which has a predetermined number of layers stacked on top of the laminated body 14a, causing the generation of excess heat in the heating element 14 to continue intermittently.

[0140] Therefore, even in this situation, the hydrogen heating device 171 for blast furnaces can heat the hydrogen gas to a specified temperature by setting the number of layers of the heating element 14, thus achieving the same effect as the hydrogen heating device 11 for blast furnaces described above. Furthermore, the hydrogen heating device 171 for blast furnaces can generate a hydrogen pressure difference between the first and second chambers without using a hydrogen flow pipeline, thus enabling miniaturization.

[0141] [Example of Variation 11] In the hydrogen heating device for blast furnace described in the above embodiments and variations, a heating element is used, and multiple heating elements may be used.

[0142] As shown in Figure 26, the blast furnace equipment 190 includes a hydrogen heating device 191 for the blast furnace and a blast furnace 12. The hydrogen heating device 191 includes a plurality of heating elements 14, a sealed container 193 housing the plurality of heating elements 14, and a non-permeable gas recovery pipeline 149. The plurality of heating elements 14 are each formed in a plate shape. The plurality of heating elements 14 are arranged with gaps between them, with their surfaces facing each other. In this example, six heating elements 14 are arranged inside the sealed container 193 (see Figures 26 and 27). A heater 16b with a temperature regulating section (not shown) is provided on the outer periphery of the sealed container 193. The heater 16b heats the plurality of heating elements 14 by receiving electricity from a power source (not shown).

[0143] A plurality of inlet ports 23, a plurality of outlet ports 24, and a plurality of non-permeable gas recovery ports 151 are provided in the sealed container 193. The inlet ports 23 are positioned opposite to the non-permeable gas recovery ports 151. The outlet ports 24 and the non-permeable gas recovery ports 151 are alternately arranged in the arrangement direction of the plurality of heating elements 14. The plurality of inlet ports 23 are connected to the inlet line 29, for example, using a gas inlet branch pipe (not shown). The plurality of outlet ports 24 are connected to the outlet line 30, for example, using a gas inlet branch pipe (not shown).

[0144] The sealed container 193 has a plurality of first chambers 194 and a plurality of second chambers 195 separated by a plurality of heating elements 14. The first chambers 194 and second chambers 195 are separated by gaps between the heating elements 14 facing each other, and are alternately arranged in the arrangement direction of the plurality of heating elements 14. The first chamber 194 has an inlet 23 and a non-permeable gas recovery port 151. The second chamber 195 has an outlet 24. The first chamber 194 is pressurized by introducing hydrogen gas through the inlet line 29. The second chamber 195 is depressurized by discharging hydrogen gas through the outlet line 30. Therefore, the hydrogen pressure in the first chamber 194 is higher than the hydrogen pressure in the second chamber 195.

[0145] As shown in Figure 27, a portion of the hydrogen gas introduced into the first chamber 194 by the hydrogen pressure difference generated between the first chamber 194 and the second chamber 195 passes through the heating element 14, which has a predetermined number of stacked bodies 14a, and moves to the second chamber 195, and is discharged along the discharge line 30. On the other hand, the non-permeable gas in the hydrogen gas introduced into the first chamber 194 that does not pass through the heating element 14 is recovered by the non-permeable gas recovery line 149. Each heating element 14 generates excess heat through the passage of hydrogen gas. Therefore, even for the blast furnace hydrogen heating device 191, similar to the above embodiment, hydrogen gas at a predetermined temperature can be obtained by presetting the number of stacked bodies 14a to a predetermined number. Furthermore, the blast furnace hydrogen heating device 191 can increase the output of excess heat by having a plurality of heating elements 14. Furthermore, in the 11th variation example above, it is shown that the laminate 14a has a plurality of laminates, but it can also have a single laminate 14a.

[0146] Furthermore, in the 11th variation described above, the non-permeable gas that does not pass through the heating element 14 is recovered using the non-permeable gas recovery line 149 and returned to the inlet line 29, thereby circulating the non-permeable gas. However, the present invention is not limited to this, and it can also be configured as a hydrogen heating device for a blast furnace without the non-permeable gas recovery line 149 and without circulating the non-permeable gas. In this case, the first chamber 194 is configured such that the non-permeable gas recovery port 151 is not provided at the position opposite to the inlet port 23, but only the inlet port 23 is provided.

[0147] Furthermore, the hydrogen gas introduced into the first chamber 194 moves to the second chamber 195 through the heating element 14 and is discharged along the outlet pipe 30. The hydrogen gas moves to the second chamber 195 by passing through each of the stacked bodies 14a of the heating element 14, generating excess heat in each stacked body 14a, and being heated by the excess heat generated in these stacked bodies 14a. Therefore, even for this hydrogen heating device for a blast furnace, similar to the 11th variation described above, hydrogen gas at a specified temperature can be obtained by presetting the number of stacked bodies 14a to a specified quantity.

[0148] Furthermore, in the 11th variation described above, the case of having a plurality of plate-shaped heating elements 14 was described. However, the present invention is not limited to this. For example, it can also be configured as a hydrogen heating device for a blast furnace having a plurality of bottomed cylindrical heating elements 90 as shown in FIG14 and FIG20, or heating elements 98 as shown in FIG16, or cylindrical heating elements 160 as shown in FIG21. Alternatively, it can also be configured as a hydrogen heating device for a blast furnace having a plurality of heating elements of different types, such as bottomed cylindrical heating elements 90 or cylindrical heating elements 160.

[0149] Furthermore, when multiple heating elements 14, 90, 98, and / or 160 are installed inside a sealed container, the temperature of each heating element can be independently adjusted within the sealed container. For example, when multiple heating elements 90 are installed inside a sealed container, one temperature sensor and heater are installed for each heating element 90. That is, the temperature of one heating element 90 is detected by one temperature sensor. The multiple temperature sensors are electrically connected to the control unit 18, and output signals corresponding to the detected temperatures of each heating element 90 to the control unit 18. The control unit 18 independently controls the output of each heater based on the temperature detected by each temperature sensor. Therefore, in this type of hydrogen heating device for blast furnaces, because the temperature of each heating element 90 is independently adjusted, the multiple heating elements 90 are maintained at a suitable temperature for heating, thus stabilizing the output of excess heat.

[0150] Furthermore, when multiple heating elements 14, 90, 98, and / or 160 are provided, the heating elements can be placed in different sealed containers. Moreover, a flow regulating valve can be provided for each heating element or each sealed container to control the flow rate of hydrogen gas introduced into each heating element.

