WO2004014788A1

WO2004014788A1 - Hydrogen generating apparatus

Info

Publication number: WO2004014788A1
Application number: PCT/JP2003/008641
Authority: WO
Inventors: Hodaka Tsuge; Akihiro Komatsuzaki; Hiroaki Shimizu
Original assignee: Honda Giken Kogyo Kabushiki Kaisha
Priority date: 2002-08-09
Filing date: 2003-07-08
Publication date: 2004-02-19
Also published as: AU2003282272A1

Abstract

A hydrogen generating apparatus utilizing the catalyst combustion method for the elevation of the temperature of a modification catalyst (61, 161), wherein a catalyst having the function as a combustion catalyst or a mixture or combination of a modification catalyst and a combustion catalyst is used as the modification catalyst (61), or wherein a combustion catalyst (171) is provided in a heater for heating the modification catalyst (161). The apparatus can be used for shortening the time required for startup operation by elevating the temperature of the modification catalyst (61, 161) to a temperature for the modification through supplying hydrogen and air to the combustion catalyst, and it allows the miniaturization of a hydrogen generating apparatus, since it needs no separate heating device for the elevation of the temperature of the modification catalyst.

Description

Hydrogen generator technical field

The present invention relates to a device for generating hydrogen required for a fuel cell, for example, and more particularly to a hydrogen generator for generating hydrogen from a source gas containing hydrocarbons.

Light

. Background Technology

In recent years, research has been conducted at a rapid pace toward the practical use of fuel cells. Fuel cells generate electrical energy by chemically reacting hydrogen and oxygen. Oxygen can be obtained from the atmosphere (air), but hydrogen requires a large-scale hydrogen generation plant facility and small-scale hydrogen requires a small hydrogen generator called a reformer.

For example, to produce hydrogen from hydrocarbons (isobutane), the hydrocarbons must be brought into contact with the reforming catalyst along with water and air. The reaction at this time is represented by the following equation.

_{C4H 10 + 8 H z O →} 1 3 H 2 + 4C0 2 (1)

C ₄ H _no + 4 H ₂ 0- ^ 9 H 2 + 4 CO (2)

C4 H 10 + 40 ₂ → 5 H _z +4 CO _z (3)

C ₄ H ₁₀ + 4 HUO + 20 ₂ → 9 H ₂ + 4C0 _2- ■ ■ ■ (5)

C ₄ H ₁₀ +2 H ₂ 0 + 〇 ₂ → 7 H ₂ +4 CO (6)

The above reaction formulas (1) and (2) show a steam reforming reaction in which isobutane and steam are brought into contact with and reacted with a reforming catalyst.

Reaction formulas (3) and (4) show the partial oxidation reaction in which isobutane and oxygen are brought into contact with the reforming catalyst to react.

Reaction equations (5) and (6) show that isobutane, steam and oxygen contact the reforming catalyst. A reaction combining the above steam reforming reaction and partial oxidation reaction

^ Show "To

Both reactions produce hydrogen and carbon dioxide or carbon monoxide.

In the above reforming reaction, it is necessary to raise the temperature to about 700 ° C, which is the oxidation activation temperature of the reforming catalyst, and the reforming catalyst must be heated by a burner or an electric heater when starting the reforming.

Examples of such a hydrogen generator include, for example, Japanese Patent Application Laid-Open No. H11-111 entitled "(1) Reforming reactor, catalyst device, heat generation used for them, catalyst body, and method of operating reforming reactor" No. 30405, (2) JP 2002-29705 entitled "Reformer", (3) JP 2002-50386 entitled "Hydrogen production apparatus for fuel cells", and (4) "Hydrogen generator" Japanese Patent Application Laid-Open No. 2002-160902, entitled "Publication".

FIG. 18 is a schematic view of the hydrogen generator disclosed in Japanese Patent Application Laid-Open No. 11-130405. This hydrogen generator has a structure in which a catalyst 310 and a heat unit 311 for heating the catalyst 310 are housed in a can 312.

