JP2000327302A - Method and apparatus for producing high-purity hydrogen - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method and an apparatus for producing high-purity hydrogen by a reforming of hydrocarbon capable of solving a problem in a conventional technique. SOLUTION: This apparatus is equipped with at least one reforming chamber 12 provided with a reforming catalyst bed 13, at least one hydrogen permeation thin film tube 14 which is built in the reforming chamber 12 so as to form a hydrogen gas isolation space 16 and permeates a hydrogen gas generated in the reforming catalyst bed 13 into the hydrogen gas isolation space 16 and at least one oxidation chamber 22 which is arranged closely to the reforming catalyst bed 13, provided with an oxidation catalyst bed 23 in the interior of the chamber, at least partially isolated from the thin film tube 14 by the reforming catalyst bed 13, burns an impermeable gas in the thin film tube 14 and supplies heat to the reforming chamber 12. A high-purity hydrogen is produced by the apparatus.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method and an apparatus for producing high-purity hydrogen by steam reforming of carbonaceous fuel, and the apparatus includes an oxidation chamber provided with a hydrogen-permeable thin-film tube and an oxidation catalyst bed.

[0002]

2. Description of the Related Art Techniques for producing hydrogen gas from hydrocarbons or carbonaceous fuels, such as methanol, ethanol, gasoline, petroleum and the like, by steam reforming for various different applications have been disclosed. In particular, the present invention is to generate hydrogen gas by steam reforming of carbonaceous fuel and supply it to electric vehicles and fuel cells used for power generation at factory sites.

[0003] Steam reforming of hydrocarbons or carbonaceous fuels, such as methanol, is a type of reversible and endothermic reaction, so it is necessary to provide heat to promote the reaction and make it react in equilibrium. Since the yield of the steam reforming reaction can reach the maximum only when the reaction is in an equilibrium state, and the yield is relatively low at a low temperature, the steam reforming reaction is usually required to obtain a sufficient hydrogen gas yield. It is necessary to raise the temperature to 700-900 ° C. Such a high reaction temperature can be lowered while maintaining the original yield by extracting one of the products in the reaction process and breaking the equilibrium state of the reaction.

Heretofore, hydrogen gas obtained by steam reforming of carbonaceous fuel generally has a purity of about 70%, and unless this purity is further advanced to about 96%, it is technically and economically necessary. Not suitable for fuel cells.

As is found in the semiconductor industry, high-purity hydrogen gas can be obtained by using thinner palladium or palladium alloy thin films. However, since the hydrogen gas permeability of these thin films is low, it is necessary to increase the surface area. Costly, and not economically viable on an industrial scale. In particular,
For use in a high temperature or high pressure environment, the thickness of the metal thin film is usually too thin to have sufficient mechanical strength.

US Pat. No. 5,451,386 discloses a tubular porous ceramic carrier obtained by depositing a palladium metal layer on the inner peripheral surface of a kind of tubular porous ceramic carrier. In comparison, the use of this type of thin film provides a relatively high hydrogen gas permeation rate and selectivity, and such a thin film is relatively excellent when, for example, hydrogen gas is separated at a high temperature, for example, for promoting the decomposition of ammonia. With mechanical strength. Although the ceramic carrier can be used under high temperature and high pressure, the thickness of the palladium metal layer thin film should be reduced so as not to cause any defects.
It must be at least 10 μm. However, in order to improve the permeation amount, it is necessary to rely on reducing the thickness of the palladium metal layer thin film, and the above-mentioned restriction hinders the improvement in the permeation amount of hydrogen gas.

According to the disclosure of Buxbaum et al. In the above-mentioned US patent specification, when extracting hydrogen gas with a 2 μm-thick palladium thin film deposited on a niobium disk, 500 ° C.
At the above temperature, the niobium metal diffuses into the palladium metal, and the hydrogen gas cannot pass through the palladium thin film and loses its function.