[0151] Alternatively, samples of the hydrogen gas that has passed through the heating element can be taken and analyzed, and heating control can be performed based on the analysis results. For example, as shown in Figure 15, an example is given where one heating element 90 is installed in one sealed container 15. In this case, a plurality of sealed containers 15 are provided, each containing a heating element 90. Furthermore, an analysis unit is provided in each sealed container 15 containing the heating element 90, and for each sealed container 15, samples of the hydrogen gas that has passed through the heating element 90 are taken and analyzed by the analysis unit.

[0152] The analysis unit analyzes the hydrogen-based gas passing through the heating element 90 to determine, for example, whether the hydrogen-based gas contains a unique generated gas produced by the heating reaction of the heating element 90. For this type of hydrogen heating device for a blast furnace, the control unit 18 can adjust the flow rate of the hydrogen-based gas for each sealed container 15 based on the analysis results, thereby maintaining the temperature of the heating element 90 at a suitable heating temperature through heating control.

[0153] Furthermore, in addition to this, the resistance of the hydrogen-absorbing metal or hydrogen-absorbing alloy can also be measured, and heating control can be performed based on the measured resistance value. For example, taking a case with multiple heating elements 90 as an example, in this case, a resistance measuring unit is provided for each heating element 90, and the resistance of the hydrogen-absorbing metal or hydrogen-absorbing alloy of the heating element 90 is measured by the resistance measuring unit. Here, the heating element 90 is configured such that the more hydrogen absorbed by the hydrogen-absorbing metal or hydrogen-absorbing alloy, the easier it is to generate a heating reaction. Also, the more hydrogen absorbed by the hydrogen-absorbing metal or hydrogen-absorbing alloy of the heating element 90, the lower its resistance. Therefore, by measuring the resistance of the hydrogen-absorbing metal or hydrogen-absorbing alloy of the heating element 90, the amount of hydrogen absorbed can be estimated. The multiple resistance measuring units are electrically connected to the control unit 18, and the resistance measurement results are output to the control unit 18.

[0154] The control unit 18 is capable of heat control. This heat control is based on the resistance value measured by the resistance measuring unit, and adjusts the circulation flow rate of hydrogen gas for each heating element 90, thereby maintaining the temperature of the heating element 90 at a suitable temperature for heating.

[0155] [Example of Variation #12] As shown in Figure 28, the hydrogen heating device 256 for the blast furnace includes a heating element 14, a plurality of temperature sensors 257a-257c for detecting the temperature of the heating element 14, and a plurality of nozzles 258a-258c for injecting hydrogen gas into the front of the heating element 14. Furthermore, regarding other components such as the blast furnace connected to the outlet pipeline 30, descriptions are omitted here due to repetition. The following description focuses on configurations different from the above-described embodiments or variations.

[0156] In this example, hydrogen gas is injected from a plurality of nozzles 258a-258c into a single heating element 14. Furthermore, in Figure 28, as an example, three temperature sensors 257a-257c and three nozzles 258a-258c are shown. However, in practice, the temperature sensors 257a-257c and the nozzles 258a-258c are ideally arranged in an array, such as in three columns and three rows.

[0157] In this configuration, temperature sensors 257a-257c are arranged in a two-dimensional pattern at equal intervals on the back surface of the heating element 14. A temperature measurement target area is defined for the heating element 14, and the temperature of each temperature measurement target area corresponding to each of the temperature sensors 257a-257c is detected. This temperature measurement target area is defined for each of the temperature sensors 257a-257c, and its temperature can be detected by the temperature sensor. For example, temperature sensor 257a detects the temperature of one defined temperature measurement target area on the back surface of the heating element 14. In the following description, when not distinguishing between temperature sensors 257a-257c, they will be referred to as temperature sensor 257.

[0158] The plurality of nozzle sections 258a to 258c are configured for each temperature measurement target area. In the following description, when the nozzle sections 258a to 258c are not distinguished, they will be referred to as nozzle section 258.

[0159] Temperature sensor 257 is electrically connected to control unit 18, and outputs a signal corresponding to the temperature of the area to be measured to control unit 18. Nozzle 258 is mounted on mounting plate 259, which is located at inlet 23 of sealed container 15. Nozzle 258 is connected to inlet line 29 via inlet 23, and sprays hydrogen gas onto the front of heating element 14.

[0160] The blast furnace hydrogen heating device 256 further includes a control unit 18, a gas inlet branch pipe 208, and a plurality of flow regulating valves 237. The gas inlet branch pipe 208 is connected at one end to the inlet line 29, and branches off at the other end to connect to a plurality of nozzle sections 258. The gas inlet branch pipe 208 and the plurality of nozzle sections 258 are easily detachable. A plurality of flow regulating valves 237 are provided on the gas inlet branch pipe 208. By providing one flow regulating valve 237 for each nozzle section 258, the blast furnace hydrogen heating device 256 can control the flow rate of hydrogen gas for each nozzle section 258.

[0161] The control unit 18 performs change control on the nozzle 258 that injects hydrogen gas based on the temperature detected by the plurality of temperature sensors 257. The change control will be explained below.

[0162] When the hydrogen heating device 256 for the blast furnace starts operating, the control unit 18 sets the input power to the heater (not shown) and the opening of all flow regulating valves 237 to predetermined initial settings. This causes the temperature of the heating element 14 to rise to a suitable temperature for heating. At the initial settings, hydrogen gas is injected from all nozzles 258. Furthermore, the heater (not shown) is, for example, installed on the outer periphery of the sealed container 15 as in the hydrogen heating device 11 for the blast furnace described above.

[0163] The control unit 18 acquires the temperatures detected by each temperature sensor 257 and compares each acquired temperature with a reference temperature. The reference temperature is, for example, a temperature at which no excess heat is generated in the temperature measurement target area. The reference temperature is pre-memorized in the control unit 18 for each temperature measurement target area.

[0164] When the temperature obtained from the temperature sensor 257 is below the reference temperature, the control unit 18 determines that no excess heat has been generated in the temperature measurement target area where the temperature has been acquired. The control unit 18 maintains the input power to the heater (not shown) and the opening of the flow regulating valve 237 corresponding to the temperature measurement target area where no excess heat has been generated at the initial setting value. In this way, the generation of excess heat in the temperature measurement target area of ​​the heating element 14 where no excess heat has been generated can be promoted.

[0165] On the other hand, when the temperature obtained from the temperature sensor 257 exceeds the reference temperature, the control unit 18 determines that excess heat has been generated in the temperature measurement target area where the temperature has been acquired. The control unit 18 increases the opening of the flow adjustment valve 237 corresponding to the temperature measurement target area where excess heat is determined to be generated, thereby increasing the flow rate of the hydrogen gas injected from the nozzle 258 into the temperature measurement target area. The temperature of the temperature measurement target area, which has risen due to excess heat, is restored to a suitable temperature for heating by increasing the flow rate of the hydrogen gas. In this way, the output of excess heat can be increased for the temperature measurement target area where excess heat is generated.

