JP5301265B2 - Fuel cell system comprising an oxygen generator and a hydrogen generator - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a fuel cell system that can supply high-purity hydrogen to the fuel cell with high energy efficiency. <P>SOLUTION: The fuel cell system is provided with: a fuel cell 300; an oxygen generation apparatus 70 using an oxygen separation membrane; a hydrogen generation apparatus 100 provided with a catalyst reaction chamber 130 and a transmitted hydrogen reception chamber 120 that are partitioned by hydrogen transmission membranes 112 and filled with hydrocarbon reforming catalyst; a means for supplying the oxygen generated in the oxygen generation apparatus 70 to the catalyst reaction chamber 130; a means for supplying light hydrocarbon to the catalyst reaction chamber 130; a means for supplying steam to the catalyst reaction chamber 130; and a hydrogen supplying means for supplying the hydrogen generated in the hydrogen generation apparatus 100 to the fuel cell 300. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to a fuel cell system including an oxygen generator and a hydrogen generator.

  In recent years, carbon dioxide is one of the causative substances of global warming, and there is a strong demand for reducing carbon dioxide emissions. For this reason, development of fuel cells that do not generate carbon dioxide due to combustion is being promoted as a power supply source for factories, buildings, automobiles, homes, and the like. Hydrogen is used as a fuel for a fuel cell, and development of a fuel cell system in which an on-site type hydrogen production apparatus and a fuel cell are combined so that hydrogen of the fuel can be supplied at any time has become active.

  As a method for producing hydrogen, steam reforming reaction (steam reforming), autothermal reforming (ATR), partial oxidation and the like using a light hydrocarbon (for example, methane) as a raw material are known. For example, in steam reforming, carbon dioxide and water vapor are added to light hydrocarbons and reacted in the presence of a reforming catalyst in a heating furnace to produce a reformed gas mainly composed of hydrogen and carbon monoxide. Then, hydrogen is produced by separating hydrogen in the reformed gas. Steam reforming is an endothermic reaction, and the reaction requires a high temperature of 800 ° C. or higher. In addition, excess water vapor must be supplied to suppress carbon deposition. For this reason, large heat energy is required for the production of hydrogen.

  ATR is a method for synthesizing hydrogen by combining a light hydrocarbon oxidation reaction and a catalytic reaction. That is, carbon dioxide and water vapor are generated by the combustion of light hydrocarbons in the first stage of the reaction, and the reforming reaction of light hydrocarbons is performed in the catalytic reaction unit using carbon dioxide and water vapor generated as sequential reactions, and hydrogen and This is a method for producing hydrogen by producing a reformed gas mainly composed of carbon monoxide and then separating hydrogen in the reformed gas. In ATR, the reaction heat generated in the first stage can be propagated to the reforming reaction on the spot. Therefore, although the loss of heat energy is small compared to steam reforming, the reaction temperature is still high (1000 ° C or higher) Carbon generation is likely to occur in the generation part, and this carbon generation easily induces troubles in downstream devices of the catalyst part and the catalytic reaction part. In addition, the reaction requires high-purity and expensive oxygen, and the equipment cost and running cost are high.

The partial oxidation method burns part of light hydrocarbons by adding O ₂ and reforms the generated high-temperature gas without using a catalyst (no catalyst). It is. However, in the partial oxidation method, the reforming is performed at a temperature higher than ATR (about 1300 ° C.), and there is a problem that carbide is easily generated. In addition, the cooling method must be based on direct cooling (direct quench), and the operation operation becomes complicated. Furthermore, expensive oxygen of high purity is required, and the equipment cost and running cost are high.

  Among the problems of the light hydrocarbon reforming method described above, for the supply of high-purity oxygen, in recent years, oxygen permeable membranes have been advanced, and oxygen permeable membranes that can efficiently separate oxygen from air have been proposed. (For example, Non-Patent Document 1). By using such an oxygen permeable membrane, high purity oxygen can be obtained at low cost.

Here, in addition to hydrogen, carbon monoxide and carbon dioxide are contained in the product gas obtained by the above light hydrocarbon reforming method. For this reason, when hydrogen supply to a polymer electrolyte fuel cell (PEFC) is considered, a step of removing carbon monoxide and carbon dioxide from the generated gas is further required. Conventionally, in order to separate carbon monoxide and carbon dioxide from the product gas, a separation step such as decarboxylation after the shift reaction is required, which complicates the hydrogen generation step, and part of the hydrogen in the separation step. There is a problem that the efficiency of hydrogen generation is reduced.
In recent years, a method has been proposed in which a high-purity hydrogen is generated by reforming methane at a low temperature using a hydrogen generator equipped with a hydrogen permeable membrane (for example, Non-Patent Document 2).
Tatsumi Ishihara, “Oxygen Permeation Using Mixed Conductors and Application to Partial Oxidation”, PETROTECH, Japan Petroleum Institute, May 2005, Vol. 28, No. 5, p372-375 Tatsumi Ishihara, 3 others "New Reforming Process for H2 Production from Natural Gas by Using H2 Permanent Membrane Reactor", 15th World Hydrogen Energy Conference Preprint (CD-ROM), Lecture No. 200D-0628 Sun, Pacifico Yokohama Conference Center

However, in order to use hydrogen produced by reforming light hydrocarbons in a fuel cell, it is necessary to produce hydrogen with higher purity. In addition, in the fuel cell system using hydrogen generated by reforming light hydrocarbons, it is required to construct a more energy efficient system.
Therefore, the present invention is directed to a fuel cell system that can supply high-purity hydrogen to a fuel cell and has high energy efficiency.

  The fuel cell system of the present invention includes a fuel cell, an air supply chamber partitioned by an oxygen permeable membrane, a permeated oxygen receiving chamber, an oxidation catalyst filled with the combustible gas in contact with the oxidation catalyst, and combusted. An oxygen generator provided with a catalytic combustion chamber for heating the catalyst, a catalytic reaction chamber partitioned by a hydrogen permeable membrane, and a permeated hydrogen receiving chamber, wherein the catalytic reaction chamber contains a hydrocarbon reforming catalyst (hereinafter referred to as a hydrocarbon reforming catalyst). A hydrogen generator filled with a catalyst, and a steam supply means for supplying steam to the catalytic reaction chamber, a means for supplying light hydrocarbons to the catalytic reaction chamber, and the oxygen generation A means for supplying oxygen produced by the apparatus to the catalytic reaction chamber; and a hydrogen supply means for supplying hydrogen produced by the hydrogen generator to the fuel cell, wherein air is circulated through the air supply chamber. The oxygen contained in the air permeates through the permeated oxygen receiving chamber partitioned by the oxygen permeable membrane and separates from the remaining air remaining in the air supply device, and the presence of oxygen and water vapor in the catalytic reaction chamber The hydrogen produced by bringing light hydrocarbons into contact with the hydrocarbon reforming catalyst is transmitted to the permeated hydrogen receiving chamber partitioned by the hydrogen permeable membrane and separated from the residual gas remaining in the catalytic reaction chamber. It is characterized by.

  The fuel cell system of the present invention preferably has means for circulating water vapor in the permeated oxygen receiving chamber, and the water vapor supplying means preferably supplies water vapor that has flowed through the permeated oxygen receiving chamber. There may be a means for circulating water vapor in the permeate hydrogen receiving chamber, and the hydrogen supply means may have a pressure reducing part for decompressing the permeate hydrogen receiving chamber. Preferably, the apparatus has a steam preheating device that heats steam using combustion heat generated in the catalyst combustion chamber, and the steam heated by the steam preheating device is preferably circulated through the permeate oxygen receiving chamber, and is generated in the catalyst combustion chamber. It is preferable to have a water vapor preheating device that heats the water vapor using the combustion heat, and to distribute the water vapor heated by the water vapor preheating device to the permeated hydrogen receiving chamber. Preferably, the apparatus has a means for supplying the residual gas to the catalytic combustion chamber, and generates a water vapor by using the residual gas remaining in the catalytic reaction chamber and / or hydrogen permeated into the permeated hydrogen receiving chamber as a heat source. It is preferable that at least one of the permeated oxygen receiving chamber, the air supply chamber, and the permeated hydrogen receiving chamber is filled with inert particles.

  According to the fuel cell system of the present invention, high-purity hydrogen can be supplied to the fuel cell, and energy efficiency can be improved.

The fuel cell system of the present invention will be described below with reference to examples. In addition, this invention is not limited to the following embodiment.
(First embodiment)
A fuel cell system according to a first embodiment of the present invention will be described with reference to FIGS. FIG. 1 is a schematic diagram of a fuel cell system 10. FIG. 2 is a cross-sectional view showing an example of an oxygen separator used in the fuel cell system 10. FIG. 3 is a cross-sectional view showing an example of a hydrogen generator used in the fuel cell system 10.

As shown in FIG. 1, the fuel cell system 10 includes a composite preheater 20, an oxygen generator 70, a hydrogen generator 100, a steam generator 150, and a fuel cell 300.
The raw material supply source 12 is connected to the composite preheater 20 by a pipe 14. A pipe 16 is connected to the pipe 14, and the pipe 16 is connected to a catalytic combustion chamber 90 of the oxygen generator 70. A pipe 94 is connected to the catalyst combustion chamber 90, and the pipe 94 is connected to the pipe 250.

  A pipe 32 is connected to the air supply source 30, and the pipe 32 is connected to a pipe 44 and a pipe 46 at a branch 45 via a second air blower 42. The piping 44 is connected to the catalytic combustion chamber 90, and the piping 46 is connected to the cathode 320 of the fuel cell 300. A pipe 34 is connected to the pipe 32, and the pipe 34 is connected to the composite preheater 20 via a first air blower 36.