Further, US Pat. No. 5,741,474 discloses that a hydrocarbon and / or an oxygen atom-containing hydrocarbon is reformed to form a hydrogen-containing reformed gas, and then the hydrogen gas is separated from the reformed gas. A system for producing high-purity hydrogen gas is disclosed, comprising a reforming chamber equipped with a catalyst used for steam reforming and partial oxidation, and a hydrogen separation membrane, such as palladium or a palladium-silver alloy. The heat generated by the partial oxidation and the heat generated by burning the impermeable gas sustain the reforming reaction. However, burning the impervious gas requires additional fuel to be burned, and at the same time, the combustion is often carried out at very high temperatures; Must be prevented from escaping, and the combustion of the impermeable gas is not necessarily released after conversion to such an extent that no polluting gas is completely generated.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method and an apparatus for producing high-purity hydrogen by reforming hydrocarbon or carbonaceous fuel, in which the above-mentioned problems have been solved.

[0010]

In order to achieve the above object, the present invention provides an apparatus for producing high-purity hydrogen by steam reforming of carbonaceous fuel according to the present invention. A reforming chamber provided with a reforming catalyst bed for producing hydrogen, and the reforming chamber is provided in the reforming chamber so as to form a hydrogen gas isolation space covered with the reforming catalyst bed, and is formed in the reforming catalyst bed. At least one hydrogen gas permeable thin-film tube capable of transmitting the hydrogen gas into the hydrogen gas isolation space, and provided in close contact with the reforming catalyst bed, and provided with an oxidation catalyst bed therein. An oxidation chamber, which is at least partially separated from the thin-film tube, and burns the impermeable gas of the thin-film tube and supplies heat to the reforming chamber.

Further, according to the method of the present invention for producing high-purity hydrogen by steam reforming of carbonaceous fuel, a reforming chamber equipped with a reforming catalyst bed is provided, and the reforming chamber is covered with the reforming catalyst bed. Providing a hydrogen gas permeable thin film tube so that a hydrogen gas isolation space is defined by the thin film tube; providing an oxidation chamber in close contact with the reforming chamber; and providing an oxidation catalyst bed in the oxidation chamber. Supplying a mixture containing a carbonaceous fuel into the reforming catalyst bed and performing a steam reforming reaction to generate hydrogen gas and other reformed gases. A step of extracting hydrogen gas and a step of introducing the other reformed gas into the oxidation chamber to perform catalytic oxidation, and converting the other reformed gas into a non-polluting gas.

Preferably, the hydrogen gas permeable thin film used in the present invention comprises a porous substrate and a thin metal layer, wherein the metal layer is selected from the group consisting of palladium and a palladium alloy. Located on the material surface. The porous substrate is selected from the group consisting of a porous stainless steel material and a porous ceramic material, the thickness of the substrate is in a range of about 0.5 mm to 2 mm, and the thickness of the metal layer is about 1 to 2 mm. It is in the range of 20 μm.

The reforming catalyst bed comprises a copper-based catalytic material,
The oxidation catalyst bed is selected from the group consisting of iron-based catalyst materials and nickel-based catalyst materials, and the oxidation catalyst bed comprises the group consisting of palladium and platinum catalysts. The steam reforming reaction of carbonaceous fuel can be performed in the range of 250-550 ° C, and the reformed hydrogen gas is extracted under the membrane permeation pressure difference of 2-20atm (0.20-2.0MPa) . The carbonaceous fuel is selected from the group consisting of methanol, ethanol, gasoline, petroleum and mixtures thereof, and the mixture delivered to the reforming chamber of one embodiment of the present invention contains methanol and steam;
The methanol has a WHSV of 0.5 to 30 h ^-1 (weight hourly space velocity (Wei
ght Hourly Space Velocity)) and the molar ratio of steam to methanol is 1: 2.