[0166] The hydrogen heating device 256 for blast furnace can stabilize the output of excess heat from the heating element 14 by changing the nozzle 258 of the hydrogen gas injection according to the heating status of the heating element 14 as time goes by, by changing the control for each of the plurality of temperature measurement target areas.

[0167] Furthermore, the hydrogen heating device 256 for blast furnace can also control the heating of temperature measurement areas that do not generate excess heat and temperature measurement areas that generate excess heat. In this way, the number of temperature measurement areas that generate excess heat can be increased, thereby increasing the output of excess heat of the entire heating element 14 and the entire device.

[0168] The hydrogen heating device 256 for blast furnace can also have a plurality of heating elements 14. By changing the control of each heating element 14, the output of excess heat of the entire device can be further increased.

[0169] [experiment] A hydrogen heating device for a blast furnace for testing was prepared by modifying part of the configuration of the hydrogen heating device 121 for a blast furnace in the sixth variation described above (see Figure 17). An experiment was conducted using the experimental hydrogen heating device for a blast furnace to evaluate the excess heat of a heating element comprising a single layer. First, the experimental hydrogen heating device for a blast furnace will be described, and then the experimental method and experimental results will be explained.

[0170] In the hydrogen heating device 121 for blast furnace described in the sixth variation above, an electric heating wire serving as a heater 16b is wound around the outer periphery of the mounting tube 125. However, in the experimental hydrogen heating device for blast furnace, the electric furnace is arranged to cover the outer periphery of the sealed container. Furthermore, in the experimental hydrogen heating device for blast furnace, a heating element comprising a multilayer body having multiple films disposed on both sides of the support is used.

[0171] The experimental hydrogen heating device for a blast furnace is described in detail. The experimental hydrogen heating device for a blast furnace includes: a heating element that generates heat by the absorption and release of hydrogen, and includes a laminate; a sealed container having a first chamber and a second chamber separated by the heating element; and a temperature regulating unit that regulates the temperature of the heating element.

[0172] The heating element is described below. The heating system consists of only one multilayer body, on which multiple films are deposited on both sides of a plate-shaped support. Two heating elements with different compositions of the multilayer films in the multilayer body are fabricated, and are designated as Experimental Example 26 and Experimental Example 27. As the support, a substrate containing Ni with a diameter of 20 mm and a thickness of 0.1 mm is used. Regarding the support, it is prepared by vacuum annealing at 900°C for 72 hours in a vacuum followed by etching of both sides using concentrated nitric acid.

[0173] A multilayer film was formed on both sides of a support using an ion beam sputtering apparatus. The multilayer film of Example 26 has a first layer containing Cu and a second layer containing Ni. The number of layers (number of layers in the multilayer film) of the first and second layers in Example 26 was set to 6. The multilayer film of Example 27 has a first layer containing Cu, a second layer containing Ni, and a third layer containing CaO. The number of layers (number of layers in the multilayer film) of the first, second, and third layers in Example 27 was set to 6.

[0174] The sealed container is described below. The sealed container includes a quartz glass tube, vacuum piping for venting the interior of the quartz glass tube, and a mounting tube for housing a heating element inside the quartz glass tube. The quartz glass tube is closed at one end and open at the other.

[0175] The vacuum piping is connected to the base of the quartz glass tube. A recovery line is connected to the vacuum piping to recover the gas inside the quartz glass tube. Here, a configuration is established where hydrogen-based gases exiting from the sealed container are recovered via the recovery line and returned to the sealed container to confirm whether the self-heating element generates excess heat. The recovery line is equipped with a vacuum exhaust section containing a turbomolecular pump and a dry pump, a pressure sensor to detect the pressure inside the quartz glass tube, and a vacuum gauge to measure the amount of hydrogen permeating through the heating element (hydrogen permeation). Furthermore, the vacuum exhaust section is not connected to the mounting tube. Therefore, the interior of the mounting tube is not vacuumed.

[0176] The mounting tube is inserted into the quartz glass tube via a vacuum piping system, with one end positioned outside the vacuum piping (outside the quartz glass tube) and the other end positioned inside the quartz glass tube. The mounting tube is made of SUS (Solid Metal Sulfate).

[0177] One end of the installation pipe is connected to an inlet line for introducing hydrogen gas into the interior of the installation pipe. The inlet line is equipped with a hydrogen storage tank for storing hydrogen gas, a pressure sensor for detecting the pressure inside the installation pipe, a hydrogen supply valve for supplying and stopping the hydrogen gas into the installation pipe, and a regulating valve for adjusting the pressure.

[0178] A VCR (Vacuum Coupling Radius Seal) connector is provided at the other end of the mounting tube to allow the heating element to be installed and removed. The VCR connector has two holes penetrating the inner and outer circumferential surfaces at the location where the heating element is placed. The heating system is disposed inside the VCR connector, sandwiched between two SUS gaskets.

[0179] Within a sealed container, a heating element separates the internal space of a mounting tube from the internal space of a quartz glass tube. The internal space of the mounting tube is pressurized by introducing hydrogen gas. The internal space of the quartz glass tube is depressurized by venting the gas through a vacuum. Thus, the hydrogen pressure inside the mounting tube is higher than the hydrogen pressure inside the quartz glass tube. The internal space of the mounting tube functions as the first chamber, and the internal space of the quartz glass tube functions as the second chamber.

[0180] A pressure difference is generated on both sides of the heating element, allowing hydrogen to pass through from the internal space of the mounting tube (high pressure side) to the internal space of the quartz glass tube (low pressure side). As described above, during the process of hydrogen passage, the heating system generates heat by absorbing hydrogen on one side (front) of the high pressure side and by releasing hydrogen on the other side (back) of the low pressure side.

[0181] The temperature control unit is described below. It includes a temperature sensor for detecting the temperature of the heating element, a heater for heating the heating element, and an output control unit for controlling the output of the heater based on the temperature detected by the temperature sensor. A thermocouple (K-type sheathed thermocouple) is used as the temperature sensor. Two thermocouples (the first thermocouple and the second thermocouple) are prepared for the experiment and inserted into each of the two holes of the VCR connector. The two thermocouples are brought into contact with the heating element, and the temperature of the heating element is measured. An electric furnace is used as the heater. The electric furnace is configured to cover the outer periphery of a quartz glass tube. A control thermocouple is installed on the electric furnace. The output control unit is electrically connected to the control thermocouple and the electric furnace, and drives the electric furnace at a specified voltage based on the temperature detected by the control thermocouple. The electric furnace is driven by a 100V AC power supply. A power meter is used to measure the input power to the electric furnace.

[0182] Next, the experimental methods and results will be explained. The heating element was sandwiched between two SUS gaskets, fixed to the other end of the mounting tube using a VCR connector, and placed inside the quartz glass tube. Before starting the experiment, the heating element was baked at 300°C for 3 days.