  A pipe 152, a pipe 210, a pipe 220, a pipe 230, a pipe 240, and a pipe 250 are connected to the composite preheater 20. The pipe 152 is connected to the water vapor generator 150 via the heat exchange device 248. The pipe 152 is connected to the pipe 74 at the branch 151, and the pipe 74 is connected to the permeated oxygen receiving chamber 72 of the oxygen generator 70. A pipe 76 is connected to the permeable oxygen receiving chamber 72, and the pipe 76 is connected to the pipe 246 at a branch 247. The pipe 246 is connected to the catalytic reaction chamber 130 of the hydrogen generator 100 via a heat exchange device 248.

  The pipe 210 is a flow path through which the air heated by the composite preheater 20 is circulated. The pipe 210 is connected to the air supply chamber 80 of the oxygen generator 70. A pipe 84 is connected to the air supply chamber 80, the pipe 84 is connected to the pipe 242, and the pipe 242 is connected to the pipe 250. The pipe 242 is provided with a first gas turbine 244, and the first gas turbine 244 is connected to a generator (not shown).

  The pipe 220 is a flow path for circulating light hydrocarbons heated by the composite preheater 20. The pipe 220 is connected to the pipe 246 between the heat exchange device 248 and the hydrogen generator 100.

  The pipe 230 is a flow path for circulating the steam heated by the composite preheater 20. The pipe 230 is connected to the permeated hydrogen receiving chamber 120 of the hydrogen generator 100.

  The pipe 240 is connected to the water vapor generator 150. The pipe 250 is connected to the pipe 94 and the pipe 242.

  A pipe 122 is connected to the permeated hydrogen receiving chamber 120, and the pipe 122 is connected to a pipe 124. The pipe 124 is connected to the steam generator 150. A pipe 132 is connected to the catalyst reaction chamber 130, and the pipe 132 is connected to the steam generator 150. The pipe 132 is provided with a second gas turbine 134, and the second gas turbine 134 is connected to a generator (not shown).

  A pipe 152, a pipe 154, a pipe 156, and a pipe 158 are connected to the steam generator 150. The pipe 152 is connected to the pipe 140 at a branch 153, and the pipe 140 is connected to the water softening device 60. The pipe 140 is provided with a steam turbine 142, and the steam turbine 142 is connected to a generator (not shown).

  The pipe 154 is connected to the gas-liquid separator 190 via the heat exchange device 155. A pipe 192 and a pipe 194 are connected to the gas-liquid separator 190. The pipe 192 is connected to the pipe 16, and the pipe 194 is connected to the water softening device 60. The pipe 158 is connected to the heat exchange device 160. A pipe 162, a pipe 166, and a pipe 68 are connected to the heat exchange device 160. The pipe 162 is connected to the hot water storage tank 164. A pipe 161 is connected to the pipe 162, and the pipe 161 is connected to the steam generator 150. The pipe 166 is connected to the gas-liquid separator 170. The pipe 68 is connected to the pipe 62 and the pipe 66 at a branch 67. A pipe 172 and a pipe 174 are connected to the gas-liquid separator 170. The pipe 172 is connected to the anode 330 of the fuel cell 300, and the pipe 174 is connected to the water softening device 60. The pipe 156 is connected to the heat exchange device 180. A pipe 182, a pipe 184, and a pipe 66 are connected to the heat exchange device 180. The pipe 182 is connected to the pipe 162, and the pipe 184 is connected to an exhaust port (not shown). The pipe 66 is connected to the pipe 62 and the pipe 68 at a branch 67. A pipe 52 and a pipe 62 are connected to the water softening device 60. The pipe 52 is connected to the water source 50, and the pipe 62 is connected to the pipe 64 at a branch 63.

  The pipe 64 is connected to the cooling unit 302 of the fuel cell 300. The cooling unit 302 is connected to the pipe 322, and the pipe 322 is connected to the pipe 162. A cathode offgas line 324 for discharging unreacted air is connected to the cathode 320. An anode off gas recycle line 334 for supplying unreacted hydrogen to the anode 330 again is connected to the anode 330, and the anode off gas recycle line 334 is connected to the pipe 172. An anode off gas recycle blower 336 is provided on the anode off gas recycle line 334.

  The “steam supply means” includes pipes 74, 76, 152, 246, an oxygen generator 70, and a heat exchange device 248. The “means for supplying light hydrocarbons to the catalytic reaction chamber” includes the pipes 14, 220, 246 and the composite preheater 20. “Means for supplying oxygen generated by the oxygen generator to the catalytic reaction chamber” includes pipes 76 and 246 and a heat exchanger 248. The “hydrogen supply means” includes pipes 122, 124, 158, 166, 172, a steam generator 150, a heat exchanger 160, and a gas-liquid separator 170. “Means for circulating water vapor in the permeation oxygen receiving chamber” is constituted by pipes 74 and 152. “Means for circulating water vapor in the permeate hydrogen receiving chamber” includes pipes 152 and 230 and the composite preheater 20. “Means for supplying the residual gas to the catalytic combustion chamber” include pipes 16, 132, 154, 192, a second gas turbine 134, a steam generator 150, a heat exchanger 155, and a gas-liquid separator 190. It consists of and.

  The oxygen generator 70 is a device that separates oxygen by bringing air into contact with the oxygen permeable membrane 82 under a predetermined temperature condition. Examples of the oxygen generator 70 include a plate type, a fixed bed type, and a fluidized bed type. Examples of the plate type include those shown in FIG. As shown in FIG. 2, the oxygen generator 70 includes a main body 71 provided with a catalytic combustion chamber 90, an air supply chamber 80, and a permeated oxygen receiving chamber 72. The catalytic combustion chamber 90 is formed by filling a space defined by a support 92 with an oxidation catalyst. On both sides of the catalytic combustion chamber 90, there are provided an air supply chamber 80 and a permeated oxygen receiving chamber 72 partitioned by an oxygen permeable membrane 82, and the air supply chamber 80 is adjacent to the catalytic combustion chamber 90 through a support 92. Are arranged as follows. Piping 16, piping 44 and piping 94 are connected to the catalytic combustion chamber 90, piping 210 and piping 84 are connected to the air supply chamber 80, respectively, and piping 74 and piping 76 are connected to the permeable oxygen receiving chamber 72, respectively. Is connected. The catalytic combustion chamber 90 is filled with an oxidation catalyst. The permeated oxygen receiving chamber 72 and the air supply chamber 80 are filled with inert particles (inert particles).

  The catalytic combustion chamber 90 is a chamber in which combustible gas and oxygen are brought into contact with an oxidation catalyst and burned, and the air supply chamber 80 is heated to a predetermined temperature by the combustion heat generated by the combustion. The combustible gas is a light hydrocarbon used as a residual gas and auxiliary fuel in the catalytic reaction chamber 130 during steady operation of the fuel cell system 10. As the oxidation catalyst, a known oxidation catalyst can be used, and examples thereof include noble metals such as platinum, palladium, ruthenium, and rhodium, or those in which these noble metals are supported on a simple substance such as an alumina porous body.

  The support 92 is not particularly limited as long as it can fix the oxidation catalyst in the catalytic combustion chamber 90 and can transfer the combustion heat generated in the catalytic combustion chamber 90 to the air supply chamber 80. For example, the support 92 is made of Incoloy 800H. A board etc. can be mentioned.

As the oxygen permeable film 82, a known oxygen permeable film can be used. For example, a perovskite compound such as La _0.2 Sr _0.8 Co _0.8 Fe _0.2 O ₃ described in Non-Patent Document 1 described above, etc. Is mentioned.

  The inert particles filled in the permeable oxygen receiving chamber 72 are not particularly limited as long as they are inert to oxygen, and examples thereof include alumina, zirconia, and silica. By filling the permeable oxygen receiving chamber 72 with inert particles, the oxygen that has passed through the oxygen permeable membrane 82 from the air supply chamber 80 and moved to the permeable oxygen receiving chamber 72 is converted to water vapor supplied to the permeable oxygen receiving chamber 72. This is because they can be mixed well and efficiently flow out of the permeation oxygen receiving chamber 72.

  The inert particles filled in the air supply chamber 80 are not particularly limited as long as they are inert to oxygen, and examples thereof include alumina, zirconia, and silica. This is because, by filling the air supply chamber 80 with inert particles, the heat transfer efficiency of the combustion heat generated in the catalytic combustion chamber 90 can be increased, and oxygen in the air can efficiently permeate the oxygen permeable membrane 82.

  In the presence of oxygen and water vapor, the hydrogen generator 100 makes a light hydrocarbon contact with a reforming catalyst to generate hydrogen, and generates the generated hydrogen and a residual gas containing unreacted light hydrocarbon and other components. It separates with a hydrogen permeable membrane. Examples of the hydrogen generator 100 include a plate type, a fixed bed type, and a fluidized bed type. Examples of the plate type include those shown in FIG. As shown in FIG. 3, the hydrogen generator 100 includes a main body 110 in which a catalytic reaction chamber 130 partitioned by a hydrogen permeable membrane 112 and a permeated hydrogen receiving chamber 120 that sandwiches the catalytic reaction chamber 130 are formed. A pipe 246 and a pipe 132 are connected to the catalyst reaction chamber 130, and a pipe 230 and a pipe 122 are connected to the permeated hydrogen receiving chamber 120, respectively. The catalyst reaction chamber 130 is filled with a reforming catalyst. The permeated hydrogen receiving chamber 120 is filled with inert particles.

