JP2007270256A - Apparatus for producing hydrogen, method for producing hydrogen and fuel cell power generator - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an apparatus for producing hydrogen at a low electrolysis voltage; a method for producing hydrogen; and a fuel cell power generator using the hydrogen produced at the low electrolysis voltage. <P>SOLUTION: The apparatus 1 for producing hydrogen H<SB>2</SB>by introducing water (S) and a reducing gas (D) therein comprises: a cathode 12 which separates water (S) into hydrogen H<SB>2</SB>and oxygen O<SP>2-</SP>through electrolysis; an anode 14 which makes the reducing gas react with oxygen; a diaphragm 10 which is arranged between a cathode chamber 20 that accommodates water to be electrolyzed in the cathode and an anode chamber 40 that accommodates the reducing gas (D) to react with oxygen in the anode, and defines the cathode chamber and the anode chamber; and a hydrogen separation member 22 which separates hydrogen generated by electrolysis from water. The fuel cell power generator 6 has: the apparatus 1 for producing hydrogen; and a fuel cell 60 for introducing the produced hydrogen H<SB>2</SB>therein and generating electricity. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a hydrogen production apparatus, a hydrogen production method, and a fuel cell power generation apparatus, and more particularly to a hydrogen production apparatus and a hydrogen production method capable of producing hydrogen at a low electrolysis voltage, and a fuel cell power generation apparatus using hydrogen produced at a low electrolysis voltage. About.

Many fuel cells being developed as distributed power generation systems generate power using hydrogen as fuel. In general, hydrogen used in a fuel cell is produced by a reforming reaction using a hydrocarbon-based raw material. However, there is a concern that a raw material gas using fossil fuels such as city gas and kerosene as a hydrocarbon-based raw material has an impact on global warming due to carbon dioxide emission, and has a large environmental load. Therefore, it is preferable to use the pyrolysis gas of biomass raw materials such as waste wood and garbage as the raw material gas. Therefore, a method for producing hydrogen at a low electrolysis voltage by producing a reducing gas using a biomass raw material, supplying water vapor to the cathode side and supplying reducing gas to the anode side has been proposed (Patent Document- 1).
Japanese Patent Laid-Open No. 2004-60041

  However, on the downstream side of the gas in the electrolyzer, the hydrogen concentration in water vapor is relatively increased on the cathode side, and the concentration of oxidized gas in the reducing gas is relatively increased on the anode side. There is a problem that the potential becomes higher than that on the cathode side, a potential opposite to electrolysis occurs, and the electrolysis voltage increases. Accordingly, an object of the present invention is to provide a hydrogen production apparatus and a hydrogen production method capable of producing hydrogen at a low electrolysis voltage, and a fuel cell power generator using hydrogen produced at a low electrolysis voltage.

In order to achieve the above object, a hydrogen production apparatus according to the invention described in claim 1 is a hydrogen production apparatus for producing hydrogen H ₂ by introducing water S and a reducing gas D as shown in FIG. 1; cathode 12 for electrolyzing water S into hydrogen H ₂ and oxygen O ²⁻ ; anode 14 for reacting reducing gas D and oxygen O ²⁻ ; water S electrolyzed at cathode 12 A diaphragm 10 that is disposed between the cathode chamber 20 that houses the anode chamber 40 and the anode chamber 40 that houses the reducing gas D that reacts with oxygen O ²⁻ at the anode 14; A hydrogen separation member 22 that separates the electrolyzed hydrogen H ₂ from the water S is provided. In addition, the water S here is water in a broad sense including water vapor, and is typically water vapor.

  With this configuration, oxygen decomposed at the cathode permeates the diaphragm and moves to the anode chamber, and hydrogen decomposed at the cathode is separated from water by the hydrogen separation member, and the partial pressure of water at the cathode is reduced. Highly maintained. Therefore, the oxygen potential of the cathode is kept high and the electrolysis voltage of water is kept low. The hydrogen separation member separates hydrogen from the water in the cathode chamber of the hydrogen production apparatus, and is typically installed in the cathode chamber.

  Further, in the hydrogen production apparatus according to the invention described in claim 2, for example, as shown in FIG. 1, in the hydrogen production apparatus 1 according to claim 1, the hydrogen separation member is constituted by a membrane 22.

  If comprised in this way, since a hydrogen separation member is comprised with a film | membrane, it will be easy to process a hydrogen separation member into arbitrary shapes, will increase the surface area of a hydrogen separation member, and will be easy to install.

  Further, in the hydrogen production apparatus according to the invention described in claim 3, as shown in FIG. 3, for example, in the hydrogen production apparatus 3 according to claim 1 or 2, the diaphragm 10 is formed in a tube shape. .

  With this configuration, a large surface area of the diaphragm, that is, the cathode and anode for electrolysis can be secured, and the hydrogen production apparatus can be downsized.

  Moreover, the hydrogen production apparatus according to the invention described in claim 4 is, for example, as shown in FIG. 2, in the hydrogen production apparatus 2 according to any one of claims 1 to 3, in the cathode chamber 20, Water S flows in a predetermined direction; in the anode chamber 40, the reducing gas D flows in a predetermined direction; the water S and the reducing gas D are counterflowing.

  With this configuration, since water and the reducing gas are counter-current, the cathode corresponding to the portion of the anode where the reducing gas has reacted with oxygen and the concentration of the reducing gas is low, the water is not much electric. It is not decomposed and the hydrogen concentration is low. Further, in the anode corresponding to the cathode portion where the hydrogen concentration is increased by electrolysis of water, the reducing gas does not react so much with oxygen, and the concentration of the reducing gas becomes high. Therefore, the oxygen potential on the cathode side is kept high and the electrolysis voltage is kept low.

  Moreover, the hydrogen production apparatus according to the invention of claim 5 is the same as the hydrogen production apparatus 2 of any one of claims 1 to 4, for example, as shown in FIG. To generate electricity.

  If comprised in this way, a hydrogen production apparatus can be used also as an electric power generating apparatus, and energy conversion efficiency can be improved.

In order to achieve the above object, the hydrogen production method according to the sixth aspect of the present invention includes, for example, as shown in FIG. 1, a step of introducing water S; a step of electrolyzing water S; A step of introducing gas D; a step of electrolyzing water S into hydrogen H ₂ and oxygen O ²⁻ ; a step of separating and removing hydrogen H ₂ from water S; and a reducing gas D and oxygen O ^2−. And a step of reacting.