[0183] The experiment began after the aforementioned baking. Hydrogen gas was supplied to the mounting tube by opening the hydrogen supply valve, and the pressure in chamber 1 (the internal space of the mounting tube) (also known as the hydrogen supply pressure) was adjusted to 100 kPa using the regulating valve. Vacuum venting was performed on the quartz glass tube, and the pressure in chamber 2 (the internal space of the quartz glass tube) was adjusted to 1 × 10⁻⁴ Pa. The electric furnace was driven to heat the heating element at a predetermined set temperature. The set temperature was changed approximately every half day, gradually increasing in stages within the range of 300°C to 900°C.

[0184] A reference experiment was conducted prior to the experiments in Examples 26 and 27. In the reference experiment, a reference sample consisting only of a support body (a Ni substrate with a diameter of 20 mm and a thickness of 0.1 mm) was fabricated and used. The reference experiment was performed twice by changing the reference sample.

[0185] Figure 29 is a graph showing the relationship between hydrogen permeation rate, hydrogen supply pressure, and sample temperature in the reference experiment. In Figure 29, the horizontal axis represents time (h), the first vertical axis on the left represents hydrogen permeation rate (SCCM), and the second vertical axis on the right represents hydrogen supply pressure (kPa), the temperature of the first sample (°C), and the temperature of the second sample (°C). The hydrogen permeation rate was calculated based on the value of a vacuum gauge with flow rate calibration. The temperature of the first sample is the detection temperature of the first thermocouple, and the temperature of the second sample is the detection temperature of the second thermocouple. According to Figure 29, it can be confirmed that the temperatures of the first and second samples are approximately the same, and the temperature of the sample used in the reference experiment can be accurately measured. Furthermore, it can also be confirmed that the hydrogen permeation rate increases as the temperature of the sample used in the reference experiment rises. Moreover, Figure 29 shows the results of the first reference experiment. The results of the second reference experiment are approximately the same as those of the first reference experiment, so they are omitted from the description.

[0186] Figure 30 is a graph showing the relationship between sample temperature and input power in the reference experiment. In Figure 30, the horizontal axis represents sample temperature (°C), and the vertical axis represents input power (W). Input power refers to the power supplied to the electric furnace. Due to the large fluctuations in the galvanometer readings caused by the switching on / off control of the AC power supply, the measured values ​​are accumulated for each set temperature, and the input power is calculated based on the slope. The calculation of input power is performed after the set temperature change, within the region where the galvanometer readings stabilize after a sufficient period of time. For each of these regions, the average value of the detection temperature of the first thermocouple and the average value of the detection temperature of the second thermocouple are calculated, and the average of these two average values ​​is taken as the sample temperature. Figure 30 is a plot of the results of two reference experiments, and is a calibration curve produced using the least squares method. In Figure 30, Y represents the function representing the calibration curve, M0 represents the constant term, M1 represents the coefficient of the first order, M2 represents the coefficient of the second order, and R represents the correlation coefficient. Based on the results of the reference experiment, the excess heat of Experiment 26 and Experiment 27 was evaluated.

[0187] Figure 31 is a graph showing the relationship between the temperature of the heating element and the excess heat in Experiment Example 26. In Figure 31, the horizontal axis represents the temperature of the heating element (°C), and the vertical axis represents the excess heat (W). The average values ​​of the measured temperatures of the first thermocouple and the second thermocouple were calculated using the same method as for the sample temperature in the reference experiment. The average of these two average values ​​was taken as the heating element temperature. The method for calculating the excess heat is explained below. First, the temperature of the heating element under a specific input power was measured (called the measured temperature). Second, using the calibration curve shown in Figure 30, the input power of the reference experiment corresponding to the measured temperature was calculated (called the converted power). Then, the difference between the converted power and the specific input power was calculated, and this was taken as the power of the excess heat. Furthermore, the specific input power was calculated using the same method as for the input power in the reference experiment. In Figure 31, the power of the excess heat is denoted as "excess heat (W)". Figure 31 confirms that excess heat is generated when the temperature of the heating element is between 300°C and 900°C. It can be confirmed that the excess heat is at most about 2 W below 600°C, increases above 700°C, and becomes about 10 W near 800°C.

[0188] Figure 32 is a graph showing the relationship between the temperature of the heating element and the excess heat in Experiment 27. In Figure 32, the horizontal axis represents the temperature of the heating element (°C), and the vertical axis represents the excess heat (W). According to Figure 32, it can be confirmed that excess heat is generated when the temperature of the heating element is in the range of 200°C to 900°C. It can be confirmed that the excess heat is at most about 4 W in the range of 200°C to 600°C, increases above 700°C, and exceeds 20 W near 800°C.

[0189] Comparing Experimental Example 26 and Experimental Example 27, it can be seen that Experimental Example 27 tends to generate more excess heat below 600℃. Both Experimental Example 26 and Experimental Example 27 show a tendency for excess heat to increase above 700℃. It can be seen that above 700℃, the excess heat of Experimental Example 27 increases to approximately twice that of Experimental Example 26.

[0190] If we calculate the excess heat per unit area near 800°C for Experiment 11 (see Figure 12), Experiment 26 (see Figure 31), and Experiment 27 (see Figure 32), it is approximately 0.5 W / cm² in Experiment 11, approximately 5 W / cm² in Experiment 26, and approximately 10 W / cm² in Experiment 27. Based on this result, it can be seen that Experiment 26 generates approximately 10 times the excess heat compared to Experiment 11, and Experiment 27 generates approximately 20 times the excess heat.

[0191] As can be seen from the above, even a heating element consisting of only one layer generates excess heat, which can then be used to heat hydrogen-based gases. Furthermore, the more layers a heating element has, the thicker it becomes, and the longer the distance the hydrogen-based gas travels through it. Therefore, the heating time also increases accordingly. The more layers a heating element has, the higher the temperature of the hydrogen-based gas after passing through the heating element. Therefore, it can be concluded that by adjusting the number of layers, the temperature of the hydrogen-based gas being heated can be adjusted.

[0192] [Second Implementation] The second embodiment is configured such that the partial pressure of hydrogen in the gas introduced into the first chamber is different from the partial pressure of hydrogen in the gas introduced into the second chamber. The hydrogen is passed through the heating element by utilizing the pressure difference between the hydrogen in the first and second chambers. In the second embodiment, "hydrogen pressure" refers to "hydrogen partial pressure".

[0193] As shown in Figure 33, the blast furnace equipment 265 includes a hydrogen heating device 266 for the blast furnace and a blast furnace 12. The hydrogen heating device 266 for the blast furnace includes: a heating element 268, which generates heat by absorbing and releasing hydrogen; a sealed container 271, which has a first chamber 269 and a second chamber 270 separated by the heating element 268; and a temperature regulating unit 272, which regulates the temperature of the heating element 268. Furthermore, the structure separating the first chamber 269 and the second chamber 270 is not limited to being composed solely of the heating element 268; it can also be a structure in which part is the heating element 268 and the other part is a wall structure made of metal or oxide to shield hydrogen.