FIG. 19 is a schematic diagram of a hydrogen generator disclosed in Japanese Patent Application Laid-Open No. 2002-29705. In this hydrogen generator, a plurality of cylinders 32 1, 322, 323, 324, 325 are arranged concentrically in order from the inside, and closing plates 326 are integrally provided at the lower ends of the cylinders 32 1, 323, 325, By providing a closing plate 327 integrally at the upper end of each of the cylinders 322 and 324, communication passages 328, 331, 332 and 333 through which gas flows are formed, and a catalyst layer is provided between the cylinders 321 and 322. 334, a catalyst layer 335 is provided between the cylindrical body 322 and the cylindrical body 323, and a reforming tank for increasing the temperature of the gas in the communication passages 328, 331, 332, 333 at the lower end of the cylindrical body 321. It has a structure with a 336.

FIG. 20 is a schematic diagram of a hydrogen generator disclosed in Japanese Patent Application Laid-Open No. 2002-50386. The hydrogen generator includes a combustion furnace 341, a combustion catalyst 342 provided on a lower periphery of the combustion furnace 341, a reforming catalyst 343 provided on the combustion catalyst 342, Pana 344 arranged at the lower end of the combustion furnace for heating the 342 and the reforming catalyst 343, and a heat insulating material 345 covering the whole thereof Have.

FIG. 21 is a diagram showing a configuration of a hydrogen generator disclosed in Japanese Patent Application Laid-Open No. 2002-160902. This hydrogen generator has a structure in which a burner 352 for heating the reforming section 351 is arranged near a reforming section 351 filled with a reforming catalyst.

If the heat capacity of each of the above hydrogen generators becomes larger, the heat unit 311 shown in Fig. 18 and the reformer burner 336 shown in Fig. 19 and Fig. 20 will be shown. It takes a lot of time to raise the temperature of the reforming catalyst by the burner 3 4 4 and the panner 3 52 shown in Fig. 21, and the time from the start of heating to the start of hydrogen generation, that is, the start of the hydrogen generator The time will be longer and productivity will decrease. Disclosure of the invention

Accordingly, the present inventors have conducted extensive research and found that if the reforming catalyst of the hydrogen generator can be heated using the heat generated by the catalytic combustion method (a method of using a catalyst to promote a chemical reaction at a high temperature without using a flame) to raise the temperature. However, they realized that the heat generation was increased to shorten the start-up time of the hydrogen generator, and that a special heating device was not required, and that the hydrogen generator could be downsized.

In the present invention, a hydrogen generator that raises the reforming catalyst to a reforming temperature of about 700 ° C. and makes the reforming catalyst come into contact with a raw material gas composed of a hydrocarbon or an aliphatic alcohol to convert the hydrogen into hydrogen. A reforming catalyst comprising a combustion catalyst which promotes a reaction between hydrogen and oxygen, or a mixture of the reforming catalyst and the combustion catalyst, and a cylindrical container for accommodating the reforming catalyst. An external hydrogen supply unit for supplying hydrogen to the cylindrical container to perform catalytic combustion, and an external air supply unit for supplying air to the cylindrical container, wherein the temperature of the reforming catalyst is raised to a reforming temperature. A hydrogen generator characterized by heating is provided.

As described above, according to the hydrogen generator, it is possible to reduce the time required to raise the temperature up to the reforming temperature with a large amount of heat generated by catalytic combustion, and to shorten the startup time of the hydrogen generator. In addition, a special heating device is not required for raising the temperature of the reforming catalyst, and the size of the hydrogen generator can be reduced.

If platinum is used as the combustion catalyst, hydrogen can be catalytically burned from room temperature. It is preferable because it can be performed.