  With this configuration, the electrolyzed oxygen reacts with the reducing gas, and the electrolyzed hydrogen is separated and removed from the water, so that the partial pressure of water is maintained high. Therefore, the oxygen potential is kept high and the electrolysis voltage of water is kept low.

In order to achieve the above object, a fuel cell power generator according to a seventh aspect of the present invention includes a hydrogen production apparatus 1 according to any one of the first to fifth aspects as shown in FIG. And a fuel cell 60 that introduces the produced hydrogen H ₂ and generates electric power.

  If comprised in this way, since hydrogen can be manufactured with the hydrogen manufacturing apparatus by which the electrolysis voltage was reduced and electric power can be generated with a fuel cell using the manufactured hydrogen, a fuel cell power generator with little electric power loss is provided. be able to.

  According to the hydrogen production apparatus for producing hydrogen by introducing water and a reducing gas according to the present invention, a cathode for electrolyzing water into hydrogen and oxygen, an anode for reacting the reducing gas and oxygen, and a cathode A diaphragm that is disposed between a cathode chamber containing water to be electrolyzed at the anode and an anode chamber containing a reducing gas that reacts with oxygen at the anode, and delimits the cathode chamber and the anode chamber; Since the hydrogen separation member for separating water and oxygen is provided, oxygen decomposed at the cathode permeates the diaphragm and moves to the anode chamber, and the hydrogen decomposed at the cathode is separated from water by the hydrogen separation member, The water partial pressure at is maintained high. Therefore, the oxygen potential of the cathode is maintained high, and the electrolysis voltage of water is kept low. Therefore, it is possible to provide a hydrogen production apparatus that produces hydrogen at a low electrolysis voltage.

  Further, according to the hydrogen production method of the present invention, a step of introducing water, a step of electrolyzing water, a step of introducing a reducing gas, a step of electrolyzing water into hydrogen and oxygen, Is separated from water and removed, and the reducing gas and oxygen are reacted with each other, so that the electrolyzed oxygen reacts with the reducing gas, and the electrolyzed hydrogen is separated from the water. Removed. Therefore, the oxygen potential is kept high and the electrolysis voltage of water is kept low. Therefore, a hydrogen production method for producing hydrogen at a low electrolysis voltage can be provided.

  Moreover, according to the fuel cell power generation device according to the present invention, since the hydrogen production device includes the above-described hydrogen production device and the fuel cell that introduces the produced hydrogen to generate power, the hydrogen production device produces hydrogen at a low electrolysis voltage. It is possible to provide a fuel cell power generation apparatus that produces hydrogen and generates power with the fuel cell using the produced hydrogen.

  Embodiments of the present invention will be described below with reference to the drawings. In addition, in each figure, the same code | symbol or a similar code | symbol is attached | subjected to the mutually same or equivalent member, and the overlapping description is abbreviate | omitted.

FIG. 1 is a schematic cross-sectional view illustrating the configuration of the hydrogen production apparatus 1. The hydrogen production apparatus 1 includes a cathode 12 and an anode 14 with a diaphragm 10 interposed therebetween, and an electric circuit 50 that applies a DC voltage is connected between the cathode 12 and the anode 14. The hydrogen production apparatus 1 includes a cathode chamber 20 into which water vapor S is introduced and an anode chamber 40 into which the reducing gas D is introduced. The cathode chamber 20 and the anode chamber 40 are defined by a diaphragm 10. The reducing gas D is a combustible gas, and includes, for example, methane CH ₄ , carbon monoxide CO, hydrogen H _{2 and the} like. Alternatively, alcohol, kerosene, biomass-derived gasification gas, methane fermentation gas, modified gas thereof, or ammonia gas may be included. The diaphragm 10 is a film formed of a solid electrolyte, and is preferably formed thin in order to reduce electric resistance. As the solid electrolyte, zirconium oxide (YSZ, CSZ, ScSZ) or the like added with yttrium Y, calcium Ca, scandium Sc, or the like that conducts ions to be oxidized is preferably used. Further, the cathode 12 and the anode 14 are exposed to an oxidizing / reducing atmosphere at a high temperature, and therefore metal cermets of metals such as nickel Ni and ruthenium Ru and ceramics are used. Preferably it is formed.

The water vapor S introduced into the cathode chamber 20 is electrolyzed at the cathode 12 and decomposed into hydrogen H ₂ and oxygen ions O ²⁻ . Oxygen ions O ^2−, which are in the form of negative ions, pass through the diaphragm 10 formed of a solid electrolyte and move to the anode 14. The oxygen ions O ²⁻ that have moved to the anode 14 undergo an oxidation reaction with the reducing gas D. For example, it reacts with methane CH ₄ as the reducing gas D to become carbon dioxide CO ₂ and water H ₂ O as the oxidizing gas, reacts with carbon monoxide CO as the reducing gas D, and carbon dioxide as the oxidizing gas It becomes CO ₂ and reacts with hydrogen H ₂ as the reducing gas D to become water H ₂ O as the oxidizing gas. In addition, these reactions are performed in a high temperature environment of 500-1100 degreeC, for example. As a result, the cathode chamber 20 is filled with the water vapor S and hydrogen H _2, and the anode chamber 40 is filled with the oxidizing gas and the reducing gas D that remains without being oxidized.

When the hydrogen H ₂ increases in the cathode chamber 20 and the water vapor S decreases accordingly, the oxygen ions O ^{2− at the} cathode 12 decrease. That is, the oxygen potential at the cathode 12 is lowered. Further, when the oxidizing gas increases in the anode chamber 40, the oxygen potential at the anode 14 increases. As a result, the oxygen ions O ²⁻ are unlikely to move from the cathode 12 to the anode 14, and the oxygen ions O ²⁻ do not move unless the voltage applied between the cathode 12 and the anode 14 is increased. That is, the electrolysis voltage increases.

In the hydrogen production apparatus 1, since the cathode chamber 20 includes the hydrogen separation membrane 22 as a hydrogen separation member, hydrogen H ₂ generated by electrolysis in the cathode chamber 20 passes through the hydrogen separation membrane 22 and is removed from the cathode chamber 20. Is done. That is, since the water vapor S remains in the cathode chamber 20 and the hydrogen H ₂ is separated from the mixed gas of the water vapor S and hydrogen H ₂ and removed from the cathode chamber 20, the hydrogen partial pressure is low and the water vapor partial pressure is kept high. Be drunk. Thus, the separation of hydrogen H ₂ from the mixed gas of water vapor S and hydrogen H ₂ is simply referred to as the separation of hydrogen H ₂ from water (water vapor S). As a result, the oxygen potential at the cathode 12 increases and the electrolysis voltage is kept low.

