JP3921300B2 - Hydrogen generator - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a hydrogen generator for generating electrolytic hydrogen from methane gas at a low temperature and a simple structure in an energy-saving manner.
[0002]
[Prior art]
Air pollution prevention problems stemming from environmental problems, and CO₂The problem of reduction is changing the power of automobiles, which are transportation means, to so-called electric cars that move an efficient electric motor from an internal combustion engine that uses fossil fuel as fuel. Conventionally, this representative one is an electric vehicle in which a secondary battery is stacked and used as a fuel source. Such an electric vehicle has the feature that it does not pollute the environment without exhaust gas while driving, but with the fact that the power source is power plant power and its energy efficiency is not very good, There are cases where the weight is extremely large, the electric vehicle needs a lot of power to carry the secondary battery, and the mileage on a single charge is less than the usual mileage. There was a problem in use.
[0003]
A hybrid vehicle with an internal combustion engine and a secondary battery that reduces battery weight, eliminates the need for charging with external power, and successfully solves the characteristic that the fuel consumption rate changes significantly with the addition of the internal combustion engine by hybridizing it with the battery. Began to be used. However, this hybrid vehicle has a significant NO_xDecline and CO₂Although the reduction has been achieved, the structure is complex, and it is regarded as an intermediate stage toward higher efficiency through future electrification.
[0004]
The final target is an electric vehicle that uses power generated by a fuel cell and an electric motor that operates with that power. However, the fuel cell itself has been improved to a considerable extent, and the remaining portion has come to the point of cost reduction, but the supply of hydrogen as a fuel has become a problem. That is, there are a method of extracting hydrogen from a fuel such as methanol by a reformer and a method of supplying hydrogen at a hydrogen gas stand. Especially in the latter case, hydrogen filling consumes a certain amount of hydrogen for cooling by itself, so as in the current gas station, hydrogen is transported from the outside and filled into the stand, which is further added to each car. There was a problem that filling would be a disadvantage in terms of basic unit and cost. Therefore, solving this hydrogen problem was a big homework.
[0005]
On the other hand, it seems that there is no problem in putting a reformer on a car.₂The generation of CO2 is not always efficient, and the consumption of methanol and natural gas, which are hydrogen sources, increases due to the heating of the reformer itself and the recombustion of the produced CO. It is said that the economy is also worsened, and there is a problem that a cold start cannot be made. At present, the technology for maintaining hydrogen gas in automobiles is being established. If hydrogen can be supplied while making it on-site on a stand, and if it can be supplied efficiently and inexpensively, some of these problems will be solved. In this case as well, high-purity electrolytic hydrogen is most desirable because it can be used as it is on the automobile side.
[0006]
Recently, high-purity hydrogen is required for generator bearing cooling and electronic material production. Currently, it is transported in a cylinder, but it is a batch operation. There were problems, such as sometimes dangerous. In such a place, there was a movement to introduce a part of the conventional electrolytic hydrogen apparatus in order to use electrolytic hydrogen, but the electrolytic voltage is considerably high from 1.8 V to 2.4 V, so there is a problem in economy. Even in such a place, it has been required economically and the purity of hydrogen is equivalent to that of electrolytic hydrogen.
[0007]
[Problems to be solved by the invention]
In order to produce electrolytic hydrogen with extremely small electric power, a method for improving the performance of the electrolyzer itself has been performed. This can be seen as a national project in the so-called WE-NET and RITE plans, which use a normal water electrolysis device of the solid electrolysis chamber type, with the idea of minimizing the loss there. is there. However, under normal conditions, there is a problem that the theoretical decomposition voltage cannot be reduced below 1.23V. Economically, hydrogen is produced using overseas hydropower and used as a storage medium to reduce CO2 generation. It is going to be used as a plan to say. Although it is more economical than the conventional electrolytic hydrogen generator, it still has the problem that the power consumption is large, and if the fuel cell is operated with this hydrogen, the generated power will be less than half of the power consumption. .