The external hydrogen supply means used in the hydrogen generator of the present invention preferably includes a small heater that accommodates the reforming catalyst in a small container smaller than a cylindrical container and raises the temperature of the reforming catalyst to a reforming temperature. Small hydrogen generator. In this way, by using a small hydrogen generator equipped with a small heater as an external hydrogen supply means, if the raw material gas and air used for reforming are supplied to the small hydrogen generator, heat generated by the partial oxidation reaction is generated. Since the temperature of the reforming catalyst in the small hydrogen generator having a small heat capacity can be quickly raised, hydrogen can be quickly generated and supplied to the combustion catalyst in the cylindrical container. Therefore, it is possible to further shorten the time required to raise the temperature from room temperature to the reforming temperature of about 700 ° C.

Furthermore, in the present invention, the reforming catalyst is raised to a reforming temperature of about 700 ° C., and the reforming catalyst is contacted with a raw material gas composed of a hydrocarbon or an aliphatic alcohol to reform it to hydrogen. A hydrogen generator, comprising: a cylindrical container for storing the reforming catalyst; a heater attached to the cylindrical container, for storing a combustion catalyst for promoting a reaction between hydrogen and oxygen; and hydrogen in the heater. And an external air supply means for supplying air to the heater, and heating the reforming catalyst to a reforming temperature by the heater. There is provided a hydrogen generator characterized by the following.

As described above, in the present invention, the combustion catalyst is housed in the heater, and hydrogen and air are supplied to the combustion catalyst when the hydrogen generator is started, so that the heater raises the temperature of the reforming catalyst to the reforming temperature. By reducing the time required to raise the temperature to the reforming temperature with a high calorific value due to catalytic combustion, the startup time of the hydrogen generator is reduced. In addition, a special heating device such as a burner or an electric heater is not required for raising the temperature of the reforming catalyst, and the hydrogen generator can be downsized. BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 is a system diagram of the hydrogen generator according to the first embodiment of the present invention.

FIG. 2 is a sectional view of the reformer main body according to the first embodiment shown in FIG.

FIG. 3 is a cross-sectional view taken along line 3-3 in FIG. 1, and is a cross-sectional view of the small reformer. FIG. 4 is a flowchart showing a reforming procedure of the hydrogen generator according to the first embodiment.

5A and 5B are partial cross-sectional views of a reformer main body showing two comparative examples when heating a reforming catalyst.

FIG. 6 is a sectional view showing a reforming catalyst of a reformer main body according to a second embodiment of the present invention.

FIG. 7 is a sectional view showing a reforming catalyst of a reformer body according to a third embodiment of the present invention.

FIG. 8 is a sectional view showing a reforming catalyst of a reformer body according to a fourth embodiment of the present invention.

FIG. 9 is a sectional view showing a reforming catalyst of a reformer main body according to a fifth embodiment of the present invention.

FIG. 10 is a system diagram of a hydrogen generator according to a sixth embodiment of the present invention.

FIG. 11 is a cross-sectional view of the reformer main body according to the sixth embodiment shown in FIG. FIG. 12 is a cross-sectional view taken along line 12-12 in FIG.

FIG. 13 is an enlarged sectional view taken along line 13-13 of FIG.

FIG. 14 is a flowchart showing the reforming operation of the hydrogen generator according to the sixth embodiment.

FIG. 15A and FIG. 15B are cross-sectional views showing Comparative Examples 1 and 2 of the hydrogen generator including the heater.

FIG. 16 is a flowchart showing the operation of the hydrogen generator of Comparative Example 1 shown in FIG. 15A.

FIG. 17 is a flowchart showing the operation of the hydrogen generator of Comparative Example 2 shown in FIG. 15B.

FIG. 18 is a schematic diagram showing a first conventional hydrogen generator.

FIG. 19 is a schematic sectional view showing a second conventional hydrogen generator.

FIG. 20 is a schematic cross-sectional view showing a third conventional hydrogen generator.