As the hydrogen separation membrane 22 used in a high temperature environment, a palladium Pd or palladium Pd alloy membrane, a vanadium V alloy membrane, a zirconium Zr-nickel Ni based amorphous alloy membrane, a ceramic proton conducting membrane or the like is used. A palladium Pd or palladium Pd alloy film is preferably used because it exhibits high permeability at a relatively high temperature. The palladium Pd alloy film may be palladium Pd-silver Ag or further added with other metals. The palladium Pd or palladium Pd alloy film may be a self-supporting palladium Pd film or a composite film with a porous support of metal or ceramic. The self-supporting palladium Pd film may be a thin palladium Pd tube so as not to be deformed by the pressure difference inside and outside. The hydrogen separation membrane 22 of palladium Pd or palladium Pd alloy membrane is generally used at 200 to 700 ° C. Since the electrolytic cell parts such as the cathode 12 and the anode 14 are used at 500 to 1100 ° C., more preferably at 600 to 800 ° C., the hydrogen separation membrane 22 is separated from the cathode 12 in the cathode chamber 20 and the temperature is slightly lowered. It is preferable to install in a different position. In order to separate hydrogen H ₂ through the hydrogen separation membrane 22, a pressure difference of hydrogen H ₂ is required. For this reason, the downstream side of the hydrogen separation membrane 22 needs to be decompressed and kept lower than the hydrogen partial pressure on the cathode chamber 20 side. As described above, since the hydrogen production apparatus 1 is operated at a high temperature, it is desirable to perform the continuous operation as much as possible from the viewpoint of thermal stress. Considering the startup time and the like, it is desirable to keep the temperature at, for example, 150 ° C. or higher even when the operation is stopped.

The hydrogen H _{2 that} has permeated the hydrogen separation membrane 22 is sent to the downstream side as hydrogen gas h. In order to make the pressure lower than that of the cathode chamber 20 as described above, it is preferable to suck the hydrogen gas h by, for example, a suction fan (not shown). Further, the reducing gas D oxidized by the oxygen ions O ²⁻ in the anode chamber 40 is discharged as the exhaust gas E.

According to the hydrogen production apparatus 1, the cathode chamber 20 includes the hydrogen separation membrane 22, and the electrolyzed hydrogen H ₂ is selectively separated from the water vapor S and discharged as hydrogen gas h, so that the oxygen potential of the cathode 12 is increased. In addition to being able to maintain high and reduce the electrolysis voltage, the hydrogen discharged as the hydrogen gas h becomes a high purity hydrogen having a purity of, for example, 99.999% or more. It can be used for hydrogen. Further, a device for separating hydrogen H ₂ from the water vapor S, for example, a gas-liquid separation device for cooling and condensing the water vapor S to separate the gas and liquid becomes unnecessary. Furthermore, almost 100% of the water vapor S introduced into the cathode chamber 20 is electrolyzed. For example, a device that circulates the water collected by the gas-liquid separator or circulates the water vapor S becomes unnecessary. In addition, the amount of water supply can be reduced. Therefore, the device itself is compact and the thermal efficiency is improved.

  Next, the operation of the hydrogen separation membrane 22 in the hydrogen production apparatus 2 will be further described with reference to the schematic cross-sectional view of FIG. FIG. 2 is a schematic cross-sectional view of a hydrogen production apparatus 2 having basically the same structure as the hydrogen production apparatus 1 of FIG. 1, and shows the hydrogen partial pressure PH at each position of the cathode 12 on the cathode 12 side in a graph. . In the graph, the broken line indicates the hydrogen partial pressure when the hydrogen separation membrane 22 is not provided. Since the hydrogen production apparatus 2 has basically the same structure as that of the hydrogen production apparatus 1, repeated description of the same parts will be omitted, and only different structures will be described. In the hydrogen production apparatus 2, instead of the electric circuit 50 (see FIG. 1) that applies a DC voltage between the cathode 12 and the anode 14, a DC voltage is similarly applied, and between the cathode 12 and the anode 14. An electric circuit 52 that can extract electric power is provided. The electric circuit 52 includes a DC / AC converter 56 for taking out a DC voltage in parallel with a DC power supply 54 for applying a DC voltage, and is connected to the DC power supply 54 side and the DC / AC converter 56 side, respectively. Are provided with switches 55 and 57. In the case of electrolyzing the water vapor S, a DC voltage is applied between the cathode 12 and the anode 14 by turning on the switch 55 and turning off the switch 57. On the other hand, when power is taken out between the cathode 12 and the anode 14, that is, when power is generated, the switch 55 is turned off and the switch 57 is turned on. The case where power is generated will be described later.

In FIG. 2, the water vapor S flows from the left side to the right side in the cathode chamber 20. The hydrogen partial pressure PH in the cathode chamber 20 is 0 on the upstream side (left side in FIG. 2) of the water vapor S, and the hydrogen partial pressure PH increases as the water vapor S is electrolyzed at the cathode 12. If the hydrogen separation membrane 22 is not provided, the hydrogen partial pressure PH continues to rise as it goes downstream, and becomes a monotonically rising graph as shown by a broken line graph. Here, for the sake of simplicity, a straight line rising to the right is shown, but it is not always a straight line. In any case, the hydrogen partial pressure PH increases as it goes downstream. However, since only hydrogen H ₂ permeates and is removed by the hydrogen separation membrane 22, the hydrogen partial pressure PH is reduced. That is, the hydrogen partial pressure PH reaches a certain level. This value is determined by the characteristics of the hydrogen separation membrane 22, the membrane area, the pressurization condition, the differential pressure between the upstream side and the downstream side of the hydrogen separation membrane 22, and can be controlled as a design value. For example, the hydrogen partial pressure PH is preferably 30% or less of the total pressure. However, if it is less than 0.5%, the possibility of steam oxidation of a metal such as nickel Ni increases, so the hydrogen partial pressure PH is preferably 0.5 to 30% of the total pressure.