[0008]
On the other hand, it has been proposed to use a halogen reaction whose theoretical decomposition voltage is lower than that of oxygen generation for the anodic reaction. As can be seen in US Pat. Nos. 5,219,671 and 5,443,804, electrolysis is performed using hydrogen halide as an electrolytic solution to obtain halogen and hydrogen in the cathode chamber. The theoretical decomposition voltage is 1.04 V in the case of bromic acid with respect to 1.24 V of water, and the anode overvoltage is almost zero in the case of bromine generation. The voltage can be reduced by about 5V. The bromine produced there is considered to be able to react with natural gas or methanol to return it to a halogen acid and to be used again as an electrolytic raw material. This method is good for power reduction, but has a drawback that the structure becomes complicated and hydrogen production cannot be performed with sufficiently low power. In addition, it requires a high temperature for the conversion to halogen acid. Overall, it is complicated in terms of equipment. At the same time, considering its operation, it is difficult to become an on-site generator. It was.
The present invention has been made to solve the above problems, and an object of the present invention is to provide an apparatus for producing electrolytic hydrogen that is low in temperature and extremely reduces power consumption.
[0009]
[Means for Solving the Problems]
As a result of diligent research to solve the above-mentioned problems, the present inventor sends natural gas mainly composed of methane to the anode as a supply gas in order to obtain electrolytic hydrogen at an extremely low voltage, and generates CO 2₂H₂It has been found that separation is extremely important for an energy-saving hydrogen generator that generates hydrogen at the anode while keeping the anode potential very low, and the present invention has been completed.
That is, this invention consists of the following structures.
[0010]
(1) In a hydrogen generator that is separated into an anode chamber and a cathode chamber by a diaphragm and generates hydrogen from the cathode using an acidic electrolyte, a gas diffusion electrode that supplies methane gas as an anode is used.CO ₂ Is generated,A hydrogen generator characterized in that a porous cathode is brought into close contact with a diaphragm and an electrolyte is supplied between the electrodes.
(2) The hydrogen generator according to (1), wherein a gas-liquid separation mechanism for separating the catholyte and the generated hydrogen gas is provided on the cathode side.
(3)A rectifying plate for venting was installed between the diaphragm and the gas diffusion electrode.The hydrogen generator according to (1) above, wherein
(4)Supply natural gas as methane gasThe hydrogen generator according to (1) above, wherein
[0011]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail.
The electrode reaction in the present invention is
Anode (fuel electrode) CH_Four+ 2H₂0^-→ CO₂+ 8H⁺+ E (E₀= 0.16V)
Cathode 2H⁺+ 2e^-→ H₂                  (E₀= 0.0V)
The theoretical decomposition voltage is 0.16V, which is characterized by being extremely small compared to the theoretical decomposition voltage of 1.24V in ordinary water electrolysis.
The idea here is that a small amount of electric power is applied from methane, which is a natural gas, as a reformer for oxygen generation by changing the reaction to an electrochemical reaction instead of the heat required for a normal reformer. It is also possible. In the reaction using a normal gas diffusion electrode, no gas is generated in the gas diffusion electrode.₂Therefore, a device different from a normal gas diffusion electrode is necessary, and as a result of these studies, the present invention has been achieved.
[0012]
That is, the electrolytic cell is separated into two chambers, an anode chamber and a cathode chamber, by a diaphragm. The main purpose is to generate CO from the anode.₂It is to separate hydrogen gas, which is a product generated at the gas and the cathode. Since the electrolytic solution is basically the same, any diaphragm may be used as long as it has a gas separation ability. As an example, a filter cloth made of polypropylene or the like is used, but if it is thick, the electrical resistance increases. Therefore, if it can achieve the purpose, it is preferably as thin as possible. An apparent thickness of about 0.1 mm to 0.3 mm seems to be good. Moreover, in order to make it thin, a porous fluororesin film | membrane etc. can be used. Since the ion exchange membrane itself has ionic conductivity, it is a desirable material, but it is expensive, and for this purpose it does not require an ion exchange effect, so it is not particularly necessary. But of course you can use it. Thus, a gas diffusion anode is installed in the anode chamber of the electrolytic cell separated into two chambers.
[0013]
The type of the gas diffusion anode is not particularly limited.₂In this case, it is desirable to use a so-called semi-hydrophobic gas diffusion electrode. That is, the gas diffusion electrode has a hydrophilic layer as a reaction part and a hydrophobic layer as a gas diffusion layer that separates liquid and gas and controls the distribution of gas supply. A gas diffusion electrode having a porous, water-repellent porous fluororesin stretched on the side of the gas chamber on the hydrophobic layer side is also preferably used. As the electrode material, a Pt / Ru alloy is preferably used because CO can be generated as a side reaction. The manufacturing method of these gas diffusion electrodes is not particularly limited, and may be performed by methods already introduced in many documents. For example, as the hydrophilic layer, a carbon black kneaded so that the PTFE resin is 40% (volume, hereinafter the same) or less is used, and this is coated on the core material of a corrosion-resistant metal mesh that is a core material, To.