  As the hydrogen permeable membrane 112, a known hydrogen permeable membrane can be used, and examples thereof include a palladium (Pd) alloy membrane. Examples of commercially available hydrogen permeable membranes include Pd—Ag membranes and Pd—Cu (copper) membranes manufactured by Tanaka Kikinzoku Kogyo Co., Ltd.

  The inert particles filled in the permeated hydrogen receiving chamber 120 are not particularly limited as long as they are inactive to hydrogen, and examples thereof include alumina, zirconia, and silica. By filling the permeated hydrogen receiving chamber 120 with inert particles, the hydrogen generated in the catalytic reaction chamber 130 and transmitted through the hydrogen permeable membrane 112 to the permeated hydrogen receiving chamber 120 is supplied to the permeated hydrogen receiving chamber 120. This is because it is sufficiently mixed with the water vapor and can flow out of the permeated hydrogen receiving chamber 116 efficiently.

The reforming catalyst filled in the catalytic reaction chamber 130 generates hydrogen from light hydrocarbons in the presence of oxygen and water vapor. A known catalyst can be used as such a reforming catalyst. For example, Ni / SiO ₂ , Ni—Rh / SiO ₂ , Ni—Pt in which reactions of the following formulas (1) to (6) occur: Nickel-based catalysts such as / SiO ₂ and Ni—Fe / SiO ₂ are preferably used. This is because by using such a reforming catalyst, hydrogen can be generated from light hydrocarbons under a relatively low temperature condition of 500 to 700 ° C.

CH ₄ ⇒ C + 2H ₂ (1)
C _n H _{2n + 2} ⇒ nC + (n + 1) H ₂ (2)
C + (1/2) O ₂ ⇒CO (3)
_{C + H 2 O⇒H 2 + CO} ··· (4)
CH ₄ + H ₂ O⇔3H ₂ + CO (5)
CO + H ₂ O⇔H ₂ + CO ₂ (6)
[In the above formula (2), n is an integer of 2 or more. ]

  The composite preheater 20 includes an air heating unit 22, a water vapor heating unit 24, and a raw material heating unit 26. The composite preheater 20 is a device that takes in the combustion heat generated in the oxygen generator 70 and heats a fluid (air) containing light hydrocarbons, water vapor, and oxygen, respectively. The steam preheating device in the present invention corresponds to the steam heating unit 24.

  The steam generator 150 includes a residual air (oxygen concentration: about 19%) after the combustion gas in the catalytic combustion chamber 90 and oxygen in the air supply chamber 80 used as a heat medium in the composite preheater 20 and a hydrogen generator. This is an apparatus for generating water vapor using the hydrogen and residual gas separated in 100 as a heat medium. Examples of such a steam generator 150 include so-called composite boilers, flue boilers, once-through boilers, and the like.

The fuel cell 300 generates electricity using hydrogen as a fuel gas, and is a polymer electrolyte fuel cell (PEFC), an alkaline electrolyte fuel cell (AFC), a phosphoric acid fuel cell (PAFC), or a solid oxide fuel cell. Any of (SOFC) may be used. The fuel cell 300 is provided with a cathode 320 and an anode 330 so as to sandwich the electrolyte 310. The fuel cell 300 includes a cell having a pair of cathodes 320 and anodes 330, an electrolyte 310 sandwiched between the cathodes 320 and anodes 330, and the outside thereof sandwiched between separators to form a plurality of cells. It also includes a stacked fuel cell stack. The electrolyte 310 can be determined according to the type of the fuel cell 300.
The fuel cell 300 is provided with a cooling unit 302 for removing heat generated by power generation. The cooling unit 302 may be a cooling plate or a cooling pipe that uses cooling water as a heat medium. When the fuel cell 300 is a fuel cell stack, a plurality of cooling units 302 may be provided according to the amount of heat generated by the fuel cell stack.

  The gas-liquid separator 170 is not particularly limited, and examples thereof include a gas-liquid separator with a demister. The gas-liquid separator 190 is the same as the gas-liquid separator 170.

The water softening device 60 is a device that removes cation components such as Mg ²⁺ and Ca ²⁺ and anion components such as Cl ⁻ contained in water supplied from the water source 50. For example, an ion exchange device filled with a cation exchanger such as a cation exchange resin and an anion exchanger such as an anion exchange resin can be used.

  Examples of the air supply source 30 include an intake port that takes in air.

The operation of the fuel cell system 10 will be described.
The water from the water source 50 is supplied to the water softening device 60 via the pipe 52, and the water softening device 60 performs a softening process to remove hardness components. A part of the softened water is supplied to the steam generator 150 through the pipes 62 and 68, the heat exchange device 160, the pipe 162, and the pipe 161 in this order. Further, the other part of the softened water is supplied to the heat exchange device 180 via the pipes 62 and 66 in order. Further, another part of the softened water is supplied to the cooling unit 302 of the fuel cell 300 through the pipes 62 and 64 in order. The water supplied to the cooling unit 302 flows while cooling the fuel cell 300 and flows into the pipe 322 as hot water. The hot water flowing out to the pipe 322 is stored in the hot water storage tank 164 via the pipe 162.

  The first air blower 36 and the second air blower 42 are activated. Air is supplied to the cathode 320 from the air supply source 30 via the pipes 32 and 46 in order. Air is supplied from the air supply source 30 to the catalytic combustion chamber 90 via the pipes 32 and 44 in order. Further, the air is supplied from the air supply source 30 to the air heating unit 22 of the composite preheater 20 via the pipes 32 and 34 in order. The air supplied to the air heating unit 22 is heated by the air heating unit 22 to become preheated air, and then flows through the pipe 210 and is supplied to the air supply chamber 80.

  The light hydrocarbons are supplied from the raw material supply source 12 via the pipe 14 to the raw material heating unit 26 of the composite preheater 20. The light hydrocarbons supplied to the raw material heating unit 26 are heated by the raw material heating unit 26 to become preheated light hydrocarbons, and then supplied to the pipe 246 via the pipe 220. Light hydrocarbons as auxiliary fuel are supplied as combustible gas from the raw material supply source 12 via the pipes 14 and 16 to the catalytic combustion chamber 90 together with the remaining gas. The combustible gas supplied to the catalytic combustion chamber 90 comes into contact with the oxidation catalyst filled in the catalytic combustion chamber 90 and burns. The combustion gas generated by this combustion is supplied to the composite preheater 20 together with the remaining air in the air supply chamber 80 through the pipe 94 and the pipe 250 in this order. The combustion gas supplied to the composite preheater 20 is used as a heat source for the air heating unit 22, the steam heating unit 24, and the raw material heating unit 26, and then supplied to the steam generating device 150 via the pipe 240.

  The steam generated by the steam generator 150 flows through the pipe 152, and a part of the steam is supplied to the steam heating unit 24. The steam supplied to the steam heating unit 24 is heated by the steam heating unit 24 and flows into the pipe 230 as preheated steam. The preheated water vapor that has flowed through the pipe 230 is supplied to the permeate hydrogen receiving chamber 120 as a sweep steam for hydrogen. Further, another part of the water vapor flowing through the pipe 152 flows through the pipe 74 from the branch 151 and is supplied to the permeate oxygen receiving chamber 72 as a sweep steam for oxygen.

  The air and the oxygen permeable membrane 82 supplied to the air supply chamber 80 reach a predetermined temperature by the combustion heat generated in the catalytic combustion chamber 90. Then, oxygen in the air passes through the oxygen permeable membrane 82 and moves to the permeable oxygen receiving chamber 72. The oxygen that has moved to the permeate oxygen receiving chamber 72 is mixed with the water vapor supplied from the pipe 74 to become an oxygen-containing fluid, and flows out from the pipe 76. The oxygen-containing fluid that has flowed out to the pipe 76 flows through the pipe 246 and is heat-exchanged with the water vapor flowing through the pipe 152 by the heat exchange device 248 to reach a predetermined temperature. Thereafter, it is mixed with the preheated light hydrocarbons supplied from the pipe 220 to become a mixed fluid and supplied to the catalytic reaction chamber 130. On the other hand, of the air supplied to the air supply chamber 80, residual air containing nitrogen and oxygen that has not permeated through the oxygen permeable membrane 82 flows out from the pipe 84. The residual air flowing out to the pipe 84 is supplied to the composite preheater 20 together with the combustion gas through the pipes 242 and 250 in order. In the meantime, the remaining air drives the first gas turbine 244 provided in the pipe 242 to generate power.

  The mixed fluid supplied to the catalytic reaction chamber 130 flows through the catalytic reaction chamber 130 adjusted to a predetermined temperature while contacting the reforming catalyst. In the meantime, the preheated light hydrocarbon generates hydrogen by the reaction of the following formulas (1) to (6), for example, in the presence of oxygen and water vapor.

CH ₄ ⇒ C + 2H ₂ (1)
C _n H _{2n + 2} ⇒ nC + (n + 1) H ₂ (2)
C + (1/2) O ₂ ⇒CO (3)
_{C + H 2 O⇒H 2 + CO} ··· (4)
CH ₄ + H ₂ O⇔3H ₂ + CO (5)
CO + H ₂ O⇔H ₂ + CO ₂ (6)
[In the above formula (2), n is an integer of 2 or more. ]

  Hydrogen generated in the catalytic reaction chamber 130 passes through the hydrogen permeable membrane 112 and moves to the permeable hydrogen receiving chamber 120. The hydrogen moved to the permeated hydrogen receiving chamber 120 is mixed with the preheated steam supplied to the permeated hydrogen receiving chamber 120 via the pipe 230 and flows out from the pipe 122 as a hydrogen-containing fluid. Then, the hydrogen-containing fluid is supplied to the steam generator 150 through the pipes 122 and 124 in order. On the other hand, unreacted light hydrocarbons that cannot permeate the hydrogen permeable membrane 112, carbon dioxide, water, etc., and residual gas containing hydrogen that has not permeated the hydrogen permeable membrane 112 flow out of the pipe 132.