[0194] The heating element 268 is formed into a bottomed cylindrical shape. The heating element 268 can, for example, be configured the same as the heating element 90 shown in FIG. 14, with a predetermined number of laminated bodies 90a. That is, the heating element 268 is formed by laminating a predetermined number of laminated bodies on the outer surface of a bottomed cylindrical support, with the support and the multilayer film alternately arranged from the inside to the outside. Furthermore, the multilayer film can be provided on the inner surface of the support, with the multilayer film and support alternately arranged from the inside to the outside, or the multilayer film can be provided on both the inner and outer surfaces of the innermost support. Also, in this embodiment, a configuration with multiple laminated bodies 90a is shown, but a configuration with only one laminated body 90a is also possible.

[0195] The support is not limited to a bottomed cylindrical shape; it can also be a bottomed corner cylindrical shape or a flat plate shape. Preferably, the support is made of a material that allows hydrogen permeability and has heat and pressure resistance; for example, it can be formed from the same material as support 61. The multilayer film can, for example, have the same structure as multilayer film 62. In this example, there is one heating element 268, but there can also be two or more.

[0196] The sealed container 271 is a hollow container that houses the heating element 268. The sealed container 271 is preferably made of a material with heat resistance and pressure resistance. Materials for the sealed container 271 include, for example, metals or ceramics. Examples of metals include Ni, Cu, Ti, carbon steel, ferrosilicon stainless steel, heat-resistant non-ferrous alloy steel, and ceramics. Examples of ceramics include Al₂O₃, SiO₂, SiC, and ZnO₂. Ideally, the outer periphery of the sealed container 271 is covered with insulation material. In this example, there is one sealed container 271 housing the heating element 268, but two or more may also be used.

[0197] The first chamber 269 is formed on the inner surface of the heating element 268. The first chamber 269 has an inlet 274 connected to the hydrogen inlet line 273. A hydrogen tank 275 for storing hydrogen-based gas is provided in the hydrogen inlet line 273. Hydrogen-based gas flowing along the hydrogen inlet line 273 is introduced into the first chamber 269 through the inlet 274.

[0198] The second chamber 270 is formed by the outer surface of the heating element 268 and the inner surface of the sealed container 271. The second chamber 270 has an inlet 277 connected to the hydrogen tank 280 and an outlet 278 connected to the outlet pipeline 276. Hydrogen gas from the hydrogen tank 280 is introduced into the second chamber 270 (sealed container 271) through the inlet 277 by a circulating blower 279. The outlet pipeline 276 is connected to the blast furnace 12.

[0199] The partial pressure of hydrogen in the hydrogen-based gas introduced into chamber 1 269 and the partial pressure of hydrogen in the hydrogen-based gas introduced into chamber 270 are measured by a hydrogen sensor (not shown). Ideally, the partial pressure of hydrogen in chamber 1 269 is set to, for example, 10 to 10,000 times that of the partial pressure of hydrogen in chamber 270. As an example, the partial pressure of hydrogen in chamber 1 269 is set to 10 kPa to 1 MPa, and the partial pressure of hydrogen in chamber 270 is set to 1 Pa to 10 kPa. In this way, hydrogen in chamber 1 269 passes through heating element 268 and moves to chamber 270. Excess heat is generated in heating element 268 by the hydrogen permeation. By circulating heat medium to chamber 270, the excess heat of heating element 268 can be transferred to heat medium, and the partial pressure of hydrogen in chamber 270 can be lower than that of hydrogen in chamber 1 269.

[0200] The hydrogen heating device 266 for the blast furnace is configured to have a control unit (not shown) that controls the hydrogen partial pressure of the first chamber 269 and the hydrogen partial pressure of the second chamber 270. For example, by increasing the hydrogen partial pressure of the first chamber 269, the difference between the hydrogen partial pressures of the first chamber 269 and the second chamber 270 is increased, thereby increasing the hydrogen permeation and promoting the generation of excess heat in the heating element 268. Conversely, by decreasing the hydrogen partial pressure of the first chamber 269, the difference between the hydrogen partial pressures of the first chamber 269 and the second chamber 270 is decreased, thereby reducing the hydrogen permeation and suppressing the generation of excess heat in the heating element 268. Alternatively, the hydrogen partial pressure of the second chamber 270 can be decreased or increased instead of changing the hydrogen partial pressure of the first chamber 269, thereby promoting or suppressing the generation of excess heat in the heating element 268. The hydrogen partial pressures of the first chamber 269 and the second chamber 270 can also be varied. Furthermore, the excess heat generated by the heating element 268 can also be adjusted by changing the flow rate or temperature of the hydrogen gas at the inlet 277.

[0201] The temperature control unit 272 includes: a temperature sensor 281 that detects the temperature of the heating element 268; a heater 282 that heats the heating element 268; and an output control unit 283 that controls the output of the heater 282 based on the temperature detected by the temperature sensor 281. In Figure 33, the temperature sensor 281 is disposed on the outer surface of the heating element 268, but it can also detect the temperature of a portion that can be used to estimate the temperature of the heating element 268. The heater 282 operates when the blast furnace hydrogen heating device 266 starts operating or when the temperature of the heating element 268 decreases. The heater 282 heats hydrogen gas from the hydrogen tank 280 and introduces the heated hydrogen gas into the second chamber 270 to heat the heating element 268.

[0202] The hydrogen heating device 266 for blast furnace can generate excess heat from the self-heating element 268 and transport the hydrogen gas heated by the heating element 268 to the blast furnace 12 via the outlet pipeline 276, where it is used as a reducing gas.

[0203] As described above, the hydrogen heating device 266 for blast furnaces is configured to raise the temperature of hydrogen-based gases to a predetermined temperature. Furthermore, it is configured to allow hydrogen to pass through the heating element 268 by utilizing the hydrogen partial pressure difference between the first chamber 269 and the second chamber 270. Therefore, in the hydrogen heating device 266 for blast furnaces, in addition to achieving the same effects as the embodiment described above, for example, it is not necessary to set the second chamber 270 to a vacuum state to generate an apparent pressure difference between the first chamber 269 and the second chamber 270 that can be obtained using a pressure sensor. Therefore, the risk of deformation or damage to the hydrogen heating device 266 for blast furnaces is reduced.

[0204] The hydrogen heating device 266 for blast furnaces of this embodiment can heat hydrogen-based gases without consuming a large amount of energy, and therefore, correspondingly, can suppress the amount of CO2 produced. Therefore, the hydrogen heating device for blast furnaces uses hydrogen-based gases heated in this way as reducing gases in the blast furnace during operation, and even when hydrogen-based gases are used as reducing gases in the blast furnace, the amount of CO2 produced can be suppressed.