In the present invention constructed as described above, since the oxidation catalyst bed is used in the oxidation chamber, the carbonaceous fuel and the impermeable reformed gas are oxidized at a relatively low temperature to generate heat in the reforming chamber. In addition to being able to be supplied, the impervious reformed gas can be completely converted into a non-polluting gas and discharged, so that no extra device is required for treating the impervious reformed gas.

Further, by improving the hydrogen gas permeation flow rate, the reforming temperature and the pressure difference between both sides of the thin film can be reduced to relatively low levels. Conversion can be increased, and in extreme cases can be increased to over 90%. Further, the entire reactor can be made of a relatively inexpensive material from the reduction of the reforming temperature and the pressure difference between both sides of the thin film, so that the heat energy can be reduced and the adverse effect on the mechanical strength and stability of the hydrogen gas permeable thin film can be reduced. At the same time, such a high hydrogen gas permeation flow rate may reduce the volume of the apparatus, and can be applied in connection with an electric vehicle or a fuel cell used for power generation at a factory site.

[0016]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be specifically described based on embodiments, but the present invention is not limited to these examples. As shown in FIG. 1, the apparatus according to the present invention is constructed as a single-jacketed tube type reactor 10, which defines a reforming chamber 12 inside an outer tube 11 serving as a casing, and defines an inner tube 14 therein. Hold concentrically. A reforming catalyst bed 13 is provided in the reforming chamber 12, and the inner tube 14 is surrounded and gripped by the reforming catalyst bed 13 in a state of being extended and fitted in a longitudinal direction. It is a thin film tube and partitions a hydrogen gas isolation space 16 inside.

[Embodiment 1] In this embodiment, a test was conducted by the equipment shown in FIG.
Is a support-type palladium thin-film tube in which the surface of a porous stainless steel carrier is subjected to electroless plating, and the porous stainless steel carrier was purchased from Mott Metallurgical Co., USA.
With a thickness of 0.5 mm and a filtration rating of 0.5 μm, the thickness of the palladium layer is about 15 μm. As a result of testing the installed supported palladium thin-film tube at various temperatures and pressures, the hydrogen gas permeation behavior of the supported thin-film tube was measured in terms of hydrogen gas permeability according to Sieverts' law. The range is about ^{3 to} 10 m ³ / m ² · h · atm ^0.5 , and the hydrogen gas selectivity range H ₂ / N ₂ is 100 to 5.000. Three types of supported palladium membrane tubes, each with a different membrane 1, membrane 2 and membrane 3, are used in some experiments.

In the experiment, hydrogen gas and nitrogen gas were
11 enters the reforming chamber 12 from one end, and the hydrogen gas in the reforming chamber continuously enters the hydrogen gas isolating space 16 due to the pressure difference between both sides of the thin film between the reforming chamber 12 and the hydrogen gas isolating space 16. The impermeable gas remaining in the reforming chamber 12 after being sucked out flows out of the outer tube 11.

Results under different temperatures and pressures of hydrogen gas permeation flow rate (hydrogen gas permeation flow rate per unit thin film surface area) and H ₂ / N ₂ selectivity (permeation ratio of single hydrogen gas to nitrogen gas). Are shown in Tables 1, 2 and 3. The permeate side (downstream) of the bearing membrane is maintained at atmospheric pressure. The pressure in units of atm in the table below is 0.101
Is converted to a value in MPa.

[0020]

[Table 1]

[0021]

[Table 2]

[0022]

[Table 3]

EXAMPLE 2 Using the equipment of FIG. 1 and the supported thin-film tube of Example 1, another test is conducted to study the hydrogen gas permeability of the supported thin-film tube. The operating temperature is 350 ° C, the concentration of hydrogen gas and the concentration of nitrogen gas are each 50%, and the internal pressure of the hydrogen gas isolation space is 1-2 atm (0.
10 ~ 0.20MPa), purity of hydrogen gas after permeation is 99.5%
It is. Table 4 shows the results of these tests.