On the other hand, in the anode chamber 40, as the oxidation reaction proceeds at the anode 14, the reducing gas partial pressure decreases. That is, the utilization factor of the reducing gas D is improved. Here, the utilization factor of the reducing gas D refers to the ratio of the gas that has been oxidized to the oxidizing gas in the reducing gas (combustible gas) contained in the reducing gas D. It is preferable to design the utilization rate of the reducing gas D to be 80% or more. That is, at the end of the anode 14 on the downstream side of the reducing gas D, the residual ratio of the reducing gas is 20% or less. The partial pressure of the reducing gas at that time is smaller than 20% of the total pressure because the reducing gas D contains water vapor or carbon dioxide that has not been reduced since it was introduced. Note that bringing the reducing gas utilization rate close to 100% is preferable because most of the exhaust gas E becomes oxidizing gas, which is advantageous for the recovery of carbon dioxide CO ₂ . Therefore, as shown in FIG. 2, it is preferable that the flow direction of the water vapor S in the cathode chamber 20 and the flow direction of the reducing gas D in the anode chamber 40 are opposite to each other, that is, opposite flow. By making the counterflow, the gas having a reduced reducing gas partial pressure is oxidized at the anode 14 corresponding to the cathode 12 having a very low hydrogen partial pressure PH, and the oxygen potential from the cathode 12 to the anode 14 is increased. Can be secured. Therefore, the electrolysis voltage can be kept low.

Here, a specific example in which the hydrogen partial pressure PH is controlled by adjusting the amount of hydrogen generated at the cathode 12 and the membrane area of the hydrogen separation membrane 22 will be described. The amount of hydrogen generated at the cathode 12 can be adjusted by adjusting the voltage applied to the cathode 12 and the anode 14 to control the current. On the other hand, the permeation rate of hydrogen H ₂ through the hydrogen separation membrane 22 is proportional to the difference in the square root of the upstream / downstream pressure if the membrane thickness, membrane area, and temperature of the hydrogen separation membrane 22 are constant. That is, the transmission speed V per unit area is V = K (Pu ^1/2 −Pd ^1/2 ). Here, K is a constant determined by the hydrogen separation membrane 22 for each temperature, Pu is a hydrogen partial pressure on the upstream side of the hydrogen separation membrane 22, and Pd is a hydrogen partial pressure on the downstream side of the hydrogen separation membrane 22. . The downstream hydrogen partial pressure is substantially equal to the total pressure. For example, in a hydrogen separation membrane, the hydrogen permeation rate is 30 ml / cm ² · min at 600 ° C., an upstream hydrogen partial pressure of 202 kPa (2 atm), and a downstream hydrogen partial pressure of 101 kPa (1 atm). The hydrogen permeation rate of 30 ml / cm ² · min is a value converted into a standard state (value at 25 ° C. and 100 kPa), and the same applies to the following. Here, when the hydrogen partial pressure on the downstream side is reduced to 0.101 kPa (0.001 atm), the permeation rate changes as follows according to the hydrogen partial pressure on the upstream side.
1) Upstream side 81.1 kPa (0.8 atm) → V = 62.5 ml / cm ² · min 2) Upstream side 20.3 kPa (0.2 atm) → V = 30.1 ml / cm ² · min 3) Upstream side 10.1 kPa (0.1 atm) → V = 20.6 ml / cm ² · min

Assuming that the current passed through the electrolytic cell parts such as the cathode 12 and the anode 14 is 1 A / cm ² , 7.5 ml / cm ² · min of hydrogen is generated. When the membrane area of the hydrogen separation membrane 22 is ¼ of the electrolytic cell portion, that is, the cathode 12 and the anode 14, the hydrogen generation amount and the hydrogen partial pressure on the upstream side are 20.3 kPa (0.2 atm). The permeation amount of hydrogen H ₂ becomes substantially the same, and the hydrogen partial pressure on the upstream side is stabilized at 20.3 kPa (0.2 atm). When the voltage applied is increased to increase the current density, the amount of hydrogen H ₂ produced increases and the hydrogen partial pressure increases. However, the pressure difference increases and the permeation speed also increases, so that it is stabilized with a slight pressure increase. Similarly, when the amount of hydrogen H ₂ produced is reduced, it is stabilized with a slight pressure drop. In other words, the hydrogen partial pressure in the cathode chamber 20 is stable against fluctuations in the electrolysis voltage. Note that lowering the hydrogen partial pressure in the cathode chamber 20, increase the membrane area of the hydrogen separation membrane 22, to increase the pressure differential by reducing the pressure on the downstream side of the hydrogen separation membrane 22, hydrogen H ₂ What is necessary is just to increase the transmission speed. Further, increasing the pressure of the water vapor S is advantageous for keeping the electrolysis voltage low because the water vapor partial pressure is relatively increased and the oxygen potential is increased. As a result, the surface area of the hydrogen separation membrane 22 can be reduced.

In the hydrogen production apparatus 2, if the water vapor partial pressure / hydrogen partial pressure at the cathode 12 can be kept higher than the oxidizing gas partial pressure / reducing gas partial pressure at the anode 14, the water vapor S at the cathode 12 becomes an electron due to the difference in chemical potential. Is decomposed into hydrogen H ₂ and oxygen ions O ²⁻ . By selectively permeating hydrogen H ₂ through the hydrogen separation membrane 22, the above conditions are achieved by reducing the hydrogen partial pressure in the cathode chamber 20. Electrolyzed oxygen ions O ²⁻ pass through the diaphragm 10 and move to the anode 14. The oxygen ions O ²⁻ and the reducing gas are oxidized at the anode 14 to emit electrons. That is, hydrogen H ₂ is generated at the cathode 12, and electrons flow through the electric circuit 52, so that power generation can be performed. In this case, the switch 55 of the electric circuit 52 is turned off and the switch 57 is turned on. Since the power generated by this power generation is a direct current, it is converted into an alternating current by the DC / AC converter 56, adjusted to a desired voltage / frequency by an inverter (not shown), and output. Note that the voltage of the direct current flowing through the electric circuit 52 is about 0.4 V or less. The obtained power is obtained as a product of the voltage and the current from the voltage drop when the current flows through the electric circuit 52. Further, the amount of hydrogen to be generated is determined by the amount of flowing current.