[0205] [Third Implementation] In the first and second embodiments described above, a hydrogen heating device for a blast furnace was described. This device is configured to have a first chamber and a second chamber inside a sealed container, through which hydrogen gas flows from the first chamber to the second chamber via a heating element. The hydrogen gas passes through the heating element, and the excess heat generated in the heating element heats the hydrogen gas. However, the present invention is not limited to this. For example, as shown in FIG34, a hydrogen heating device 301 for a blast furnace can also be described. This device is configured not to have a first chamber and a second chamber inside a sealed container 302, but to generate excess heat in a heating element 14 inside the sealed container 302. The temperature of the hydrogen gas is adjusted by adjusting the number of layers of the stacked body disposed in the heating element.

[0206] Figure 34 shows a schematic diagram of the hydrogen heating device 301 for a blast furnace according to the third embodiment. In this case, the blast furnace equipment 300 includes the hydrogen heating device 301 for a blast furnace and the blast furnace 12. The hydrogen heating device 301 for a blast furnace includes: a sealed container 302 into which hydrogen gas is introduced; a heating structure 303 disposed inside the sealed container 302; and a temperature regulating unit 320 that regulates the temperature of the heating element 14 of the heating structure 303. The hydrogen heating device 301 for a blast furnace is similar to that in the first embodiment described above. After the hydrogen gas is introduced into the sealed container 302, the heating element 14 is heated in the heating structure 303 by the temperature regulating unit 320, thereby generating excess heat in the heating element 14. Furthermore, since the structure of the heating element 14 is the same as that in the first embodiment described above, its description is omitted here to avoid repetition.

[0207] The sealed container 302 is made of materials such as stainless steel (SUS306 or SUS316). 302a is a window made of a transparent component such as Kovar glass, which maintains the seal within the sealed container 302 and allows operators to directly visually inspect the interior. An inlet line 316 is provided in the sealed container 302, through which hydrogen gas is introduced into the sealed container 302 via regulating valves 317a and 317b. Subsequently, the introduction of hydrogen gas from the inlet line 316 is stopped by regulating valves 317a and 317b, storing a fixed amount of hydrogen gas inside the sealed container 302. Furthermore, 319 is a dry pump, which can, as needed, discharge the gas inside the sealed container 302 to the outside via the outlet line 318 and regulating valve 317c for vacuum venting or pressure adjustment.

[0208] The temperature regulating unit 320 regulates the temperature of the heating element 14 and maintains it at a suitable temperature for heating. For example, the suitable temperature for heating the heating element 14 is in the range of 50°C to 1000°C. The temperature regulating unit 320 includes temperature sensors 311a, 311b, 312a, 312b, and 312c, and a heater (not shown) for heating the heating element 14.

[0209] In this embodiment, temperature sensors 311a and 311b are disposed along the inner wall of the sealed container 302 to measure the temperature of the inner wall. Other temperature sensors 312a to 312c are disposed in the holder 304 that holds the heating element 14 in the heating structure 303 to measure the temperature in the holder 304. Furthermore, the lengths of the temperature sensors 312a to 312c are different, for example, measuring the temperature of various parts of the holder 304, including the lower layer near the heating element 14, the upper layer away from the heating element 14, and the middle layer located between the lower and upper layers.

[0210] Temperature sensors 311a, 311b, 312a, 312b, and 312c are electrically connected to a control unit 18 (not shown) and output a signal corresponding to the detected temperature to the control unit.

[0211] The heater for the heating element 14 is, for example, a resistance heating type electric heating wire wound around the outer periphery of the sealed container 302, or disposed on the holder 304. The heater is electrically connected to the power supply 313 and heats up by receiving electricity from the power supply 313. Alternatively, the heater can also be an electric furnace arranged to cover the outer periphery of the sealed container 302. Furthermore, a heater can also be installed in the inlet pipe 316, thereby heating the heating element 14 by heating the hydrogen gas flowing along the inlet pipe 316.

[0212] In this embodiment, for example, a heater is provided in the holder 304, and the heater is connected to the power supply 313 via wiring 310a and 310b. 314 is a current and voltmeter provided in wiring 310a and 310b, which can measure the input current and input power applied to the heater when it is heated.

[0213] Next, the heating structure 303 will be described. As shown in FIG35, the heating structure 303 has a retainer 304 including a pair of retainer halves 304a and 304b, and a heating element 14 formed by stacking a plurality of laminated bodies 14a formed of a support body 61 and a multilayer film 62 is sandwiched between the retainer halves 304a and 304b. Furthermore, although the heater is not shown, it is, for example, a plate-shaped ceramic heater, and is provided at a predetermined position in the retainer 304. Alternatively, the heater and the heating element 14 may be sandwiched together between the retainer halves 304a and 304b.

[0214] One of the retainer halves 304a constituting the retainer 304 is formed of ceramic in a rectangular shape, and has an opening 309a formed at a predetermined position. A heating element 14 is disposed in the opening 309a of the retainer halves 304a, and the heating element 14 is exposed from the area of ​​the opening 309a. The other retainer halves 304b are similarly formed of ceramic in a rectangular shape, like the retainer halves 304a. When the other retainer halves 304b overlaps with and is integral with the retainer halves 304a, an opening 309b is provided at the position where it overlaps with the opening 309a of the retainer halves 304a.

[0215] A stepped portion 309c is provided around the opening 309b of the contact surface 309d that abuts against the retainer half 304a in another retainer half 304b. A heating element 14 is embedded and positioned in the stepped portion 309c. Thus, the heating element 14 is positioned in the opening 309b by the other retainer half 304b being embedded in the stepped portion 309c, and the heating element 14 is exposed from the area of ​​the opening 309b. The heating element 14 embedded in the stepped portion 309c is contained within the stepped portion 309c by the contact surface around the opening 309a in one retainer half 304a when the retainer halves 304a and 304b overlap, thereby being internally housed within the retainer 304.

[0216] As described above, the hydrogen heating device 301 for blast furnace in the third embodiment is similar to that in the first embodiment, absorbing and releasing hydrogen in the heating element 14. Heat is generated by absorbing hydrogen in the heating element 14 and by releasing hydrogen, thereby producing excess heat. The hydrogen-based gas is heated in the heating element 14 by the excess heat generated therein. The thicker the heating element 14, the easier it is for the hydrogen-based gas to be heated by the excess heat generated in the heating element 14, thus increasing the temperature of the hydrogen-based gas.