[0024]

[Table 4]

Table 4 illustrates the feasibility of the high pressure operation in the hydrogen gas isolation space, which saves the energy required for compression in the subsequent step of injecting hydrogen gas into the pressure vessel. can do.

Example 3 The hydrogen gas outlet concentration of the single-jacket tube reactor 10 of FIG. 1 is compared with that of a conventional reactor having no thin-film tube.

As shown in FIG. 1, carbonaceous fuel and water are
Is fed into the reforming chamber 12 from one end, and a steam reforming reaction is performed by the reforming catalyst. The reformed hydrogen gas in the reforming chamber 12 is continuously extracted into the hydrogen gas isolation space 16 due to the pressure difference between both sides of the thin film between the reforming chamber 12 and the hydrogen gas isolation space 16 during the reforming process. Hydrogen gas not extracted into the gas isolation space 16 and residual gas in the reformed gas are exhausted as exhaust gas.

The single-jacket tube reactor 10
And the operating conditions of the conventional reactor are the same, the catalyst used for steam reforming is a copper-zinc catalyst, using Nissan Girdler product G66B. The operating temperature was 350 ° C, methanol was used as the raw material for steam reforming, and the amount of the raw material supplied to the reactor was 8h ^-1 WHSV (weight hourly space velocity), and the ratio of steam to carbon was 1.2: 1. It is. Table 5 shows the test results.

[0029]

[Table 5]

Compared with the conventional reactor, the apparatus of FIG. 1 of the present invention can directly produce substantially pure hydrogen gas, and the hydrogen gas produced by the conventional reactor must be further purified if it is pure hydrogen gas. I can't get it. It should be noted that the methanol conversion of the apparatus of FIG. 1 of the present invention is slightly higher than the conventional reactor.

FIG. 2 shows a double jacketed tube reactor 20 formed in accordance with the present invention, which, when compared to the single jacketed tube reactor 10 of FIG. twenty one
With the outer casing partitioning the oxidation chamber 22;
The oxidation chamber 22 includes an oxidation catalyst bed 23, and the oxidation catalyst bed 23 corresponds to the single-jacketed tubular reactor 10 of FIG.
Is coated. The oxidizing chamber 22 communicates with the reforming chamber 12 via a connecting device (not shown), and the opaque gas is oxidized and converted by the oxidizing chamber 22 and discharged as a non-polluting gas.

[Embodiment 4] The oxidation chamber of the double-jacketed tube reactor 20 shown in FIG. 2 and the oxidation catalyst Pd / Al in the inside thereof
Except for ₂ O ₃ , the double jacketed tube reactor 20 and the single jacketed tube reactor 10 of FIG. 1 are subjected to multiple tests under the same operating conditions.

A copper-zinc catalyst is used as a reforming catalyst bed. The reaction temperature and pressure in the reforming chamber were 350 ° C and 6 atm (0.61 MPa), respectively, and the feed rate of methanol was 8
h ^-1 WHSV and the ratio of water vapor to carbon is 1.2: 1. The air velocity for oxidizing the impermeable gas to the oxidation chamber 22 is 1200
^-1 GHSV (gas hourly space velocity). Table 6 shows the results of the test.

[0034]

[Table 6]

As shown in Table 6, the hydrogen gas and the carbon monoxide content of the gas discharged at the outlet of the double jacketed tube reactor 20 equipped with the oxidation catalyst 23 are greatly reduced.

Example 5 In this example, the effect of the methanol supply rate on the hydrogen gas generation rate was examined. The methanol supply rate WHSV and the material / membrane area ratio (the ratio of the methanol supply rate to the palladium thin film surface area ratio) ),
The experimental reactor and conditions in this example are the same as in Example 4. Table 7 shows the results of the test according to this example.

[0037]

[Table 7]

From the results shown in Table 7, it can be seen that the hydrogen gas generation rate decreases as the methanol supply rate increases.