FIG. 21 is a system diagram of a fourth conventional hydrogen generator. BEST MODE FOR CARRYING OUT THE INVENTION

1 to 4 show a hydrogen generator according to a first embodiment of the present invention.

In FIG. 1, the hydrogen generator 10 includes a reformer main body 11 and a small reformer 12. The small reformer 12 is an external hydrogen supply means for supplying hydrogen to the reformer main body 11 for catalytic combustion. The small reformer 12 is smaller than the reformer body 11.

The reformer main body 11 has a reforming catalyst described later. Hydrocarbon, air and water, which are raw material gases, are supplied to the reformer main body 11 via pipes 17, 18 and 19 and valves 14, 15 and 16. The valve 15 and the pipe 18 constitute external air supply means. The temperature of the reforming catalyst in the reformer body 11 is measured by a temperature measuring device 22. The reformed hydrogen and other gases are discharged from the gas outlet 26.

The small reformer 12 includes a burner 31 and a cross-shaped container 72 in which a reforming catalyst 76 is housed as shown in FIG. The burner 31 is a small heater that heats the reforming catalyst 76. Hydrocarbons, air and water are externally supplied to the small reformer 12 via pipes 36, 37, 38 having valves 32, 33, 34, respectively, and an inlet pipe 39. The temperature of the reforming catalyst in the small reformer 12 is measured by the temperature measuring device 41. The reformed hydrogen and other gases are taken out through a connection pipe 44 as an outlet, and supplied to the reformer main body 11 through a valve 46.

FIG. 2 shows a cross section of the reformer main body 11 according to the first embodiment. The reformer main body 11 according to the first embodiment includes a cylindrical container 51. The cylindrical container 51 is made of, for example, a stainless steel plate of Japanese Industrial Standard SUS316 having an inner diameter of 120 mm, an outer diameter of 124 mm, and a plate thickness of 2 mm. It is a corrosion-resistant and heat-resistant sealed container closed with a lower end plate 67.

An upper porous plate 52 and a lower porous plate 53 are provided in the cylindrical container 51 so as to be vertically separated from each other at an upper portion thereof. The cylindrical container 51 has a gas dispersion chamber 56 defined between the upper perforated plate 52 and the upper end plate 54. A gas ring (granules, wire mesh, etc.) 57 is provided in the gas dispersion chamber 56.

A reforming space 58 for filling the reforming catalyst 61 is defined between the upper perforated plate 52 and the lower perforated plate 53. In a space 62 formed below the lower porous plate 53, a CO shift catalyst 63 (consisting of an upper shift catalyst 63a and a lower shift catalyst 63b) is provided. A CO removal catalyst 64 is provided underneath.

The outer periphery of the upper part of the cylindrical container 51 is covered with a heat insulating material 66 so as to cover the upper surface of the container 51 and the reforming space 58. The lash ring 57 prevents the gas flow from being biased in the gas dispersion chamber 56.

The reforming catalyst 61 is composed of, for example, a number of particles having platinum supported on the surface of a spherical alumina carrier having a diameter of about 3 mm. The reforming catalyst 61 is also a combustion catalyst that promotes a reaction between hydrogen and oxygen by using platinum as a catalyst, and is capable of catalytically burning hydrogen at room temperature. That is, platinum has a reforming catalyst function and a combustion catalyst function.

For the CO shift catalyst 63, an upper shift catalyst 63 3a is preferably an iron-chromium (Fe_Cr) catalyst, and a lower shift catalyst 63 3b is preferably a copper-zinc (Cu-Zn) catalyst. is there.

As the CO removal catalyst 64, a ruthenium-based catalyst is desirable.

The pipes 17, 18, 19 and the connecting pipe 44 are attached to the upper end plate 54. The gas outlet 26 is attached to the lower end plate 67 of the cylindrical container 51.