  Next, a configuration example of the hydrogen production apparatus will be described with reference to the schematic diagrams of FIGS. FIG. 3 shows a hydrogen production apparatus 3 in which a cathode 12 is arranged outside a diaphragm 10 formed in a tube shape, an anode 14 is arranged inside, and a tubular hydrogen separation membrane 22 is arranged downstream of the water vapor S. Yes. The hydrogen production apparatus 3 includes a container 30 that stores the diaphragm 10, the cathode 12, the anode 14, and the hydrogen separation membrane 22 and demarcates the flow path of the water vapor S, and the container 30 has a water vapor inlet 24 that introduces water vapor. Is formed. The container 30 typically has a cylindrical shape and is made of a metal such as stainless steel having corrosion resistance against high-temperature steam. FIG. 3 shows a cross section of a cylindrical container 30 having a central axis in the horizontal direction. In FIG. 3, the container 30 is shown as a short cylinder with little difference in diameter and length, but the container 30 is generally longer in length than the diameter. From the cylindrical end surface 31 of the container 30, the tubular diaphragm 10 is disposed in parallel with the cylindrical central axis of the container 30. The diaphragm 10 and the end surface 31 are joined in an airtight manner, and an opening is formed in the end surface 31 on the inner peripheral side of the diaphragm 10. The diaphragm 10 is shorter than the container 30, and the tip (the end opposite to the end face 31) does not extend to the end face of the container 30. The distal end of the diaphragm 10 is closed, and the diaphragm 10 is shaped like a test tube with the end of the tube closed in a round shape. The shape like this test tube is also included in the tube-like concept.

  A cylindrical cathode 12 is formed in contact with the outer periphery of the diaphragm 10, and a cylindrical anode 14 is formed in contact with the inner periphery. In the hydrogen production apparatus 3, the cathode 12 and the anode 14 are not formed at the tip of the diaphragm 10, but may be formed. The cathode 12 is not formed in contact with the end surface 31 of the container 30 but is formed only before the diaphragm 10 is in contact with the end surface 31. In this way, the cathode 12 is electrically insulated from the container 30. By electrically insulating the container 30, the risk of short-circuiting with the anode 14 is reduced. The cathode 12 is electrically connected to the electric circuit 52 (see FIG. 2). The anode 14 is formed beyond the end face 31 and is electrically connected to the electric circuit 52 there.

  A reducing gas pipe 38 is disposed in the space inside the anode 14. The reducing gas pipe 38 is disposed concentrically with the anode 14 in the space inside the cylindrical anode 14. The reducing gas pipe 38 is a pipe having a diameter smaller than the inner circumference of the anode 14, and a flow path 37 is formed between the outer circumference of the reducing gas pipe 38 and the inner circumference of the anode 14. The flow path 37 corresponds to the anode chamber 40 (see FIG. 1) in which the reducing gas D flows in contact with the anode 14. The reducing gas pipe 38 extends beyond the end face 31, further extends beyond an end face 42 described later, and is piped from an external reducing gas supply source (not shown) through the reducing gas inlet 34 ( (Not shown). Further, the anode 14 opens at a position beyond the end face 31, and the flow path 37 constitutes an exhaust gas discharge port 36 there. The reducing gas pipe 38 has an open end before the tip of the diaphragm 10, typically beyond the position where the anode 14 is not formed, or at the same position. With this configuration, the reducing gas D supplied from the reducing gas supply source is supplied to the vicinity of the distal end of the tube-shaped diaphragm 10 and flows from there to the flow path 37 in the direction of the end face 31. That is, the reducing gas D flows from the front end side to the end face 31 side along the anode 14.

  The container 30 is extended to the outside of the end surface 31 (on the side opposite to the side where the diaphragm 10 is disposed), and the end surface 42 is disposed there, and an exhaust gas accumulation path 44 is formed. The exhaust gas accumulation path 44 is a space sandwiched between the end face 31 and the end face 42, and communicates with the flow path 37 through the exhaust gas discharge port 36. Further, an exhaust gas accumulation path outlet 46 is formed in the cylindrical body of the container 30 at the position of the exhaust gas accumulation path 44.

  The hydrogen production apparatus 3 includes a plurality of electrolysis cell units composed of the above-described diaphragm 10, cathode 12, anode 14, and the like. In FIG. 3, two sets of electrolysis cell parts are shown, but the number of sets is not limited to two and may be any number. In addition, you may provide only one set of electrolysis cell part.

  A hydrogen separation membrane 22 is disposed at the tip of the diaphragm 10. The hydrogen separation membrane 22 is formed in a tube shape and is disposed in a direction orthogonal to the central axis of the container 30. One end of the hydrogen separation membrane 22 extends beyond the container 30 and is connected to a hydrogen pipe (not shown) outside the container 30. The other end of the hydrogen separation membrane 22 is closed in the container 30, but the hydrogen separation membrane 22 may penetrate the container 30 and both ends thereof may be connected to hydrogen piping. The shape of the hydrogen separation membrane 22 is not limited to a tube shape, but may be a hollow disk shape or other shapes, but a shape that can take a large surface area is preferable. The tube shape is preferable because it can be easily formed while increasing the surface area and the shape can be easily stabilized against a pressure difference. The hydrogen production apparatus 3 includes only one set of hydrogen separation membranes 22 but may include a plurality of hydrogen separation membranes 22. The water vapor inlet 24 is formed at a position separated from the position where the hydrogen separation membrane 22 is disposed in the container 30, that is, at the end face 31 side of the container 30. As is clear from the above description, the space inside the container 30 and not including the hydrogen separation membrane 22 around the electrolytic cell portion corresponds to the cathode chamber 20 (see FIG. 1) through which the water vapor S flows.

Then, the effect | action of the hydrogen production apparatus 3 is demonstrated. A predetermined DC voltage is applied between the cathode 12 and the anode 14 from the electric circuit 52 (see FIG. 2), and the cathode 12 is negatively charged and the anode 14 is positively charged. Steam S is introduced into the container 30 from the steam inlet 24. The steam S flows along the cathode 12 from the steam inlet 24 toward the distal end of the diaphragm 10, that is, from right to left in FIG. While flowing along the cathode 12, the water vapor S is electrolyzed into hydrogen H ₂ and oxygen ions O ²⁻ at the cathode 12. The electrolyzed oxygen ions O ²⁻ permeate the diaphragm 10 formed of a solid electrolyte and move to the anode 14. On the other hand, the reducing gas D is sent from the reducing gas supply source (not shown) to the reducing gas introduction port 34, and the reducing gas D flows through the reducing gas pipe 38 from the opening end near the tip of the diaphragm 10. It flows out to the flow path 37, and flows along the anode 14 in the direction returning to the end surface 31, that is, from the left to the right in FIG. The reducing gas D flowing through the flow path 37 along the anode 14 undergoes an oxidation reaction with oxygen ions O ²⁻ and becomes an oxidizing gas. A part of the reducing gas D is oxidized in this way, and the concentration of the oxidizing gas increases as it goes downstream (right side in FIG. 3). It flows out to 44. In the exhaust gas accumulation path 44, the exhaust gas E discharged from the exhaust gas discharge ports 36 of the plurality of electrolysis cell portions is united and discharged from the exhaust gas accumulation path discharge port 46 to the outside process, or sent to a subsequent process, or , And released into the atmosphere as exhaust gas.