[0014]
On the other hand, the hydrophobic layer is made of carbon black and a paste kneaded so that the PTFE resin is 60% or more, and this is also made into a sheet, but here it is stretched on the hydrophilic layer sheet to combine the hydrophilic layer and the hydrophobic layer. Bake with a hot press to make an electrode sheet. Hot press conditions are pressures from 0.1 to 10 kg / cm²The temperature is 100 to 300 ° C. When a porous PTFE sheet is attached, this sheet may be hot pressed together. In consideration of power supply, normal porous PTFE sheet is an insulator, and uniform power supply from the back side is impossible. Therefore, it is necessary to use conductive PTFE resin impregnated with conductive material such as graphite in PTFE. desirable. An electrode material, for example, a salt solution in which platinum and ruthenium are mixed at a predetermined ratio is applied to the hydrophilic layer side of the electrode body thus formed, and 200 to 350 ° C. in a reducing atmosphere such as hydrogen gas. A gas diffusion electrode can be obtained by pyrolyzing with the above.
[0015]
Of course, the electrode material may be any electrode material effective for oxidation of natural gas mainly composed of methane, platinum group metal oxides such as iridium oxide and ruthenium oxide, pyrochlore type oxides containing these, Perovskite oxides that are corrosion resistant in acidic solutions are used. These supporting methods are not particularly limited, and those previously supported on carbon black particles may be applied with a hot press at the time of electrode production, or may be a normal pyrolysis method, and there are methods suitable for electrode materials. Can be adopted. At this time, however, special care must be taken so as not to damage the gas diffusion electrode body. The gas diffusion electrode thus produced is installed in the anode chamber together with the current collector. The current collector material is not particularly limited, but in order to prevent insufficient supply of gas by pressing the current collector against the gas diffusion electrode, there is little contact with the current collector, and power is effectively supplied. In order to be able to do it, a metal, for example, a knitted mesh of a metal wire, is good.
[0016]
The material of the current collector is not particularly limited, but a corrosion resistant alloy called trade name Hastelloy with titanium or silver plating is used. This is because the anode side potential is almost zero, and even if it is hydrophobic, the electrolytic solution may ooze out into the gas chamber through the gas diffusion electrode, so it is desirable to have corrosion resistance against this. A gas diffusion electrode backed with a porous fluororesin serves as a support, not as a current collector, but the material is the same. In this case, the power supply is performed through a metal mesh which is a support material in the electrode. If the metal mesh is not contained as a support material in the gas diffusion electrode itself, the electrical conductivity is not necessarily good, so the current collector must be able to distribute the current evenly with as fine an eye as possible. .
[0017]
For installation in the electrolytic cell, in the case of this gas diffusion electrode, gas generation, that is, CO₂Therefore, it is necessary to create a gas venting space between the diaphragm and the gas diffusion electrode. This space should be as small as possible in terms of electrical resistance.₂Since gas tends to have a relatively large bubble, it is desirable to take into consideration that it is about 0.5 to 2 mm. In order to maintain this distance, it also serves as a spacer between the diaphragm and the gas diffusion electrode. It is desirable to provide a rectifying plate for venting gas.
[0018]
On the other hand, it is desirable that the cathode side has a hydrogen generation overvoltage as small as possible, and a so-called activated cathode in which an electrode material is formed on the surface of a porous body having a three-dimensional form is used. Although the material is not particularly limited, since it is used in an acidic atmosphere, it is desirable to have resistance to the material. For metals, titanium, silver, copper, or the like is used. However, it should be noted that titanium may be in a subtle potential range of corrosion and stability due to the potential relationship during energization. Silver and copper are relatively stable, but if chloride ions are contained in the electrolytic solution, they may be corroded, so it is necessary to select them according to the electrolytic solution. As a more stable cathode material, there is a sheet obtained by sintering carbon using PTFE resin as a binder. This can be made porous by selecting carbon particles, and since hydrogen bubbles are extremely small, even porous bodies that seem to be dense can be used as porous bodies with almost no problems. You can also.