[0217] Therefore, the hydrogen heating device 301 for blast furnace, like the first embodiment described above, is capable of obtaining hydrogen gas at a specified temperature. Thus, in the hydrogen heating device 301 for blast furnace, a heating element that generates heat through the absorption and release of hydrogen is used to heat the hydrogen gas, enabling the supply of hydrogen gas heated using a low-cost, clean, and safe heat source as a reducing gas to the blast furnace 12.

[0218] In this embodiment, it is shown that the laminate 14a has a plurality of laminates, but it may also have a single laminate 14a.

[0219] The hydrogen heating device for blast furnaces of this embodiment can heat hydrogen-based gases without consuming a large amount of energy, and therefore, can suppress the production of CO2. Thus, the hydrogen heating device for blast furnaces uses hydrogen-based gases heated in this manner as reducing gases in the blast furnace during operation, and even when using hydrogen-based gases as reducing gases in the blast furnace, the production of CO2 can be suppressed.

[0220] Furthermore, the heating element is not limited to being formed in the form of a plate or a cylinder. For example, each layer of the heating element can also be formed by containing powder formed of hydrogen-absorbing metal or hydrogen-absorbing alloy in a container formed of a hydrogen-permeable material (e.g., a porous material, a hydrogen-permeable membrane, and a proton conductor).

[0221] The hydrogen heating device for blast furnaces is not limited to the embodiments and variations described above. It can also be constructed by appropriately combining the hydrogen heating devices for blast furnaces described in the embodiments and variations above. For example, a pump 33 can be installed in the inlet pipeline 29 to set a predetermined pressure in the sealed container 15 and transport hydrogen gas to the blast furnace 12. However, the present invention is not limited to this. A pump 33 can also be installed in the outlet pipeline 30 to set a predetermined pressure in the sealed container 15 and transport hydrogen gas to the blast furnace 12.

[0222] Furthermore, in the above embodiments, the following situation was described: as a heating element having a multilayer body, a heating element having a multiple multilayer body is used by combining multiple multilayer bodies obtained by laminating a support body with a multilayer film, but the present invention is not limited to this. In all embodiments, for example, a heating element including one multilayer body (one support body and one multilayer film) or a heating element having more than one multilayer body may also be used.

[0223] 10: Blast Furnace Equipment 11,96,121,146,156,166,191,256,266,301: Hydrogen heating device for blast furnace 12: Blast Furnace 14,19,74,75,80,90,98,160,268: Heating element 14a: Laminated body 15,123,173,193,271,302: Closed containers 16: Temperature Control Unit 16a: Temperature sensor 16b: Heater 17: Hydrogen flow pipeline 18: Control Department 20: Setup Department 21,126,184,194,269: Room 1 22,127,185,195,270: Room 2 23: Inlet Port 24: Export port 26: Power Supply 28: Hydrogen Tank 29: Inlet Pipeline 30: Outlet Pipeline 31: Filter 32: Pressure regulating valve 33: Pump 51: Thermal insulation material 61,91,91a: Support 62,92: Multilayer film 71: Level 1 72: Level 2 73: Interface of different substances 77: Level 3 78: Interface of different substances 82: 4th floor 83: Interface of different substances 90a:Laminated body 90b: Laminated body 91a: Support 95: Blast Furnace Equipment 97: Installation pipe 115: Blast Furnace Equipment 125: Installation pipe 137: Heater 145: Blast Furnace Equipment 148: Nozzle section 149: Non-permeable gas recovery pipeline 151: Non-permeable gas recovery port 152: Non-permeable gas flow control unit 153: Circulating pump 155: Blast Furnace Equipment 158: Nozzle section 159: Injector nozzle 160a: Laminated body 161: Support 162: Multilayer film 165: Blast Furnace Equipment 171: Hydrogen heating device for blast furnace 174: First Hydrogen Absorption and Release Section 175: Second Hydrogen Absorption and Release Section 176: First temperature sensor 177: Second temperature sensor 178: First Heater 179: Second heater 180: First pressure gauge 181: Second pressure gauge 182: Hydrogen Pressure Control Unit 187: Power Supply 188: Power Supply 190: Blast Furnace Equipment 208: Branch pipe for gas introduction 237: Flow regulating valve 257a~257c: Temperature sensor 258a~258c: Nozzle section 259: Mounting plate 265: Blast Furnace Equipment 272: Temperature Control Unit 273: Hydrogen introduction pipeline 274: Inlet Port 275: Hydrogen Tank 276: Outlet Pipeline 277: Import Port 278: Export port 279: Circulating blower 280: Hydrogen Tank 281: Temperature sensor 282: Heater 283: Output Control Unit 300: Blast Furnace Equipment 302a: Window 303: Heating Structure 304: Retainer 304a: Retainer half 304b: Retainer half 309a: Opening 309b: Opening 309c: Step difference part 309d: Abutment surface 310a: Wiring 310b: Wiring 311a: Temperature sensor 311b: Temperature sensor 312a: Temperature sensor 312b: Temperature sensor 312c: Temperature sensor 313: Power Supply 314: Ammeter / Voltmeter 316: Inlet Pipeline 317a: Adjusting valve 317b: Adjustment valve 317c: Adjustment valve 318: Outlet Pipeline 319: Dry pump 320: Temperature Control Unit

Claims

1. A hydrogen heating device for a blast furnace, comprising heating and supplying a hydrogen-based gas containing hydrogen to the blast furnace, and comprising: a sealed container into which the hydrogen-based gas is introduced; a heating element disposed inside the sealed container, generating heat by absorbing and releasing the hydrogen; a temperature regulating unit for regulating the temperature of the heating element; and inlet and outlet pipelines; wherein the heating element has one or more laminates formed of a support and a multilayer film, the support being formed of at least one of a porous material, a hydrogen-permeable membrane, and a proton conductor, and the multilayer film being supported by the support; wherein the multilayer film comprises: a first layer formed of a hydrogen-absorbing metal or a hydrogen-absorbing alloy, with a thickness of less than 1000 nm; and a second layer formed of a hydrogen-absorbing metal, hydrogen-absorbing alloy, or ceramic different from the first layer, with a thickness of less than 1000 nm; wherein the hydrogen-based gas is heated to a predetermined temperature by heating with the heating element. The aforementioned sealed container is divided into a first chamber and a second chamber by the aforementioned heating element. The hydrogen pressure in the first chamber and the second chamber is different. By utilizing the pressure difference between the hydrogen in the first chamber and the second chamber, the hydrogen passes through the heating element and generates heat. The first chamber has an inlet for introducing the hydrogen-based gas, and the second chamber has an outlet for discharging the hydrogen-based gas. The hydrogen pressure in the first chamber is higher than that in the second chamber. The inlet pipeline connects a hydrogen tank storing the hydrogen-based gas to the inlet of the first chamber and introduces the hydrogen-based gas from the hydrogen tank into the first chamber. The outlet pipeline connects the outlet of the second chamber to the blast furnace and supplies the hydrogen-based gas, which has been heated to a predetermined temperature by the heating element as it passes through the first chamber into the second chamber, to the blast furnace.