The water vapor S is electrolyzed at the cathode 12, and the oxygen ions O ²⁻ move to the anode 14 and are removed, and thus flow downstream along the cathode 12 (left side in FIG. 3) while mixing with the hydrogen H ₂ . As it flows downstream along the cathode 12, the concentration of hydrogen H ₂ increases. However, the hydrogen separation membrane 22 is disposed at the tip of the electrolytic cell portion. There, only hydrogen H ₂ passes through the hydrogen separation membrane 22 and flows inside the tubular hydrogen separation membrane 22. Hydrogen H ₂ is sucked by a suction fan (not shown) or the like, and supplied as hydrogen gas h from the hydrogen discharge port 26 to downstream applications. Since the hydrogen gas h is a high-purity hydrogen gas, it can be used for various applications such as a fuel cell. Thus, by separating hydrogen H ₂ using the hydrogen separation membrane 22, high-purity hydrogen H ₂ can be easily obtained.

The concentration of hydrogen H ₂ decreases around the hydrogen separation membrane 22. Therefore, the concentration of hydrogen H ₂ does not increase as it goes downstream along the cathode 12, and becomes substantially constant at a certain value. Therefore, the water vapor partial pressure is kept high at the cathode 12, and electrolysis is actively performed. As a result, the oxygen potential is maintained high, oxygen ions O ²⁻ are actively transferred from the cathode 12 to the anode 14, and the electrolysis voltage between the cathode 12 and the anode 14 can be kept low. Further, since the flow of the water vapor S along the cathode 12 and the flow of the reducing gas D along the anode 14 are counterflows, in the vicinity of the end face 31 where the oxidizing gas concentration in the reducing gas D is high, the water vapor S has just been introduced from the water vapor inlet 24 and does not substantially contain hydrogen H ₂ and has a high water vapor pressure. That is, there is no portion where the oxygen potential is lowered over the entire electrolytic cell portion. Therefore, the oxygen potential is kept high and the electrolysis voltage can be kept low. Further, if the force for sucking hydrogen H ₂ from the hydrogen separation membrane 22 is increased, specifically, if the suction side is depressurized or if the pressure for supplying the steam S is increased, the steam S side in the container 30 and the hydrogen The pressure difference with the inside of the separation membrane 22 becomes large, and the production rate of hydrogen H ₂ can be easily increased.

Further, the hydrogen H _{2 that} has passed through the hydrogen separation membrane 22 is discharged from the inside of the container 30 to the outside, and the water vapor S is not discharged. That is, only the portion of the water vapor S introduced into the container 30 that has been electrolyzed permeates the hydrogen separation membrane 22 as hydrogen H ₂ , and permeates the diaphragm 10 as oxygen ions O ²⁻ and reduces the reducing gas D. It is oxidized and discharged. Therefore, it is only necessary to replenish the water vapor S that has been electrolyzed and reduced, and the utilization efficiency of the water vapor S is increased.

Next, the configuration of the hydrogen production apparatus 4 as a modification of the hydrogen production apparatus 3 (see FIG. 3) will be described with reference to the schematic diagram of FIG. In the hydrogen production apparatus 4, a hydrogen separation membrane 22 formed in a tube shape is spirally arranged around an electrolytic cell portion formed in a tube shape. By arranging in this way, the surface area of the hydrogen separation membrane 22 is increased, the amount of hydrogen H ₂ permeated is increased, and the partial pressure of the hydrogen H ₂ in the container 30 is kept low throughout the electrolysis of the water vapor S. Can be made more active and the electrolysis voltage can be reduced.

  Next, a hydrogen production apparatus 5 in which a cylindrical anode 14 is arranged on the outer periphery of a diaphragm 10 formed in a tube shape and a cylindrical cathode 12 is arranged on the inner periphery will be described with reference to the schematic diagram of FIG. Since the hydrogen production apparatus 5 is basically similar to the hydrogen production apparatus 3 (see FIG. 3), the differences will be mainly described. Also in the hydrogen production apparatus 5, the tubular diaphragm 10 is disposed in parallel to the central axis of the container 30 from the one end surface 31, and the anode 14 is disposed on the outer periphery and the cathode 12 is disposed on the inner periphery. The anode 14 does not contact the end face 31, and the cathode 12 extends beyond the end face. A tubular hydrogen separation membrane 22 is disposed in the space inside the cathode 12. The hydrogen separation membrane 22 is a space inside the cylindrical cathode 12, is concentrically arranged with the cathode 12, has a smaller diameter than the inner periphery of the cathode 12, and is between the outer periphery of the hydrogen separation membrane 22 and the inner periphery of the cathode 12. A cathode chamber 27 through which water vapor S flows is formed. A portion between the end of the cathode 14 beyond the end face 31 and the outer periphery of the hydrogen separation membrane 22 is a hydrogen inlet 24. Further, the end of the hydrogen separation membrane 22 beyond the end face 31 constitutes a hydrogen discharge port 26 and is connected to a pipe (not shown) to supply the produced hydrogen gas h to downstream applications. The container 30 is formed with a reducing gas inlet 34 for introducing the reducing gas D into the container 30 and an exhaust gas outlet 36 for discharging the exhaust gas E. The reducing gas introduction port 34 is formed on the cylindrical end surface of the container 30 opposite to the end surface 31, and the exhaust gas discharge port 36 is formed on the cylindrical body of the container 30 close to the end surface 31.

Also in the hydrogen production apparatus 5, a predetermined DC voltage is applied between the cathode 12 and the anode 14 from the electric circuit 52 (see FIG. 2), and the cathode 12 is negatively charged and the anode 14 is positively charged. The water vapor S is introduced into the cathode chamber 27 from the hydrogen inlet 24 and flows along the cathode 12 toward the distal end direction of the diaphragm 10 (left side in FIG. 5). While flowing through the cathode chamber 27, the water vapor S is electrolyzed by the cathode 12 into hydrogen H ₂ and oxygen ions O ²⁻ . The electrolyzed oxygen ion O ²⁻ passes through the diaphragm 10 and moves to the anode 14 on the outer peripheral side. On the other hand, the reducing gas D is sent from the reducing gas supply source (not shown) to the reducing gas inlet 34, and the reducing gas D passes through the container 30 from the front end direction of the diaphragm 10 toward the end face 31 (in FIG. 5). Flows along the anode 14 (from left to right). The reducing gas D undergoes an oxidation reaction with oxygen ions O ²⁻ at the anode 14 to become an oxidizing gas, and finally flows out from the exhaust gas outlet 36 as exhaust gas E.