[0019]
However, in any base material, it is necessary to form and activate an electrode material on these surfaces to minimize the hydrogen overvoltage. As a typical example, a silver foam obtained by electrodepositing silver on urethane foam and then removing the urethane foam by incineration is used as a base material, and a material whose porosity is about 70 to 40% by pressing is used as a base material. An active silver fine powder having an average particle diameter of 1 μm or less is coated with a PTFE resin as a binder and fixed at 150 to 300 ° C. This works effectively in dilute sulfuric acid aqueous solution as an electrolyte, and the overvoltage becomes almost zero. The cathode thus prepared is attached in close contact with the diaphragm. In the case of the cathode, unlike the anode, it is observed that the removal of the bubble is hardly a problem because of the size of the hydrogen bubble, and the voltage decreases as the distance from the anode becomes shorter. The cathode is preferably a metal, but in the case of carbon or the like, its own electrical conductivity is not sufficient and voltage loss due to electrical resistance is likely to occur. A fine metal expanded mesh, a knitted mesh, or a sintered metal wire is used.
[0020]
Electrolysis is performed using an electrolytic cell incorporating these to obtain electrolytic hydrogen, but the electrolytic solution must be an acid. That is, in the case of an alkaline solution, CO generated on the anode side₂This is because there is a possibility that carbonate having low solubility is generated and the electrolytic cell and the electrode are blocked. Therefore, it is desirable to use dilute sulfuric acid, which is an acid having good conductivity and no excessive reaction, as the electrolyte. The concentration is not particularly limited, but usually 3N to 5N is desirable, and if it is lower than 3N, the electric conductivity tends to be insufficient, and if it is higher than 5N, the corrosiveness increases, which causes problems in the electrolytic cell and electrode materials. there is a possibility. Of course, it is also effective means to add a salt such as sodium sulfate and keep it acidic to the extent that carbonate is not formed. This is rather desirable.
[0021]
From the viewpoint of the action on the gas diffusion electrode, it is desirable that the temperature be higher, and the temperature may be any condition that does not cause the electrolyte to boil. For example, it is desirable to perform electrolysis at a temperature of about 100 ° C. to 120 ° C. by applying a pressure of about 2 to 3 atm to the electrolytic cell. However, the present invention is not limited to this, and it is most desirable if the gas diffusion electrode can be electrolyzed with a sufficiently low overvoltage and with minimal side reactions.
It is desirable to make the device so that it can withstand a certain amount of pressure. Even if the pressure is not applied from the outside, it can be easily applied if the generated gas itself is about 10 atm. Therefore, it is desirable that the apparatus has a sufficient pressure resistance.
[0022]
The electrolyte solution is supplied on the cathode side. The anolyte may be a liquid that oozes from the cathode side through the diaphragm, and for this purpose, the diaphragm is preferably a liquid-permeable type and excellent in gas separation function. Of course, a liquid circulation mechanism may be provided on the anode side. Although the liquid is circulated in the cathode chamber, hydrogen gas bubbles generated on the cathode side are extremely small, so that separation from the liquid tends to be insufficient. Therefore, it is desirable to provide a gas-liquid separation mechanism on the cathode side. The structure may be anything and may be a simple tank, but as described above, it must be able to withstand pressure. Also, almost pure CO from the anode chamber side₂Although gas comes out, it is not released into the atmosphere due to environmental problems.₂In order to use gas, it is safe to attach a trap mechanism. However, even in this case, it is necessary to sufficiently consider the pressure.
[0023]
【Example】
Embodiments of the present invention will be described below with reference to the drawings. However, it goes without saying that the present invention is not limited to these examples.
[0024]
Example 1
FIG. 1 is a schematic explanatory diagram of an example of the hydrogen generator of the present invention. As the diaphragm 1, a filtration membrane (microfilter) made of a porous PTFE resin membrane having a thickness of 100 μm and an aperture of 2 μm was used, and a cathode 2 was adhered to one side thereof.
Cathode 2 is made by pressing a copper copper 1 mm thick apparently to a thickness of 200 μm with a press and silver plating on the surface of the copper base material. In addition, a material in which platinum was supported on one side surface by thermal decomposition was used. The platinum loading method was such that a butanol solution of chloroplatinic acid was applied to the surface and treated at 300 ° C. for 15 minutes in a hydrogen gas stream. This is repeated 10 times and the loading is 10 g / m²Got.