Example 6 In this example, the effect of the material / membrane area ratio on the amount of hydrogen gas generated was examined. In addition to the methanol supply rate WHSV and the material / membrane area ratio, the experimental reactor was used. The conditions are the same as in Example 4. The results of the test are shown in Table 8.

[0040]

[Table 8]

It can be seen from Table 8 that the hydrogen gas generation rate doubles when the material / membrane area ratio is reduced by half.

Example 7 This example proves that the exhaust gas of a double-jacketed tube reactor is a non-polluting gas. Except for the methanol feed rate WHSV and the feed / membrane area ratio, it was used for experiments. The reactor and conditions were the same as in Example 4, and the results of the test are shown in Table 9.

[0043]

[Table 9]

Table 9 shows that the hydrogen gas and carbon monoxide in the impermeable gas in the reformed gas are completely converted and discharged as a non-polluting gas.

[Embodiment 8] In this embodiment, the relationship between the hydrogen gas generation rate and the reforming pressure is examined. In addition to the pressure in the reforming chamber, the experimental reactor and the conditions were the same as those in the above-mentioned Embodiment 4. Similarly, the results of the test are shown in Table 10.

[0046]

[Table 10]

From Table 10, it can be seen that the hydrogen gas generation rate increases as the reaction pressure increases.

[Embodiment 9] In this embodiment, the relationship between the hydrogen gas generation rate and the reforming temperature was examined. In addition to the temperature inside the reforming chamber, the experimental reactor and conditions were the same as those in the above embodiment. Table 4 shows the results of the test.

[0049]

[Table 11]

It can be seen from Table 11 that the hydrogen gas generation rate increases as the reaction temperature increases.

As shown in FIG. 3, the multi-jacketed tubular reactor 30 includes an outer casing 31 which defines an oxidation chamber used to accommodate an oxidation catalyst bed 33 and includes four outer casings. Each of the tubular members 34 is housed in the oxidation chamber 32 and covered with the oxidation catalyst bed 33.
34 is a reforming catalyst bed 35 and a hydrogen gas permeable thin film tube 14
And the thin film tubes 14 are isolated by the oxidation catalyst bed 33.

FIG. 4 shows another multi-jacketed tubular reactor 40 for producing hydrogen gas formed according to the present invention, the multi-jacketed tubular reactor 40 having an outer casing 41. The outer casing
41 defines a reforming chamber 42 filled with a reforming catalyst bed 43,
The tubular members 45 are provided at predetermined intervals in the reforming chamber 42,
Each of the tubular members 45 further defines an oxidation chamber 46 in which an oxidation catalyst bed 47 is provided, and a plurality of thin film tubes 14 are provided in the reforming catalyst bed 43 at predetermined intervals. ,
The thin film tubes 14 are isolated by the oxidation catalyst bed 47.

[0053]

According to the present invention having the above-described structure, the carbonaceous fuel and the impermeable reformed gas can be oxidized at a relatively low temperature to supply heat to the reforming chamber, while the impermeable reformed gas is completely oxidized. It can be converted to non-polluting gas and discharged, and there is no need to provide extra equipment for treating the impermeable reformed gas.
In addition, since the reforming temperature and the pressure difference between both sides of the thin film can be reduced to a relatively low level by providing a high hydrogen gas permeation flow rate, the conversion rate of the carbonaceous fuel or hydrocarbon is increased, and the reforming temperature and the pressure across the thin film are increased. The overall reactor can be made of relatively inexpensive materials due to the reduced difference, which can reduce the heat energy, reduce the adverse effect on the mechanical strength and stability of the hydrogen gas permeable thin film, and especially reduce the volume of the equipment to a smaller size It can be connected to a fuel cell and applied to electric vehicles and factory power generation.

[Brief description of the drawings]

FIG. 1 is a longitudinal sectional view of a single-jacket tube reactor of the present invention.