  The residual gas that has flowed out to the pipe 132 is supplied to the steam generator 150 via the pipe 132. During this time, the remaining gas generates power by driving the second gas turbine 134 provided in the pipe 132.

  The residual gas supplied to the steam generator 150 flows out of the pipe 154 after exchanging heat with water in the steam generator 150. The hydrogen-containing fluid supplied to the steam generator 150 flows out of the pipe 158 after exchanging heat with water in the steam generator 150. The combustion gas supplied to the steam generator 150 via the pipe 240 flows out of the pipe 156 after exchanging heat with water in the steam generator 150. During this time, water in the steam generator 150 becomes steam and flows out from the pipe 152. Of the steam generated by the steam generator 150, surplus steam generates electricity by driving the steam turbine 142 via the pipes 152 and 140.

  The residual gas flowing out from the pipe 154 is cooled to, for example, room temperature by the heat exchange device 155, and then separated into a gas component containing light hydrocarbons and water by the gas-liquid separation device 190. The gas component of the separated residual gas reaches the pipe 16 via the pipe 192 and is supplied to the oxygen generator 70. On the other hand, the separated water is supplied to the water softening device 60 via the pipe 194 and softened. Here, in the case where the gas component separated from the residual gas can cover the amount of heat necessary for the oxygen generator 70, the supply of light hydrocarbons from the raw material supply source 12 can be stopped.

  The combustion gas flowing out from the pipe 156 is sent to an exhaust port (not shown) through the heat exchange device 180 through the pipe 184. During this time, the heat exchange device 180 exchanges heat with the water supplied from the pipe 66. And water turns into warm water of arbitrary temperature (for example, 60-70 degreeC), and is stored in the warm water storage tank 164 through piping 182 and 162 in order. The hydrogen-containing fluid flowing out from the pipe 158 is heat-exchanged with the water supplied from the pipe 68 by the heat exchange device 160, cooled to a predetermined temperature, and then supplied to the gas-liquid separator 170 by the pipe 166. The heat-exchanged water becomes warm water having an arbitrary temperature (for example, 60 to 70 ° C.) and reaches the warm water storage tank 164 via the pipe 162. The hydrogen-containing fluid supplied to the gas-liquid separator 170 is separated into water and hydrogen which is a gas component. The separated hydrogen is supplied to the anode 330 through the pipe 172. On the other hand, the separated water is supplied to the water softening device 60 through the pipe 174 and softened.

  When air is supplied to the cathode 320 and hydrogen is supplied to the anode 330, a chemical reaction such as the following formula (7) occurs at the cathode 320, and a chemical reaction such as the following formula (8) occurs at the anode 330. Power generation is performed.

(1/2) O ₂ + 2H ⁺ + 2e ⁻ → H ₂ O (7)
H ₂ ⇒2H ⁺ + 2e ⁻ (8)

  Then, the anode off-gas recycle blower 336 is activated, and unreacted hydrogen in the anode 330 is supplied to the anode 330 via the anode off-gas recycle line 334 and the pipe 172 in this order. The water produced at the cathode 320 is discharged from the cathode offgas line 324 together with the unreacted air in the cathode 320.

  Light hydrocarbon refers to natural gas, oil field associated gas, LPG, and the like, and indicates a hydrocarbon having 1 to 5 carbon atoms.

The temperature of the preheated light hydrocarbon at the outlet of the composite preheater 20 can be determined according to the type of reforming catalyst used in the hydrogen generator 100 and the type of the hydrogen permeable membrane 112, and is set to 300 to 500 ° C. Is preferable, and 350 to 450 ° C. is more preferable.
The temperature of the preheated steam at the outlet of the composite preheater 20 can be determined according to the type of reforming catalyst used in the hydrogen generator 100 and the type of the hydrogen permeable membrane 112, and should be 450 to 650 ° C. Preferably, it is 500-600 degreeC.
The temperature of the preheated air at the outlet of the composite preheater 20 can be determined according to the type of the oxygen permeable membrane 82, preferably 600 to 800 ° C, more preferably 650 to 750 ° C.

The amount of water vapor supplied to the permeation oxygen receiving chamber 72 takes into account the mixing ratio of water vapor in the mixed fluid supplied to the catalytic reaction chamber 130, the amount of air supplied to the air supply chamber 80, the type of the oxygen permeable membrane 82, and the like. Can be determined. The amount of air supplied to the air supply chamber 80 is preferably determined in consideration of the type of the oxygen permeable membrane 82 and the mixing ratio of oxygen in the mixed fluid. For example, the oxygen partial pressure ratio represented by (oxygen partial pressure of residual air at the outlet of the air supply chamber) / (oxygen partial pressure of oxygen-containing fluid at the outlet of the permeated oxygen receiving chamber) is 1.0 to 1. It is preferable to adjust so that it becomes .1. Within the above range, oxygen can smoothly pass through the oxygen permeable membrane 82 from the air in the air supply chamber 80, and the oxygen generation efficiency is improved.
The amount of the preheated light hydrocarbon supplied from the pipe 220 to the pipe 246 can be determined in consideration of the power generation capacity of the fuel cell 300 and the raw material conversion rate.

  The mixing ratio of light hydrocarbons, water vapor, and air in the mixed fluid can be determined according to the type of reforming catalyst charged in the catalytic reaction chamber 130. For example, the mixing ratio of water vapor in the mixed fluid is preferably 1.0 to 2.0 in the S / C ratio represented by the number of moles of water vapor / the number of moles of light hydrocarbon carbon. The mixing ratio of air in the mixed fluid can be determined in consideration of the carbon number of the light hydrocarbon, and is expressed by the molar ratio of oxygen in the mixed fluid / the molar ratio of carbon of the light hydrocarbon. The / C ratio is preferably 0.2 to 0.5.

  The pressure of water vapor supplied to the permeation oxygen receiving chamber 72 can be determined in consideration of the pressure in the downstream catalytic reaction chamber (catalytic reaction chamber 130), the pressure in the air supply chamber 80, and the oxygen partial pressure ratio. For example, it can be determined in the range of 250 to 350 kPa or 750 to 850 kPa. This is because the fuel cell system 10 can be operated with an emphasis on hot water production efficiency if it is 250 to 350 kPa, and the fuel cell system 10 can be operated with an emphasis on power transmission end efficiency if it is 750 to 850 kPa. In addition, if it is within the above range, oxygen in the permeable oxygen receiving chamber 72 is efficiently pushed out from the permeable oxygen receiving chamber 72, and the oxygen partial pressure ratio is appropriately maintained, so that the air supply chamber 80 transfers to the permeable oxygen receiving chamber 72. This facilitates the movement of oxygen and improves the oxygen generation efficiency.

  The pressure of the mixed fluid supplied to the catalytic reaction chamber 130 is preferably determined in consideration of the type of the hydrogen permeable membrane 112, the type of reforming catalyst, the scale of the hydrogen generator 100, the capacity of the fuel cell 300, and the like. For example, the pressure of the mixed fluid supplied to the catalytic reaction chamber 130 may be adjusted so that the pressure of the residual gas at the outlet of the catalytic reaction chamber 130 is a so-called low pressure condition of 253.3 to 353.3 kPa, or the catalytic reaction The pressure of the mixed fluid supplied to the catalytic reaction chamber 130 may be adjusted so that the pressure of the residual gas at the outlet of the chamber 130 is a so-called medium pressure condition of 744.3 to 844.3 kPa. The fuel cell system 10 improves the hot water production efficiency under the low pressure condition, and the power transmission end efficiency of the fuel cell system 10 improves under the medium pressure condition.

  The supply amount of the preheated water vapor supplied to the permeated hydrogen receiving chamber 120 can be determined in consideration of the supply amount of the mixed fluid supplied to the catalytic reaction chamber 130. For example, the hydrogen partial pressure ratio represented by (hydrogen partial pressure of residual gas at the outlet of the catalytic reaction chamber) / (hydrogen partial pressure of hydrogen-containing fluid at the outlet of the permeated hydrogen receiving chamber) is 1.0 to 1.1. It is preferable to adjust so that. Within the above range, the hydrogen generated in the catalytic reaction chamber 130 can smoothly pass through the hydrogen permeable membrane 112, and the hydrogen generation efficiency is improved.

  The pressure of the preheated water vapor supplied to the permeated hydrogen receiving chamber 120 can be determined in consideration of the type of the hydrogen permeable membrane 112, the pressure in the catalytic reaction chamber 130, and the hydrogen partial pressure ratio, for example, 110 to 200 kPa. It is preferable to determine the range. Within the above range, hydrogen in the permeated hydrogen receiving chamber 120 can be efficiently pushed out of the permeated hydrogen receiving chamber 120 to keep the hydrogen partial pressure in the permeated hydrogen receiving chamber 120 appropriately. The hydrogen generated in the catalytic reaction chamber 130 can smoothly pass through the hydrogen permeable membrane 112.