The above-described diaphragm 1 was brought into close contact with the platinum carrying side by hot pressing using a fluororesin ion exchange resin liquid (Dafon Nafion liquid) as a binder. The adhesion conditions are a temperature of 180 ° C. and a pressure of 2 kg / cm.²Met. The reason for using Nafion was that the sintering temperature was low, the electrical conductivity was not lost, and the porosity was easy to maintain.
[0025]
On the other hand, the gas diffusion electrode (anode) 3 is based on a commercially available gas diffusion electrode (trade name ELAT manufactured by E-TEK Co., USA), and carries a 1: 1 alloy of platinum and ruthenium on the hydrophilic layer side. used. The carrying method is the same as that of the cathode 2, and the coating solution is a mixed butanol solution of ruthenic acid chloride and chloroplatinic acid. The loading conditions are the same, and the total amount of platinum and ruthenium is 10 g / m after 10 repetitions.²It was made to become. A porous PTFE resin film having a thickness of 10 μm impregnated with graphite particles was attached to the hydrophobic layer side of the gas diffusion electrode 3 by hot pressing. The hot press conditions were the same as those of the cathode 2. As a result, power supply from the back side became possible, and separation of gas and liquid was completed.
The gas diffusion electrode and the cathode / diaphragm thus prepared were attached to an electrolytic cell 4 made of polypropylene. As the cathode-side current collector 5, a net-like body obtained by sintering titanium long fibers was baked in air at 450 ° C. to make the surface oxide, and was brought into close contact with the cathode surface. Further, the anode side current collector 6 used was a gold-plated surface of a knitted mesh formed by knitting a titanium wire having a wire diameter of 0.3 mm. In order to keep the distance between the diaphragm 1 and the diffusion electrode 3 constant, PTFE resin wires having a wire diameter of 1 mm were arranged as spacers 7 at 15 mm intervals in the vertical direction.
[0026]
On the cathode 2 side, a liquid supply mechanism 8 is provided below, and a liquid / gas discharge port 9 is provided on the ceiling. The liquid / gas discharge port 9 is separated at the tip of the liquid / gas discharge port 9 by a cylinder with a pan. The gas-liquid separation mechanism 10 was attached, and the gas was evacuated upward and the liquid was taken out from the side and circulated. A valve 12 is attached to the pipe 11 on the degassing side so that the pressure can be adjusted. Similarly, a valve 14 is attached to the liquid side of the anode chamber 13 to generate CO.₂It was made possible to adjust the pressure. The entire system was made airtight so that the pressure could be adjusted as a whole.
[0027]
1NH from the cathode 2 side of the electrolytic cell 4 thus prepared.₂SO_FourNa in aqueous solution to 100g / liter₂SO_FourThe electrolytic solution 15 in which was dissolved was circulated. This is continued for about 1 hour, and after the liquid has sufficiently spread on both the anode 3 and cathode 2 sides, the anode gas 16 is CH._Four(Methane) was supplied and the temperature was raised while applying a slight voltage. When the temperature reaches 110 ° C., the current density is increased to 10 A / dm while gradually increasing the voltage.²It was made to become. Hydrogen from the cathode 2 side, CO from the anode chamber 13 liquid side₂The occurrence of was seen. Pressure is 2kg / cm²When the electrolysis was carried out while maintaining such that, the electrolysis voltage was 0.32V. The current efficiency of hydrogen generation is 93% to 96%, and CH_FourWas 125% of the theoretical amount.
[0028]
Example 2
An electrolytic cell 4 was made in the same manner as in Example 1. As the cathode 2, a sintered body of short titanium fibers was used, which was fired in air at 500 ° C. for 1 hour to oxidize the surface and then plated with ruthenium black on the surface of the diaphragm 1 side. Ruthenium black has a current density of 1 A / dm using a solution obtained by dissolving ruthenium chloride in 3N sulfuric acid so as to be 30 g / liter.²Obtained according to the formation conditions consisting of plating. Adhering amount is 10g / m²Met.