FIG. 2 is a longitudinal sectional view of the double-jacketed tube reactor of the present invention.

FIG. 3 is a cross-sectional view of the multi-jacket tube reactor of the present invention.

FIG. 4 is a cross-sectional view of another multi-jacketed tube reactor of the present invention.

[Explanation of symbols]

 10 ... Single-jacket tube reactor 11 ... Outer tube 12 ... Reforming chamber 13 ... Reforming catalyst bed 14 ... Hydrogen gas permeable thin film tube 16 ... Hydrogen gas isolation space 21 ... Outer casing 22 ... Oxidation chamber 23 ... Oxidation catalyst bed

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[Procedure amendment]

[Submission date] July 25, 2000 (2007.2
5)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claims

[Correction method] Change

[Correction contents]

[Claims]

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (Reference) C01B 3/38 C01B 3/38 // H01M 8/06 H01M 8/06 G (72) Inventor Ray Min-Hong Taiwan, Taipei, Thin-High, 4 Toan, 101 Cyan, 140 Non, 64 How to 8 F Term (Reference) 4D006 GA41 HA28 JA26A KA01 KA15 KB30 KE03P KE05P KE06R KE08P KE12P KE13P KE16R MA02 MA06 MA22 MA31 MB03 MB04 MC02X MC03 PA01 PB18 PB20 PB66 PC69 PC80 4G040 EA02 EA03 EA06 EB12 EB33 EB44 EB46 EC01 EC03 EC08 4G069 AA01 AA02 AA11 BA13A BA13B BA18 BB02A BB02B BC31A BC31B BC35B BC66A BC68A BC72A BC07A01 BC17A02 BC17B01A02

Claims (25)