  The temperature of the catalyst reaction chamber 130 can be determined according to the type of reforming catalyst, and is preferably set to 500 to 800 ° C, and more preferably 600 to 700 ° C, for example. It is because hydrogen can be efficiently generated from light hydrocarbons within the above range.

  The outlet temperature of the combustion gas generated in the catalytic combustion chamber 90 can be determined in consideration of the heat load of the composite preheater 20, the supply amount of light hydrocarbons, water vapor, air, etc., for example, 900-1300 ° C. It is preferable that

  Although the temperature of the water vapor | steam generated with the water vapor generator 150 is not specifically limited, For example, it is preferable to adjust in the range of 140-200 degreeC.

  The temperature of the hydrogen-containing fluid after cooling in the heat exchange device 160 can be determined according to the type of the fuel cell 300. For example, when PEFC is used as the fuel cell 300, the hydrogen-containing fluid is preferably cooled to 70 to 80 ° C. For example, when PAFC is used as the fuel cell 300, it is preferable to cool the hydrogen-containing fluid to 180 to 210 ° C.

  As described above, by using an oxygen generator using an oxygen permeable membrane, high-purity oxygen can be obtained at a low cost, and the reformed reaction of light hydrocarbons is promoted by supplying the obtained oxygen to the catalytic reaction chamber. Can be planned. In addition, by using a hydrogen generator using a hydrogen permeable membrane, high-purity hydrogen can be obtained without providing new steps such as shift reaction and decarboxylation.

  The fuel cell system of the present embodiment supplies sweep steam to the permeate hydrogen receiving chamber and forcibly pushes out the hydrogen permeated to the permeate hydrogen accepting chamber, so that the hydrogen permeation rate from the catalytic reaction chamber to the permeate hydrogen accepting chamber Can be improved. In addition, since the water vapor used as the oxygen sweep steam is used in the reforming reaction of light hydrocarbons, the water vapor can be used effectively, and the energy efficiency of the entire fuel cell system can be improved. Furthermore, by using preheated water vapor as the sweep steam supplied to the permeate hydrogen receiving chamber, the temperature of the hydrogen generator can be stabilized and hydrogen can be generated efficiently.

  In the fuel cell system of the present embodiment, the residual gas separated by the permeated hydrogen receiving chamber hydrogen generator is supplied as a combustible gas to the catalytic combustion chamber, so that the energy efficiency of the entire fuel cell system can be improved. Further, since the residual gas and the hydrogen-containing fluid are used to generate water vapor, the thermal energy can be effectively used, and the energy efficiency of the entire fuel cell system can be improved. By filling the permeated hydrogen receiving chamber with inert particles, the hydrogen permeating through the hydrogen permeable membrane and the water vapor flowing through the permeated hydrogen receiving chamber are rectified, and the hydrogen partial pressure in the catalytic reaction chamber / permeated hydrogen receiving chamber is rectified. The hydrogen partial pressure ratio expressed by the hydrogen partial pressure can be kept appropriate. As a result, hydrogen production efficiency can be improved.

(Second embodiment)
A fuel cell system according to a first embodiment of the present invention will be described with reference to FIGS. FIG. 4 is a schematic diagram of the fuel cell system 400.

As shown in FIG. 4, the fuel cell system 400 includes the composite preheater 20, the oxygen generator 70, the hydrogen generator 410, the steam generator 150, the fuel cell 300, and the decompression unit 454.
The raw material supply source 12 is connected to the composite preheater 20 by a pipe 14. A pipe 16 is connected to the pipe 14, and the pipe 16 is connected to a catalytic combustion chamber 90 of the oxygen generator 70. A pipe 94 is connected to the catalyst combustion chamber 90, and the pipe 94 is connected to the pipe 250.

  A pipe 32 is connected to the air supply source 30, and the pipe 32 is connected to a pipe 44 and a pipe 46 at a branch 45 via a second air blower 42. The piping 44 is connected to the catalytic combustion chamber 90, and the piping 46 is connected to the cathode 320 of the fuel cell 300. A pipe 34 is connected to the pipe 32, and the pipe 34 is connected to the composite preheater 20 via a first air blower 36.

  A pipe 152, a pipe 210, a pipe 220, a pipe 240, a pipe 250, and a pipe 430 are connected to the composite preheater 20. The pipe 152 is connected to the water vapor generator 150 via the heat exchange device 248.

  The pipe 210 is connected to the air supply chamber 80 of the oxygen generator 70. A pipe 84 is connected to the air supply chamber 80, the pipe 84 is connected to the pipe 242, and the pipe 242 is connected to the pipe 250. The pipe 242 is provided with a first gas turbine 244, and the first gas turbine 244 is connected to a generator (not shown).

  The pipe 220 is connected to the pipe 246 between the heat exchange device 248 and the hydrogen generator 400.

  The pipe 240 is connected to the water vapor generator 150. The pipe 250 is connected to the pipe 94 and the pipe 242.

  The pipe 430 is a flow path through which the water vapor heated by the composite preheater 20 is circulated. The pipe 430 is connected to the permeable oxygen receiving chamber 72. A pipe 76 is connected to the permeable oxygen receiving chamber 72, and the pipe 76 is connected to the pipe 246 at a branch 247. The pipe 246 is connected to the catalyst reaction chamber 414 of the hydrogen generator 400 via the heat exchange device 248.

  A pipe 122 is connected to the permeated hydrogen receiving chamber 412, and the pipe 122 is connected to the pipe 124. The pipe 124 is connected to the steam generator 150. A pipe 132 is connected to the catalyst reaction chamber 414, and the pipe 132 is connected to the steam generator 150. The pipe 132 is provided with a second gas turbine 134, and the second gas turbine 134 is connected to a generator (not shown).

  A pipe 152, a pipe 154, a pipe 156, and a pipe 450 are connected to the steam generator 150. The pipe 152 is connected to the pipe 140 at a branch 153, and the pipe 140 is connected to the water softening device 60. The pipe 140 is provided with a steam turbine 142, and the steam turbine 142 is connected to a generator (not shown).

  The pipe 154 is connected to the gas-liquid separator 190 via the heat exchange device 155. A pipe 192 and a pipe 194 are connected to the gas-liquid separator 190. The pipe 192 is connected to the pipe 16, and the pipe 194 is connected to the water softening device 60. The pipe 450 is connected to the gas-liquid separator 170 via a heat exchange device 452 and a decompression unit 454. A pipe 172 and a pipe 174 are connected to the gas-liquid separator 170. The pipe 172 is connected to the anode 330 of the fuel cell 300, and the pipe 174 is connected to the water softening device 60. The pipe 156 is connected to the heat exchange device 180. A pipe 182, a pipe 184, and a pipe 462 are connected to the heat exchange device 180. The pipe 182 is connected to the pipe 484 and the pipe 486 at the branch 482. The pipe 484 is connected to the hot water storage tank 164, and the pipe 486 is connected to the water vapor generator 150. The pipe 184 is connected to an exhaust port (not shown). The pipe 462 is connected to the water softening device 60. The pipe 462 is connected to the pipe 64 at a branch 463. The water softening device 60 is connected to the water source 50 by a pipe 52.

  The pipe 64 is connected to the cooling unit 302 of the fuel cell 300. The cooling unit 302 is connected to the pipe 322, and the pipe 322 is connected to the pipe 484. A cathode offgas line 324 for discharging unreacted air is connected to the cathode 320. An anode off gas recycle line 334 for supplying unreacted hydrogen to the anode 330 again is connected to the anode 330, and the anode off gas recycle line 334 is connected to the pipe 172. An anode off gas recycle blower 336 is provided on the anode off gas recycle line 334.

  The “steam supply means” includes pipes 76, 152, 246, and 430, the composite preheater 20, the oxygen generation device 70, and the heat exchange device 248. The “means for supplying light hydrocarbons to the catalytic reaction chamber” includes the pipes 14, 220, 246 and the composite preheater 20. “Means for supplying oxygen generated by the oxygen generator to the catalytic reaction chamber” includes pipes 76 and 246 and a heat exchanger 248. The “hydrogen supply means” includes pipes 122, 124, 172, 450, a steam generator 150, a heat exchange device 452, a decompression unit 454, and a gas-liquid separator 170. “Means for circulating water vapor in the permeate oxygen receiving chamber” includes pipes 152 and 430 and the composite preheater 20. “Means for supplying the residual gas to the catalytic combustion chamber” include pipes 16, 132, 154, 192, a second gas turbine 134, a steam generator 150, a heat exchanger 155, and a gas-liquid separator. 190.

  The hydrogen generator 410 includes a plate type, a fixed bed type, a fluidized bed type, and the like, like the hydrogen generator 100 in the first embodiment. For example, the hydrogen generator 410 is partitioned by the hydrogen permeable membrane 112, and a catalytic reaction chamber 414 and a permeable hydrogen receiving chamber 412 that sandwiches the catalytic reaction chamber 414 are formed. The catalyst reaction chamber 414 is filled with a reforming catalyst. The permeate hydrogen receiving chamber 412 is filled with inert particles. The inert particles filled in the permeable hydrogen receiving chamber 412 are the same as the inert particles filled in the permeable hydrogen receiving chamber 120 in the first embodiment.

The reforming catalyst filled in the catalytic reaction chamber 414 generates hydrogen from light hydrocarbons in the presence of oxygen and water vapor. As such reforming catalyst, a known catalyst can be used. For example, Ni / SiO ₂ , Ni—Rh / SiO ₂ , Ni—Pt in which the reactions of the above formulas (1) to (6) occur. Nickel-based catalysts such as / SiO ₂ and Ni—Fe / SiO ₂ are preferably used. This is because by using such a reforming catalyst, hydrogen can be generated from light hydrocarbons under a relatively low temperature condition of 500 to 700 ° C.