The anode 3 was prepared by kneading a 40% amount of PTFE resin in hydrophilic carbon black as a hydrophilic layer in accordance with a conventional method for producing a semi-hydrophobic gas diffusion electrode. % Kneaded with PTFE resin, using a knitted mesh surface of copper with a wire diameter of 0.2 mm as the electrifying and structural base material with gold plating, hydrophilic carbon black kneaded material on one side, A hydrophobic carbon black kneaded material was uniformly applied to the opposite surface to form a sheet, which was hot pressed to obtain an electrode. Hot press condition is pressure 5kg / m²The temperature was 300 ° C. for 30 minutes.
[0029]
An electrode material layer made of a 1: 1 alloy of ruthenium and platinum was formed on the hydrophobic layer side of the electrode in the same manner as in Example 1.
As the diaphragm 1, a 0.2-mm-thick polypropylene filter membrane is used, and as the cathode-side current collector 5, a copper expanded mesh plated with silver is used, and the anode-side current collector 6 is an electrode structure base material. Power was supplied to a certain copper mesh from the frame around the structure.
The electrode was fixed by applying the same metal knitted mesh as in Example 1 with a spring material in the middle to the back of the electrode. Further, a PTFE plate having a thickness of 0.75 mm was sandwiched between the diaphragm 1 and the gas diffusion electrode 3 so as to have an apparent thickness of 2 mm. The anode chamber 13 of the electrolytic cell 4 has 2NH₂SO_FourAn aqueous solution was supplied. The gas-liquid separator 10 is attached to the anode 3 side as in the first embodiment. A gas collector was attached to the anode chamber 13 gas.
[0030]
Pressure 2kg / cm², Current density 10A / dm²When electrolysis was performed at a temperature of 100 ° C., the voltage was 0.34 V, and the current efficiency of hydrogen generation was 93%. The pressure on the anode 3 side is 0.2 kg / cm from the cathode 2 side.²When increased, the current efficiency of hydrogen generation was improved to 95%. It was found that when both the cathode 2 and the anode 3 are at the same pressure, hydrogen passes through the diaphragm 1 to the anode 3. CO generated₂When the gas of₂In addition, about 1% hydrogen was mixed.
[0031]
【The invention's effect】
The following effects were recognized by the present invention.
(1) As a reformer of methane gas, electrolytic hydrogen was obtained by supplying a small amount of electricity by electrolysis instead of the conventional high-temperature pyrolysis type.
(2) It was found that the driving conditions were extremely mild and the driving was easy.
(3) Since the pressure and temperature may be low and the generated hydrogen is electrolytic hydrogen, it can be easily used as an on-site hydrogen generator, and from the purity of the generated hydrogen, there is almost no need for post-treatment. It turns out that it is obtained.
(4) Since it is high-pressure hydrogen of several atmospheres, it turned out that it can be used without a pressure | voltage riser.
(5) CO from the anode side₂However, since it can be used because of its high purity, it does not have to be released to the outside as it is, so it does not affect the problem of global warming.
As described above, according to the present invention, the above-described various effects were obtained, and a highly practical hydrogen generator for on-site use was obtained.
[Brief description of the drawings]
FIG. 1 is a schematic cross-sectional view showing an example of a hydrogen generator of the present invention.
[Explanation of symbols]
1 Diaphragm
2 Cathode
3 Gas diffusion electrode (anode)
4 Electrolysis tank
5 Current collector on the cathode side
6 Anode-side current collector
7 Spacer
8 Liquid supply mechanism
9 Liquid / gas outlet
10 Gas-liquid separation mechanism
11 Degassing pipe
12 Valve
13 Anode chamber
14 Valve
15 Electrolyte
16 Methane gas

Claims (4)

In a hydrogen generator that is separated into an anode chamber and a cathode chamber by a diaphragm and generates hydrogen from a cathode using an acidic electrolyte, a gas diffusion electrode that supplies methane gas is used as an anode, CO ₂ is generated, and porous A hydrogen generator characterized in that a cathode is in close contact with a diaphragm and an electrolyte is supplied between the electrodes.   2. The hydrogen generator according to claim 1, wherein a gas-liquid separation mechanism for separating the catholyte and the generated hydrogen gas is provided on the cathode side. The hydrogen generator according to claim 1, wherein a rectifying plate for venting gas is provided between the diaphragm and the gas diffusion electrode . 2. The hydrogen generator according to claim 1, wherein natural gas is supplied as methane gas .

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