[Claims] At least one reforming chamber in which a reforming catalyst bed for generating hydrogen gas by steam reforming a carbonaceous fuel by the catalytic action thereof is provided; At least one hydrogen gas permeable thin film tube which is provided in the reforming chamber so as to form a gas isolation space and is capable of transmitting hydrogen gas generated in the reforming catalyst bed into the hydrogen gas isolation space; The reforming catalyst bed is provided in close contact with the porous catalyst bed, and is separated from the thin-film tube by at least a portion of the reforming catalyst bed while holding the oxidation catalyst bed therein. An apparatus for producing high-purity hydrogen, comprising: at least one oxidation chamber for supplying the chamber. 2. An outer casing comprising: a tubular member concentrically disposed within the outer casing; the tubular member defining a reforming chamber and accommodating a reforming catalyst bed; 2. The height of claim 1, wherein the oxidizing chamber is provided between the outer casing and the tubular member to accommodate the oxidation catalyst bed. Purity hydrogen production equipment. 3. A reforming catalyst bed housed in a reforming chamber defined by an outer casing and a plurality of tubular members extending longitudinally in the outer casing at a predetermined distance from each other. Covers a plurality of thin-film tubes, the plurality of thin-film tubes extend longitudinally into the reforming chamber at a predetermined interval from each other, and the plurality of tubular members are arranged at appropriate intervals with the plurality of thin-film tubes. The apparatus for producing high-purity hydrogen according to claim 1, wherein the tubular member defines a plurality of oxidation chambers by being coated on the reforming catalyst bed. 4. An outer casing and a plurality of tubular members extending longitudinally in the outer casing at a predetermined distance from each other, the tubular members defining a plurality of reforming chambers, and the outer casing is Defining an oxidation chamber, the oxidation catalyst bed covering the tubular member and the reforming catalyst bed in the tubular member,
The apparatus for producing high-purity hydrogen according to claim 1, wherein each tubular member contains at least one thin-film tube, and the reforming catalyst in each tubular member covers the thin-film tube. 5. The apparatus for producing high-purity hydrogen according to claim 1, wherein the hydrogen gas-permeable thin-film tube includes a porous substrate and a thin metal layer located on the porous surface. 6. The apparatus for producing high-purity hydrogen according to claim 5, wherein the porous substrate comprises a porous stainless steel. 7. The apparatus for producing high-purity hydrogen according to claim 5, wherein the porous substrate comprises a porous ceramic material. 8. The apparatus for producing high-purity hydrogen according to claim 6, wherein the thin metal layer is selected from the group consisting of palladium and a palladium alloy. 9. The apparatus for producing high-purity hydrogen according to claim 7, wherein the thin metal layer is selected from the group consisting of palladium and a palladium alloy. 10. The thickness range of the porous substrate is 0.5-2.
The high-purity hydrogen producing apparatus according to claim 5, wherein the thickness of the thin metal layer is 1 to 20 µm. 11. The high-purity catalyst according to claim 1, wherein the reforming catalyst bed is selected from the group consisting of copper as a main catalyst material, iron as a main catalyst material and nickel as a main catalyst material. Hydrogen production equipment. 12. The apparatus for producing high-purity hydrogen according to claim 1, wherein the oxidation catalyst bed is selected from the group consisting of palladium and platinum. 13. A reforming chamber equipped with a reforming catalyst bed is provided, and a hydrogen gas permeable thin film tube is provided in the reforming chamber so as to be covered with the reforming catalyst bed. A step of partitioning an isolated space; a step of providing an oxidation chamber in close contact with the reforming chamber; and a step of installing an oxidation catalyst bed in the oxidation chamber; and supplying a mixture containing a carbonaceous fuel into the reforming catalyst bed. Performing a steam reforming reaction to generate hydrogen gas and other reformed gas; extracting hydrogen gas from the hydrogen gas isolation space; and supplying the other reformed gas to the oxidation chamber. Introducing a catalytic oxidation to convert the other reformed gas into a non-polluting gas. 14. The method for producing high-purity hydrogen according to claim 13, wherein the hydrogen gas-permeable thin-film tube comprises a porous substrate and a thin metal layer located on the porous surface. 15. The method for producing high-purity hydrogen according to claim 14, wherein the porous substrate comprises a porous stainless steel material. 16. The method for producing high-purity hydrogen according to claim 14, wherein the porous substrate comprises a porous ceramic material. 17. The method for producing high-purity hydrogen according to claim 15, wherein the thin metal layer is selected from the group consisting of palladium and a palladium alloy. 18. The method for producing high-purity hydrogen according to claim 16, wherein the thin metal layer is selected from the group consisting of palladium and a palladium alloy. 19. The thickness range of the porous substrate is 0.5 to 2
15. The method for producing high-purity hydrogen according to claim 14, wherein the thickness of the thin metal layer is 1 mm to 20 mm. 20. The production of high-purity hydrogen according to claim 13, wherein the reforming catalyst bed is selected from the group consisting of copper as a main catalyst material, iron as a main catalyst material and nickel as a main catalyst material. Method. 21. The method for producing high-purity hydrogen according to claim 13, wherein the oxidation catalyst bed is selected from the group consisting of palladium and platinum. 22. The method for producing high-purity hydrogen according to claim 13, wherein the steam reforming reaction is performed in a temperature range of 250 to 550 ° C. 23. The hydrogen gas is supplied at 2 to 20 atm (0.20 to 2.
14. The method for producing high-purity hydrogen according to claim 13, wherein the extraction is performed with a permeation pressure difference in the range of 0 MPa). 24. The method for producing high-purity hydrogen according to claim 13, wherein the carbonaceous fuel is selected from the group consisting of methanol, ethanol, gasoline, petroleum, and a mixture thereof. 25. The mixture comprises methanol and water vapor, the methanol having a feed rate (WHSV) of 0.5 to 30 h ^-1.
And the molar ratio of the steam to the methanol is 1: 2
25. The method for producing high-purity hydrogen according to claim 24, wherein