  The decompression unit 454 is not particularly limited as long as the inside of the permeated hydrogen receiving chamber 412 can be decompressed and the hydrogen fluid can be sucked, and examples thereof include an IDF (Induced Draft Fan). In addition, the decompression unit 454 may be configured by one IDF or the like, or may be configured by arranging two or more IDFs or the like in series.

The operation of the fuel cell system 400 will be described.
Water from the water source 50 is supplied to the water softening device 60 via the pipe 52 and softened. A part of the softened water is supplied to the heat exchange device 180 via the pipe 462. In addition, another part of the softened water is supplied to the cooling unit 302 of the fuel cell 300 via the pipes 462 and 64 in order. The water supplied to the cooling unit 302 circulates while cooling the fuel cell 300 and flows out from the pipe 322 as hot water. The hot water flowing out to the pipe 322 is stored in the hot water storage tank 164 via the pipe 484.

  The first air blower 36, the second air blower 42, and the decompression unit 454 are activated. The air is supplied to the catalytic combustion chamber 90 through the pipes 32 and 44 in order. Light hydrocarbons, which are auxiliary fuels, pass through the pipes 14 and 16 in order, and are supplied as combustible gas to the catalytic combustion chamber 90 together with the remaining gas. The combustible gas supplied to the catalytic combustion chamber 90 comes into contact with the oxidation catalyst filled in the catalytic combustion chamber 90 and burns. The combustion gas generated by this combustion is supplied to the composite preheater 20 together with the remaining air in the air supply chamber 80 through the pipe 94 and the pipe 250 in this order. The combustion gas supplied to the composite preheater 20 is used as a heat source, and then circulates through the piping 240 and is supplied to the steam generator 150.

  The preheated air heated by the air heating unit 22 flows through the pipe 210 and is supplied to the air supply chamber 80. The air and the oxygen permeable membrane 82 supplied to the air supply chamber 80 reach a predetermined temperature by the combustion heat generated in the catalytic combustion chamber 90. Then, oxygen in the air passes through the oxygen permeable membrane 82 and moves to the permeable oxygen receiving chamber 72. The oxygen that has moved to the permeation oxygen receiving chamber 72 is mixed with the water vapor supplied from the pipe 430 to become an oxygen-containing fluid and flows out from the pipe 76. The oxygen-containing fluid that has flowed out to the pipe 76 flows through the pipe 246 and is heat-exchanged with the water vapor flowing through the pipe 152 by the heat exchange device 248 to reach a predetermined temperature. Thereafter, it is mixed with the preheated light hydrocarbons supplied from the pipe 220 to form a mixed fluid, which is supplied to the catalytic reaction chamber 414. On the other hand, of the air supplied to the air supply chamber 80, residual air containing nitrogen and oxygen that has not permeated through the oxygen permeable membrane 82 flows out from the pipe 84. The residual air flowing out to the pipe 84 is supplied to the composite preheater 20 together with the combustion gas through the pipes 242 and 250 in order. In the meantime, the remaining air drives the first gas turbine 244 provided in the pipe 242 to generate power.

  The preheated light hydrocarbon heated in the raw material heating unit 26 is mixed with the hydrogen-containing fluid in the pipe 246 via the pipe 220 to become a mixed fluid, and is supplied to the catalytic reaction chamber 414. The mixed fluid supplied to the catalyst reaction chamber 414 flows through the catalyst reaction chamber 414 adjusted to a predetermined temperature while being in contact with the reforming catalyst. During this time, hydrogen is produced from the preheated light hydrocarbons by, for example, the reactions of the above formulas (1) to (6).

  Hydrogen generated in the catalytic reaction chamber 414 passes through the hydrogen permeable membrane 112 and moves to the permeable hydrogen receiving chamber 412. The hydrogen that has moved to the permeated hydrogen receiving chamber 412 is sucked by the pressure reducing unit 454 and supplied to the water vapor generating device 150 via the pipes 122 and 124. On the other hand, unreacted light hydrocarbons that cannot permeate the hydrogen permeable membrane 112, carbon dioxide, water, etc., and residual gas containing hydrogen that has not permeated the hydrogen permeable membrane 112 pass through the pipe 132 to the water vapor generator 150. And is used as a heat source for the steam generator 150 and then flows out from the pipe 154.

  The hydrogen supplied to the steam generator 150 is used as a heat source of the steam generator 150 and then flows out to the pipe 450. The hydrogen flowing out from the pipe 450 is cooled to a predetermined temperature by the heat exchange device 452, and then supplied to the gas-liquid separation device 170 via the decompression unit 454. The hydrogen supplied to the gas-liquid separator 170 is dehumidified and supplied to the anode 330. Then, the fuel cell 300 generates power using the air supplied from the pipe 46 to the cathode 320 and the hydrogen supplied from the pipe 172 to the anode 330.

  The combustion gas supplied to the steam generator 150 flows out of the pipe 156 after being used as a heat source for the steam generator 150. The combustion gas flowing out from the pipe 156 is sent to an exhaust port (not shown) through the heat exchange device 180 through the pipe 184. During this time, the heat exchange device 180 exchanges heat with the water supplied from the pipe 462. And water turns into warm water of arbitrary temperature (for example, 60-70 degreeC), and is stored in the warm water storage tank 164 via piping 182 and 484 in order. Alternatively, the water vapor is supplied to the water vapor generator 150 via the pipe 182 and the pipe 486.

  The temperature of the hydrogen-containing fluid after cooling in the heat exchange device 452 can be determined according to the type of the fuel cell 300. For example, when PEFC is used as the fuel cell 300, the hydrogen-containing fluid is preferably cooled to 70 to 80 ° C. For example, when PAFC is used as the fuel cell 300, it is preferable to cool the hydrogen-containing fluid to 180 to 210 ° C.

  The degree of pressure reduction of the permeated hydrogen receiving chamber 412 by the pressure reducing unit 454 is expressed by (hydrogen partial pressure of residual gas at the outlet of the catalytic reaction chamber) / (hydrogen partial pressure of hydrogen-containing fluid at the outlet of the permeated hydrogen receiving chamber). It is preferable to adjust the hydrogen partial pressure ratio to be 1.0 to 1.1. If it is in the said range, the hydrogen produced | generated in the catalyst reaction chamber 414 can permeate | transmit the hydrogen permeable membrane 112 smoothly, and the production | generation efficiency of hydrogen will improve. The discharge pressure on the secondary side of the decompression unit 454 is preferably determined according to the operating conditions of the fuel cell 300.

  As described above, in the present embodiment, the hydrogen in the permeated hydrogen receiving chamber is sucked by the decompression unit, so that (hydrogen partial pressure of the residual gas at the outlet of the catalytic reaction chamber) / (hydrogen-containing fluid at the outlet of the permeated hydrogen receiving chamber) The hydrogen partial pressure ratio expressed by the following formula can be maintained appropriately. In addition, the heat energy for generating the sweep steam for hydrogen becomes unnecessary, and the power generation efficiency of the fuel cell system can be improved. And since the sweep steam for hydrogen is unnecessary, a water vapor generator can be reduced in size and a fuel cell system can be reduced in size. Furthermore, by supplying the oxygen sweep steam after it is heated by the composite preheater, the temperature of the oxygen permeable membrane can be kept appropriate, and the oxygen generation efficiency in the oxygen generator can be improved.

The present invention is not limited to the above-described embodiment.
In the first and second embodiments, the permeation oxygen receiving chamber is filled with inert particles, but the inert particles may not be filled. However, from the viewpoint of rectifying oxygen and water vapor in the permeable oxygen receiving chamber and improving the efficiency of oxygen generation, it is preferable to fill the permeable oxygen receiving chamber with inert particles.

  In the first and second embodiments, the air supply chamber is filled with inert particles, but the inert particles may not be filled. However, from the viewpoint of efficiently transmitting the combustion heat generated in the catalyst combustion chamber to the air supply chamber and improving the oxygen generation efficiency, it is preferable to fill the air supply chamber with inert particles.

  In the first and second embodiments, the permeation hydrogen receiving chamber is filled with inert particles, but the inert particles may not be filled. However, from the viewpoint of rectifying hydrogen and water vapor in the permeate hydrogen receiving chamber and improving the hydrogen generation efficiency, it is preferable to fill the permeate hydrogen receiving chamber with inert particles.

In the first and second embodiments, the first and second gas turbines are provided on the secondary side of the air supply chamber and the hydrogen generator, but the gas turbine may not be provided. Only one of the gas turbines may be provided.
In the first and second embodiments, the steam turbine is provided, but the steam turbine may not be provided.

  In the first and second embodiments, steam is generated by using the hydrogen-containing fluid generated by the hydrogen generator, the residual gas, and the combustion gas generated by the catalytic combustion device and passing through the composite preheater as the heat source. The heat source used in the apparatus may be only one of the aforementioned hydrogen-containing fluid, residual gas, and combustion gas.

  In the first and second embodiments, the raw material preheating device, the oxygen preheating device, and the steam preheating device have a combined preheater. However, the raw material preheating device, the oxygen preheating device, and the steam preheating device are individually provided. May be provided.

  In the first embodiment, no decompression unit is provided, but a decompression unit may be further provided in the first embodiment. Alternatively, in the second embodiment, water vapor may be supplied as sweep steam to the permeate hydrogen receiving chamber.