In the cathode chamber 27, the water vapor S is electrolyzed into hydrogen H ₂ and oxygen ions O ²⁻ , but the oxygen ions O ²⁻ move toward the anode 14, so that the water vapor S and hydrogen H ₂ remain. Become. However, the hydrogen separation membrane 22 is disposed at the center of the cathode chamber 27, and hydrogen H ₂ permeates the hydrogen separation membrane 22, reaches the hydrogen discharge port 26 from the tubular inner side of the hydrogen separation membrane 22, and is downstream. Supplied for use. Thus, the electrolyzed hydrogen H ₂ is separated by the hydrogen separation membrane 22, and the partial pressure of the hydrogen H ₂ is low and the partial pressure of the water vapor S is kept high throughout the cathode chamber 27. Therefore, the electrolysis voltage is kept low as described above. Moreover, since the flow of the water vapor S in the cathode chamber 27 and the flow of the reducing gas D along the anode 14 in the container 30 are counterflows, the electrolysis voltage can be kept lower. In the hydrogen production apparatus 5, since the water vapor partial pressure is kept high everywhere, the arrangement of the reducing gas introduction port 34 and the exhaust gas discharge port 36 may be changed, and a parallel flow may be used instead of a counter flow. Even in this case, the increase in the electrolysis voltage can be suppressed to a small level.

Next, the fuel cell power generation apparatus 6 using the hydrogen production apparatus according to the present invention will be described with reference to the block diagram of FIG. FIG. 6 is a block diagram illustrating a fuel cell power generator 6 that generates power using the hydrogen gas h manufactured by the hydrogen generator 1 (see FIG. 1). The fuel cell power generator 6 includes a gasifier 74 that gasifies raw material fuel into a combustible gas G containing hydrocarbons, and reforms the combustible gas G into a highly reducible reducing gas D using water vapor S ( A reformer 72 for lightening (that is, reducing the number of carbon atoms), a hydrogen production apparatus 1 for producing hydrogen gas h from the reducing gas D and the steam S, and heat for cooling the hydrogen gas h discharged from the hydrogen production apparatus 1 An exchanger 70 and a fuel cell 60 that generates power using hydrogen gas h and air O are provided. In addition, since it has already demonstrated about the hydrogen production apparatus 1, the overlapping description is abbreviate | omitted. The gasifier 74 is an apparatus that produces a combustible gas G from biomass such as waste material. Typically, the combustible gas G includes hydrocarbon C _m H _n , carbon monoxide CO, hydrogen H _{2, and the} like. . For example, natural gas, city gas, kerosene or the like may be introduced from the outside of the system as the combustible gas G without including the gasifier 74. The reformer 72 reforms the hydrocarbon C _n H _m in the combustible gas G using the steam S. The water vapor S may be the same as or different from the water vapor S supplied to the hydrogen production apparatus 1. When the reducing gas contains a large amount of hydrocarbon compounds, it is desirable to promote reforming because carbon is deposited by pyrolysis at a high temperature and this carbon adversely affects the anode 14 of the hydrogen production apparatus 1. . For this purpose, the reformer 72 reforms the mixed gas of the high-temperature combustible gas G and the water vapor S under the reforming catalyst. As the reforming catalyst, a metal catalyst such as nickel Ni, ruthenium Ru, platinum Pt, rhodium Rh, palladium Pd, or an alloy catalyst thereof is used alone or in combination and held on a carrier such as alumina, zirconia, or silica. It is done. Note that the fuel cell power generator 6 may not include the reformer 72. In particular, when a light flammable gas G is used, it may not be provided. When the combustible gas G contains a sulfur compound, it is preferable to provide a desulfurization device (not shown) as a pretreatment in order to reduce the activity of the reforming catalyst and the anode 14. Furthermore, when the flammable gas G contains an organosilicon compound, it decomposes at high temperatures to become inorganic particles, clogs the multi-anode anode 14 and reduces its activity, and therefore it is preferable to remove it by pretreatment. .

The hydrogen production apparatus 1 introduces a reducing gas D and water vapor S to produce hydrogen gas h. Hydrogen gas h produced by the hydrogen production apparatus 1 is sent to the fuel electrode 64 of the fuel cell 60. Air O as an oxidant gas is sent to the air electrode 66 of the fuel cell 60. The fuel cell 60 includes a solid polymer electrolyte membrane 62 between the fuel electrode 64 and the air electrode 66, and hydrogen H ₂ of the hydrogen gas h of the fuel electrode 64 and oxygen O in the air O of the air electrode 86. Electricity is generated by an electrochemical reaction between the _two . Since a so-called solid polymer fuel cell using a solid polymer electrolyte membrane is typically operated at 80 ° C. to 100 ° C., for example, hydrogen gas h discharged from the hydrogen production apparatus 1 that reacts at 500 ° C. Is cooled to 80 ° C. to 100 ° C. by the heat exchanger 70. Furthermore, in the heat exchanger 70, since the air O is heated to 80 ° C. to 100 ° C., heat exchange between the hydrogen gas h and the air O may be performed.

Since the fuel cell power generation device 6 includes the hydrogen production device 1, the high purity hydrogen gas h can be produced with a low electrolysis voltage, and the fuel cell 60 can generate power using the hydrogen gas h. Therefore, it becomes an efficient power generation device. In the above description, the fuel cell power generation device 6 has been described as including the hydrogen production device 1, but it goes without saying that other hydrogen production devices such as the other hydrogen production devices 2 to 4 described above are provided. Also good. Although described as using air O as an oxidizing agent gas, oxidant gas is not limited to air O, it may be any gas containing oxygen (O ₂₎ to oxidize hydrogen H ₂ in hydrogen gas h, oxygen Gas or the like is also preferably used. Furthermore, in the above description, the fuel cell 60 has been described as a polymer electrolyte fuel cell, but the fuel cell may be any other type of fuel cell.