2. The hydrogen heating device for a blast furnace as claimed in claim 1, wherein the aforementioned stacked volume layers are multiple.

3. The hydrogen heating device for a blast furnace as claimed in claim 1, wherein the heating element is formed in the shape of a bottomed cylinder, the first chamber is formed by the inner surface of the heating element, and the second chamber is formed by the outer surface of the heating element and the inner surface of the sealed container.

4. The hydrogen heating device for a blast furnace as claimed in claim 1, which includes a non-permeable gas recovery pipeline, wherein the first chamber has a non-permeable gas recovery port, and the non-permeable gas recovery pipeline connects the non-permeable gas recovery port of the first chamber to the hydrogen tank, so that the non-permeable gas in the hydrogen gas introduced into the first chamber from the inlet that does not permeate the heating element is recovered from the non-permeable gas recovery port and sent back to the hydrogen tank.

5. The hydrogen heating device for a blast furnace as claimed in claim 4, wherein the aforementioned non-permeable gas recovery pipeline has a non-permeable gas flow control unit, which controls the flow rate of the aforementioned non-permeable gas based on the temperature of the aforementioned heating element detected by a temperature sensor installed in the aforementioned temperature regulating unit.

6. The hydrogen heating device for a blast furnace as claimed in claim 1, which includes a nozzle portion disposed between the inlet and the heating element, which sprays the hydrogen gas that is led out from the inlet into the interior of the sealed container toward the heating element.

7. The hydrogen heating device for a blast furnace as claimed in claim 6, wherein the heating element is formed in the shape of a bottomed cylinder, and the nozzle portion has a plurality of injection ports arranged along the axial direction of the heating element, wherein the hydrogen gas is injected from the plurality of injection ports onto the entire area of ​​the inner surface of the heating element.

8. The hydrogen heating device for a blast furnace as claimed in claim 6, wherein the heating element is formed in the shape of a plate, and the nozzle portion sprays the hydrogen gas onto the entire area of ​​one side of the heating element.

9. The hydrogen heating device for a blast furnace as claimed in claim 4, wherein the heating element is formed as a cylinder with openings at both ends, one end of which is connected to the inlet and the other end of which is connected to the non-permeable gas recovery pipeline.

10. The hydrogen heating device for a blast furnace as claimed in claim 1, wherein the temperature regulating unit heats the hydrogen gas flowing in the inlet pipeline by means of a heater provided in the inlet pipeline, and heats the heating element by means of the hydrogen gas heated by the heater and introduced into the first chamber through the inlet.

11. The hydrogen heating apparatus for a blast furnace as claimed in claim 1, comprising: a first hydrogen absorption and release unit disposed in the first chamber, formed of a hydrogen absorption metal or a hydrogen absorption alloy, for absorbing and releasing hydrogen; a second hydrogen absorption and release unit disposed in the second chamber, formed of a hydrogen absorption metal or a hydrogen absorption alloy, for absorbing and releasing hydrogen; and a hydrogen pressure control unit for controlling the switching between a first mode and a second mode, wherein the first mode is such that the hydrogen pressure in the first chamber is higher than the hydrogen pressure in the second chamber, and the second mode is such that the hydrogen pressure in the second chamber is higher than the hydrogen pressure in the first chamber.

12. The hydrogen heating device for a blast furnace as claimed in claim 11, wherein the hydrogen pressure control unit heats the first hydrogen absorption and release unit and cools the second hydrogen absorption and release unit in the first mode, and heats the second hydrogen absorption and release unit and cools the first hydrogen absorption and release unit in the second mode.

13. The hydrogen heating device for a blast furnace as claimed in claim 1, wherein the sealed container houses a plurality of the heating elements, the plurality of the heating elements are plate-shaped and arranged with gaps between them so that their surfaces face each other, and the first chamber and the second chamber are provided inside the sealed container and are alternately arranged in the arrangement direction of the plurality of the heating elements.

14. The hydrogen heating apparatus for a blast furnace as claimed in claim 1, wherein the first layer is formed of any one of Ni, Pd, Cu, Mn, Cr, Fe, Mg, Co, and their alloys, and the second layer is formed of any one of Ni, Pd, Cu, Mn, Cr, Fe, Mg, Co, their alloys, and SiC.

15. The hydrogen heating device for a blast furnace as claimed in claim 1, wherein the multilayer film has a third layer in addition to the first layer and the second layer, the third layer being formed of a hydrogen-absorbing metal, hydrogen-absorbing alloy or ceramic different from the first layer and the second layer, and having a thickness of less than 1000 nm.

16. The hydrogen heating apparatus for a blast furnace as claimed in claim 15, wherein the third layer is formed of any one of CaO, Y2O3, TiC, LaB6, SrO, and BaO.

17. The hydrogen heating apparatus for a blast furnace as claimed in claim 15, wherein the multilayer film, in addition to having the first layer, the second layer and the third layer, also has a fourth layer, which is formed of a hydrogen-absorbing metal, hydrogen-absorbing alloy or ceramic that is different from the first layer, the second layer and the third layer, and has a thickness of less than 1000 nm.

18. The hydrogen heating apparatus for a blast furnace as claimed in claim 17, wherein the fourth layer is formed of any one of Ni, Pd, Cu, Cr, Fe, Mg, Co, alloys thereof, SiC, CaO, Y2O3, TiC, LaB6, SrO, and BaO.

19. A method for heating hydrogen in a blast furnace, comprising heating a hydrogen-containing gas using a hydrogen heating device for a blast furnace as described in any one of claims 1 to 18 and supplying it to the blast furnace, and comprising: an introduction step, wherein the hydrogen-containing gas is introduced into the sealed container; a temperature adjustment step, wherein the temperature of a heating element disposed inside the sealed container is adjusted by the temperature adjustment unit; and a heat generation step, wherein heat is generated from the heating element by absorbing and releasing the hydrogen in the heating element; the hydrogen-containing gas is heated to a predetermined temperature by the heating of the heating element generated in the heat generation step, and the hydrogen-containing gas heated to the predetermined temperature is supplied to the blast furnace via the outlet pipeline of the hydrogen heating device for a blast furnace.

20. A blast furnace operation method, comprising: a blowing step, wherein hydrogen gas is blown into the interior of the blast furnace as a reducing gas from the tuyeres of the blast furnace; and the hydrogen gas system is hydrogen gas heated by a blast furnace hydrogen heating device according to any one of claims 1 to 18, wherein in the blowing step, the hydrogen gas heated to a predetermined temperature by the heating element of the blast furnace hydrogen heating device is supplied to the blast furnace via the outlet pipeline.

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