  In 2nd embodiment, although the pressure reduction part is provided in one place, the pressure reduction part may be provided in two or more places. In addition, the decompression unit may be provided at any position of the hydrogen supply unit. For example, the decompression unit may be provided in a pipe 172 (FIG. 4) that is an outlet line of the gas-liquid separator 170.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated concretely, it is not limited to an Example.

Production Example 1 Production of Oxygen Permeation Membrane 1 Perovskite La _0.2 Sr _0.8 Co _0.8 Fe _0.2 O ₃ was produced as the oxygen permeable membrane 1. For the oxygen permeable membrane 1, lanthanum, strontium, cobalt and iron were weighed according to the molar ratio of each metal, and dry mixed for 1 hour to obtain a raw material powder. The obtained raw material powder was calcined in an electric furnace in an air atmosphere at a temperature of 1000 ° C. for 6 hours. After the obtained product was pulverized, this powder was molded into a predetermined shape with a mold to obtain a molded body. The obtained molded body was vacuum-dried and then subjected to isotropic isostatic pressing at a pressure of 2.7 t / cm ² (265 MPa) for 15 minutes. Then, the oxygen permeable film 1 was obtained by baking at a temperature of 1300 ° C. for 6 hours in an air atmosphere.

Preparation according to the description of (preparation 2) reforming catalyst 1 of manufacturing the aforementioned non-patent document 2, so as to be 10 mass% of the total mass of the reforming catalyst 1, the Ni / SiO ₂ supported on a SiO ₂ to Ni did. Nickel nitrate was used as a Ni supply source, and SiO ₂ (surface area: 380 m ² / g) manufactured by Aerosil Co. was used as a simple substance, and it was prepared by a known impregnation method. SiO ₂ was impregnated with an aqueous nickel nitrate solution and dried, followed by sintering at 300 ° C. for 4 hours and further heating at 400 ° C. for 5 hours to obtain a reforming catalyst 1.

Example 1
A fuel cell system A having the same configuration as the fuel cell system 10 shown in FIG. 1 was manufactured and a power generation test was performed.
The fuel cell stack of PEFC was adopted as the fuel cell, and the capacity of the test facility was set to 1.223 kW at the power generation end output (direct current) and 1 kW class as the power transmission end output (alternating current). The oxygen generator was a plate type having the same structure as that of the oxygen generator 70 shown in FIG. As the oxygen permeable membrane, the oxygen permeable membrane 1 obtained in Production Example 1 was used, and the permeation area was 0.217 m ² . The catalyst combustion chamber was filled with 5.4 L of a palladium catalyst (hydrocarbon oxidation catalyst, manufactured by Zude Chemie Catalysts) as an oxidation catalyst. The air supply chamber was filled with 8.64 L of inert particles (alumina, mass average particle diameter: 5 mmφ, manufactured by Chipton Co., Ltd.). The permeated oxygen receiving chamber was filled with 6.48 L of inert particles.

The hydrogen generator was a plate type having the same structure as the hydrogen generator 100 shown in FIG. As the hydrogen permeable membrane of the hydrogen generator, a commercially available Pd-Ag membrane (manufactured by Tanaka Kikinzoku Kogyo Co., Ltd.) is used, the permeation area is 0.176 m ² , and the hydrogen permeation flux is 0.173 kg-mol / h-H _2. / M ² . The catalyst reaction chamber was filled with 3.52 L of reforming catalyst 1 obtained in Production Example 2. The permeated hydrogen receiving chamber was filled with 5.28 L of inert particles. A composite boiler was used as the steam generator. The “hydrogen permeation flux” is a permeated hydrogen flow rate (kg-mol / h) per hour in the permeation membrane unit area (m ² ) (the same applies hereinafter).

Natural gas was used as the light hydrocarbon of the raw material. After the raw natural gas was heated to 400 ° C. with a composite preheater, the inlet pressure of the catalyst reaction chamber was set to 305.3 kPa and supplied to the catalyst reaction chamber at 0.298 Nm ³ / h. After heating the air to 700 ° C. with a composite preheater, preheated air was supplied to the air supply chamber at 4.482 Nm ³ / h. The oxygen permeation flux was 0.51 Nm ³ / h—O ₂ / m ² . 0.448 Nm ³ / h of water vapor (temperature: 144 ° C., pressure: 395.5 kPa) generated by the water vapor generator was supplied to the permeation oxygen receiving chamber as a sweep steam for oxygen. Further, 1.470 Nm ³ / h of the water vapor generated by the water vapor generator was heated to 540 ° C. with a composite preheater and then supplied to the permeate hydrogen receiving chamber as a hydrogen sweep steam.
The flow rate of natural gas as auxiliary fuel supplied to the catalyst combustion chamber is 0.026 Nm ³ / h, and the combustion gas reference SV of the oxidation catalyst is 2120 (m ³ / h) / m ³ -Cat, The heat transfer flux to the air supply chamber was 2951 kJ / m ² / h (705 kcal / m ² / h).
Other process conditions were as shown in Table 1. “Nm ³ ” represents “m ³ (standard state)” (the same applies hereinafter). The “oxygen permeation flux” is the permeation oxygen flow rate (Nm ³ / h—O ₂ ) per hour in the permeation membrane unit area (m ² ) (the same applies hereinafter). The “combustion gas standard SV” is the amount of combustion gas generated per hour (m ³ / h) per unit volume (m ³ -Cat) of the oxidation catalyst, and the unit (m ³ / h) / m ³ A value represented by -Cat (the same applies hereinafter). “Electric heat flux” is a heat transfer amount (kJ) per unit area (m ² ) per hour (h), and is represented by kJ / m ² / h.

Hydrogen generated in the catalytic reaction chamber of the hydrogen generator is 0.756 Nm ³ / h, and hydrogen generated in the hydrogen permeation receiving chamber is 0.682 Nm ³ / h. the value of the reference W / F was 26.1kg-Cat / kg-mol / h-H 2. “W / F” is the amount of catalyst (kg-Cat) per hour of hydrogen production (kg-mol / h-H ₂ ), and kg-Cat / kg-mol / h-H ₂ Expressed (same in the following).

The value of the produced hydrogen was equivalent to 72.6% as a raw material natural gas conversion rate. The cold gas efficiency defined by the following formula (9) was 70.8%. In the following formula (9), LHV (kJ / Nm ³ ) indicates a lower heating value.

Cold gas efficiency = (LHV of produced H ₂ + CO (Nm ³ / h)) / (LHV of supplied natural gas (Nm ³ / h)) × 100 (9)

  Thus, the fuel cell system A is operated, and the power generation efficiency of the fuel cell system A is measured. The results are shown in Table 1. In Table 1, “accessory power consumption” is described as “air blower” as a total value of power consumption of the first air blower and the second air blower (same in Example 2).

(Example 2)
A power generation test using the fuel cell system A was performed in the same manner as in Example 1 except that the following operating conditions were used.

Natural gas was used as the light hydrocarbon of the raw material. After the raw natural gas was heated to 400 ° C. with a composite preheater, the inlet pressure of the catalyst reaction chamber was 796.3 kPa and supplied to the catalyst reaction chamber at 0.311 Nm ³ / h. After heating the air to 700 ° C. with a composite preheater, preheated oxygen was supplied to the catalytic reaction chamber of the hydrogen generator at 4.674 Nm ³ / h. At this time, the oxygen permeation flux was 0.53 Nm ³ / h—O ₂ / m ² . Of the water vapor (temperature 170.6 ° C., pressure 803.3 kPa) generated by the water vapor generator, 0.467 Nm ³ / h was supplied as a sweep steam for oxygen to the permeation oxygen receiving chamber. Further, 0.208 Nm ³ / h of the water vapor generated by the water vapor generator was heated to 540 ° C. with a composite preheater, and then supplied to the permeated hydrogen receiving chamber as a hydrogen sweep steam.
The flow rate of natural gas as auxiliary fuel supplied to the catalytic combustion chamber is 0.019 Nm ³ / h, and the combustion gas reference SV of the oxidation catalyst is 2211 (m ³ / h) / m ³ -Cat, The heat transfer flux to the air supply chamber was 2574 kJ / m ² / h (615 kcal / m ² / h). Other process conditions were as shown in Table 1.

Hydrogen produced in the catalytic reaction chamber of the hydrogen generator was 0.755 Nm ³ / h, and hydrogen permeated into the hydrogen permeation receiving chamber was 0.682 Nm ³ / h. The W / F value of the reforming catalyst 1 in the hydrogen generator was 26.2 kg-Cat / kg-mol / h-H ₂ .

  The value of the produced hydrogen was equivalent to 70.3% as a raw material natural gas conversion rate. The cold gas efficiency defined by the formula (9) was 68.2%. Thus, the fuel cell system A is operated, and the power generation efficiency of the fuel cell system A is measured. The results are shown in Table 1.

(Example 3)
A fuel cell system B having the same configuration as the fuel cell system 400 shown in FIG. 4 was manufactured and a power generation test was performed. Two turbo IDFs (hereinafter simply referred to as IDFs) were installed in series in the decompression unit. Of the two IDFs, the upstream side is the first IDF and the downstream side is the second IDF. The fuel cell, oxygen generator, hydrogen generator, and water vapor generator all have the same specifications as in Example 1.