Next, the result of confirming the effect of the hydrogen production apparatus according to the present invention will be described using the embodiment shown in FIG. FIG. 7 is a cross-sectional view illustrating the hydrogen production apparatus 7 used as an example. A tube-type yttria-stabilized zirconia (YSZ) with one end closed was used as a solid oxide electrolyte diaphragm 10, and a nickel-zirconia cermet electrode as a cathode 12 and an anode 14 was disposed on the outer peripheral side and inner peripheral side thereof. In the hydrogen production device 7, the cathode 12 and the anode 14 are also arranged at the tip of the diaphragm 10. This electrolysis cell part was arrange | positioned in the tube-shaped outer wall 32 with which the front-end | tip closed. A reducing gas inlet 34 is formed at the tip of the outer wall 32. Inside the anode 14, a tube made of palladium Pd 25% -silver Ag alloy having a thickness of 0.1 mm, a diameter of 5 mm, and a length of 200 mm closed on one side was disposed as the hydrogen separation membrane 22. The space between the outer wall 32 and the cathode 12 constitutes the cathode chamber 20 (see FIG. 1), and the space between the anode 14 and the hydrogen separation membrane 22 constitutes the anode chamber 40 (see FIG. 1). The open end of the hydrogen separation membrane 22 (on the side opposite to the tip) constitutes a hydrogen discharge port 26. An exhaust pipe (not shown) was connected to the hydrogen discharge port 26, and further connected to a nitrogen cylinder (not shown) and a mass analyzer (not shown) with a three-way valve. The cathode chamber 20 was connected to a high-temperature steam pipe (not shown) for supplying steam at 700 ° C., and the anode chamber 40 was connected to a gas introduction pipe (not shown) for supplying methane CH ₄ as a reducing gas.

  First, nitrogen was injected into the hydrogen separation membrane 22 from a nitrogen cylinder and replaced with nitrogen. Subsequently, methane is supplied from the gas introduction pipe to the anode chamber 40 and water vapor is supplied from the high temperature steam pipe to the cathode chamber 20, and a voltage of 0.2 V is applied from the electric circuit 50 to the anode 14 and the cathode 12 at 700 ° C. High temperature steam electrolysis was performed by supplying 6A DC power. In this state, the three-way valve connecting the inside of the hydrogen separation membrane 22 and the mass analyzer was opened, and gas was introduced into the mass analyzer for gas analysis. As a result, it was confirmed that hydrogen was present and no water vapor was present.

[Comparative example]
Next, as shown in FIG. 8, as a comparative example for comparison with the above-described embodiment, a hydrogen production apparatus 8 provided with an exhaust pipe 82 that is a metal pipe having an open end instead of the hydrogen separation membrane 22 is provided. The same measurement as in the above example was performed. As a result, it was confirmed that hydrogen was produced but was exhausted as a mixed gas of hydrogen and water vapor. Further, it was found that the voltage applied between the cathode 12 and the anode 14 in order to pass a current of 6 A was 0.4 V, which was higher than that of the hydrogen production apparatus 7 according to the present invention.

It is a typical sectional view explaining composition of a hydrogen production device concerning the present invention. It is typical sectional drawing of the hydrogen production apparatus which concerns on this invention, and also shows the hydrogen partial pressure in each position of a cathode with a graph. It is a schematic diagram explaining the structural example of a hydrogen production apparatus. A hydrogen production apparatus is shown in which a cathode is arranged outside a diaphragm formed in a tube shape, an anode is arranged inside, and a tubular hydrogen separation membrane is installed downstream of water vapor. It is a schematic diagram explaining the structural example of a hydrogen production apparatus. In the modification of the hydrogen production apparatus shown in FIG. 3, a hydrogen separation membrane formed in a tube shape is spirally arranged around the electrolytic cell portion formed in a tube shape. It is a schematic diagram explaining the structural example of a hydrogen production apparatus. A cylindrical anode was arranged on the outer periphery of the diaphragm formed in a tube shape, and a cylindrical cathode was arranged on the inner periphery. FIG. 2 is a block diagram illustrating a fuel cell power generation device that generates power using hydrogen gas produced by the hydrogen production device shown in FIG. 1. It is sectional drawing explaining the hydrogen production apparatus used as an Example. It is sectional drawing explaining the hydrogen production apparatus used as a comparative example.

Explanation of symbols

1-5 Hydrogen production apparatus 6 Fuel cell power generation apparatus 10 Membrane 12 Cathode 14 Anode 20 Cathode chamber 22 Hydrogen separation membrane (member)
24 Steam inlet 26 Hydrogen outlet 27 Cathode chamber 30 Container 31 End face 32 Outer wall 34 Reducing gas inlet 36 Exhaust gas outlet 37 Flow path 38 Reducing gas pipe 40 Anode chamber 42 End face 44 Exhaust gas accumulation path 44 Exhaust gas accumulation path outlet 50, 52 Electric circuit 54 Power supply 55, 57 Switch 56 DC / AC converter 60 Fuel cell 62 Solid polymer electrolyte membrane 64 Fuel electrode 66 Air electrode 70 Heat exchanger 72 Reformer 74 Gasifier 82 Exhaust pipe D Reducing gas E exhaust gas h hydrogen O air S water vapor (water)

Claims (7)

A hydrogen production device that produces hydrogen by introducing water and a reducing gas:
A cathode that electrolyzes the water into hydrogen and oxygen;
An anode for reacting the reducing gas with the oxygen;
Disposed between the cathode chamber containing the water to be electrolyzed at the cathode and the anode chamber containing the reducing gas that reacts with the oxygen at the anode, and defines the cathode chamber and the anode chamber A separating membrane;
A hydrogen separation member for separating the electrolyzed hydrogen from the water;
Hydrogen production equipment. The hydrogen separation member comprises a membrane;
The hydrogen production apparatus according to claim 1. The diaphragm is formed in a tube shape;
The hydrogen production apparatus according to claim 1 or 2. In the cathode chamber, the water flows in a predetermined direction;
In the anode chamber, the reducing gas flows in a predetermined direction;
The water and the reducing gas are countercurrent;
The hydrogen production apparatus according to any one of claims 1 to 3. Generating electricity between the cathode and the anode;
The hydrogen production apparatus according to any one of claims 1 to 4. Introducing water;
Introducing a reducing gas;
Electrolyzing the water into hydrogen and oxygen;
Separating and removing the hydrogen from the water;
Reacting the reducing gas with the oxygen;
Hydrogen production method. A hydrogen production apparatus according to any one of claims 1 to 5;
A fuel cell that introduces the produced hydrogen and generates electricity;
Fuel cell power generator.

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