Natural gas was used as the light hydrocarbon of the raw material. After the raw natural gas was heated to 400 ° C. with a composite preheater, the inlet pressure of the catalyst reaction chamber was set to 264.3 kPa and supplied to the catalyst reaction chamber at 0.296 Nm ³ / h. After heating the air to 700 ° C. with a composite preheater, preheated air was supplied to the air supply chamber at 4.454 Nm ³ / h. The oxygen permeation flux was 0.51 Nm ³ / h—O ₂ / m ² . 0.445 Nm ³ / h of water vapor (temperature: 144 ° C., pressure: 395.5 kPa) generated by the water vapor generator was heated to 426 ° C. with a composite boiler, and then supplied to the permeation oxygen receiving chamber as sweep steam for oxygen.
Further, no natural gas was supplied to the catalytic combustion chamber as auxiliary fuel. The combustion gas reference SV of the oxidation catalyst was 1601 (m ³ / h) / m ³ -Cat, and the heat transfer flux to the air supply chamber was 2185 kJ / m ² / h (522 kcal / m ² / h). . The other process conditions were as shown in Table 2, and the first IDF and the second IDF were started, and the fuel cell system C was operated while the permeated hydrogen receiving chamber of the hydrogen generator was depressurized. The cold gas efficiency defined by the formula (9) was 68.2%.

Hydrogen produced in the catalytic reaction chamber of the hydrogen generator was 0.756 Nm ³ / h, and of the produced hydrogen, hydrogen permeated into the hydrogen permeation receiving chamber was 0.682 Nm ³ / h. The value of the produced hydrogen was equivalent to 72.9% as a raw material natural gas conversion rate.

  Thus, the fuel cell system B is operated, and the power generation efficiency of the fuel cell system B is measured. The results are shown in Table 2. In Table 2, the power consumption of the first air blower and the second air blower among the “accessory power consumption” is described as “air blower”. Moreover, the power consumption of 1st IDF and 2nd IDF described the total value as "IDF."

  As shown in the results of Example 1 in Table 1, the energy input to the fuel cell system A was raw material natural gas + auxiliary fuel natural gas, and the amount of heat was 3.696 kW. The power generation end output (direct current) from the PEFC fuel cell stack of fuel cell system A was 1.223 kW, and the inverter (direct current to alternating current converter) loss was 0.122 kW. In addition, the consumption power of an accessory such as an air blower constituting the fuel cell system A was 0.287 kW, and the recovery power (gas turbine) was 0.299 kW. With the above balance, 1.112 kW was obtained as the power transmission end output (AC) of the fuel cell system A, and the power transmission end efficiency of the fuel cell system A was 30.1%. The hot water (65 ° C.) produced by cooling the PEFC fuel cell stack, the hydrogen-containing fluid and the residual gas is 34.61 kg / h, which corresponds to 1.683 kW in terms of calorie, It was 45.5%. Therefore, 75.6% was obtained as the value of the total thermal efficiency (power transmission end efficiency + warm water production rate).

  As shown in the results of Example 2 in Table 1, the energy input to the fuel cell system A was raw material natural gas + auxiliary fuel natural gas, and the amount of heat was 3.758 kW. The power generation end output (direct current) from the PEFC fuel cell stack of fuel cell system A was 1.223 kW, and the inverter (direct current to alternating current converter) loss was 0.122 kW. Further, the power consumption of the accessory devices such as an air blower constituting the fuel cell system B was 0.530 kW, and the recovery power (gas turbine and steam turbine) was 0.683 kW. With the above balance, 1.253 kW was obtained as the power transmission end output (AC) of the fuel cell system A, and the power transmission end efficiency of the fuel cell system A was 33.3%. The hot water (65 ° C.) produced by cooling the PEFC fuel cell stack, the hydrogen-containing fluid and the residual gas is 22.53 kg / h, and this value is equivalent to 1.102 kW in terms of calorific value. It was 29.3%. Therefore, 62.6% was obtained as a value of total thermal efficiency (power transmission end efficiency + warm water production rate).

  As shown in the results of Example 3 in Table 2, the energy input to the fuel cell system B was raw material natural gas, and the amount of heat was 3.375 kW. The power generation end output (direct current) from the PEFC fuel cell stack of fuel cell system B was 1.223 kW, and the inverter (direct current to alternating current converter) loss was 0.122 kW. In addition, the power consumption of accessory devices such as an air blower and IDF constituting the fuel cell system B was 0.319 kW, and the recovery power (gas turbine and steam turbine) was 0.385 kW. With the above balance, 1.166 kW was obtained as the power transmission end output (AC) of the fuel cell system B, and the power transmission end efficiency of the fuel cell system b was 34.5%. The hot water (65 ° C.) produced by cooling the PEFC fuel cell stack, hydrogen and residual gas is 19.76 kg / h, this value corresponds to 0.959 kW in terms of calorie, and the hot water production efficiency is 28. 4%. Therefore, 62.9% was obtained as a value of the total thermal efficiency (power transmission end efficiency + warm water production rate).

  As described above, in all of Examples 1 to 3, the power transmission end efficiency exceeds 30%, and it can be said that the fuel cell systems A and B are systems with high energy efficiency. In addition, since the power transmission end efficiency of Example 2 is higher than that of Example 1, it was found that the power transmission end efficiency can be increased by increasing the pressure of the mixed fluid supplied to the catalyst reaction chamber. Furthermore, since Example 3 has lower 65 ° C. warm water production efficiency and higher power transmission end efficiency than Example 1, energy used for hot water production is reduced by decompressing the permeated hydrogen receiving chamber by the decompression unit. As a result, it was found that the transmission end efficiency can be improved. That is, it has been found that the optimum system among Examples 1 to 3 can be applied according to the energy demand pattern (power transmission end efficiency or hot water production efficiency) of the fuel cell system.

1 is a schematic diagram showing a fuel cell system according to a first embodiment of the present invention. It is sectional drawing which shows an example of the oxygen generator used for the fuel cell system of this invention. It is sectional drawing which shows an example of the hydrogen generator used for the fuel cell system of this invention. It is a schematic diagram which shows the fuel cell system concerning 2nd embodiment of this invention.

Explanation of symbols

10,400 Fuel cell system 16, 74, 76, 122, 124, 132, 152, 154, 158, 166, 172, 192, 220, 230, 246, 430, 450 Piping 20 Composite preheater 24 Steam heating unit 70 Oxygen Generator 72 Permeated oxygen receiving chamber 80 Air supply chamber 82 Oxygen permeable membrane 90 Catalytic combustion chamber 100, 410 Hydrogen generating device 112 Hydrogen permeable membrane 120, 412 Permeated hydrogen receiving chamber 130, 414 Catalytic reaction chamber 134 Second gas turbine 150 Water vapor Generators 155, 160, 248, 452 Heat exchangers 170, 190 Gas-liquid separator 300 Fuel cell 454 Decompression unit

Claims (10)

A fuel cell;
Oxygen provided with an air supply chamber and a permeated oxygen receiving chamber partitioned by an oxygen permeable membrane, and a catalytic combustion chamber filled with an oxidation catalyst and in contact with the oxidation catalyst to burn a combustible gas and heat the air supply chamber A generating device;
A hydrogen generating device in which a catalytic reaction chamber and a permeating hydrogen receiving chamber partitioned by a hydrogen permeable membrane are provided, and the catalytic reaction chamber is filled with a hydrocarbon reforming catalyst;
Water vapor supply means for supplying water vapor to the catalytic reaction chamber;
Means for supplying light hydrocarbons to the catalytic reaction chamber;
Means for supplying oxygen generated by the oxygen generator to the catalytic reaction chamber;
Hydrogen supply means for supplying hydrogen generated by the hydrogen generator to the fuel cell;
Air is circulated through the air supply chamber, oxygen contained in the air is transmitted to the permeated oxygen receiving chamber partitioned by the oxygen permeable membrane, and separated from residual air remaining in the air supply device;
In the catalytic reaction chamber, hydrogen produced by contacting light hydrocarbons with the hydrocarbon reforming catalyst in the presence of oxygen and water vapor passes through the permeated hydrogen receiving chamber partitioned by the hydrogen permeable membrane, and the catalyst. A fuel cell system, wherein the fuel cell system is separated from residual gas remaining in a reaction chamber.   The fuel cell system according to claim 1, further comprising means for circulating water vapor in the permeate oxygen receiving chamber.   3. The fuel cell system according to claim 2, wherein the water vapor supply means supplies water vapor that has flowed through the permeate oxygen receiving chamber.   The fuel cell system according to any one of claims 1 to 3, further comprising means for circulating water vapor in the permeate hydrogen receiving chamber.   The fuel cell system according to any one of claims 1 to 4, wherein the hydrogen supply means includes a pressure reducing unit that decompresses the permeated hydrogen receiving chamber.   It has a water vapor preheating device which heats water vapor using the combustion heat generated in the catalyst combustion chamber, and the water vapor heated by the water vapor preheating device is circulated through the permeation oxygen receiving chamber. The fuel cell system according to any one of 5.   It has a water vapor preheating device which heats water vapor using combustion heat generated in the catalyst combustion chamber, and water vapor heated by the water vapor preheating device is circulated through the permeated hydrogen receiving chamber. The fuel cell system according to any one of 6.   The fuel cell system according to any one of claims 1 to 7, further comprising means for supplying the residual gas to the catalytic combustion chamber.   The fuel cell according to any one of claims 1 to 8, further comprising a water vapor generating device that generates water vapor using the residual gas remaining in the catalytic reaction chamber and / or hydrogen permeated in the permeated hydrogen receiving chamber as a heat source. system. The fuel according to any one of claims 1 to 9, wherein at least one of the permeated oxygen receiving chamber, the air supply chamber, and the permeated hydrogen receiving chamber is filled with an inert particle. Battery system.

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