The temperature measuring device 22 includes a sensor 68 inserted into the reforming catalyst 61, and a temperature display section 69 for calculating and displaying a temperature based on a signal from the sensor 68. The tip 68 a of the sensor 68 is a temperature measuring part and is located at the center of the reforming space 58.

The small reformer 12 shown in Fig. 3 has a cruciform container 7 2 in which four corners of a rectangle are cut out in an arc shape to form a substantially cruciform box, and a cruciform container 7 in which the above-mentioned inlet piping 39 is attached. A lashing ring 7 4 arranged on the front side 7 3 side of 2 and a reforming catalyst 7 arranged on the downstream side of the gas flow with respect to the lashing ring 7 4 and arranged long so as to be orthogonal to the gas flow. 6 and a lash ring 77 arranged downstream of the gas flow with respect to the reforming catalyst 76. The connecting pipe 44 is attached to the rear side 78 of the cruciform container 72.

The lashing rings 74, 77 prevent the gas flow in the cross-shaped container 72 from being biased.

For example, the reforming catalyst 76 is made of ruthenium on spherical alumina with an outer diameter of about 3 mm. It is composed of a large number of particles that bear a ru.

The temperature measuring device 41 includes a sensor 81 inserted into the reforming catalyst 76, and a temperature display section 82 for calculating and displaying a temperature based on a signal from the sensor 81. The tip 81 a of the sensor 81 is a temperature measuring portion and is located at the center of the reforming catalyst 76.

Next, the operation of the hydrogen generator 10 according to the above-described first embodiment will be described with reference to FIGS. 1 and 4.

Step (hereinafter abbreviated as ST) 01: The reforming catalyst 76 of the small reformer 12 shown in FIG. 3 is heated to 200 ° C. by a 2 kW burner 31 (see FIG. 1) and heated. This temperature of 200 ° C is the oxidation activation temperature of the reforming catalyst 76, and the reaction is promoted above this temperature.

ST02: Open the valve 32 of the pipe 36 and the valve 33 of the pipe 37 shown in FIG. 1, supply the following raw material gas to the small reformer 12, and raise the temperature of the reforming catalyst 76 to 600 ° C.

Source gas:

Amount of isobutane: δ

η (gas)

Air volume: 1 5600 cmVmin (gas)

S TO 3: When the temperature of the reforming catalyst 76 reaches 600 ° C, open the valve 34 of the pipe 38 and supply the following raw material gas to the small reformer 12.

Source gas:

Amount of isobutane: 500 cms / min (gas)

Air volume: 4800 cm ³ / min (gas)

Water volume: 3 cm ³ / min (liquid)

As a result, the following product gas was obtained.

Generated gas:

The amount of hydrogen: 2800 cm ³ / mn

Methane amount: 200 cm ³ / mn

Amount of carbon dioxide 1 200 cm ³ / mn

Amount of carbon monoxide 500 cmVm n

3800 cm ³ / min ST04: Connect the gas (hydrogen, methane, carbon dioxide, —carbon oxide and nitrogen) and air generated by the small reformer 1 2 and 6800 cm ³ / min. Open the valve 46 of the piping 44 and the valve 15 of the piping 18 It is supplied to the reformer body 11 and the temperature of the reforming catalyst 61 (see Fig. 2) in the reformer body 11 is raised to 200 ° C. This temperature of 200 ° C. is the oxidation activation temperature of the reforming catalyst 61, and the reaction is promoted above this temperature.

S TO 5: Open the valve 14 of the pipe 17, supply the raw material gas shown below to the reformer body 11, and raise the reforming catalyst 61 to 700 ° C, that is, the reforming temperature required for reforming. Warm up.

Source gas:

Amount of isobutane: 2000 cm ³ Zm in (gas)

Air volume: 60000 cmVmin (gas)

S TO 6: When the temperature of the reforming catalyst 61 reaches 700 ° C, open the pulp 16 of the pipe 19 and supply the raw material gas shown below to the reformer main body 11 and mix it with the reforming catalyst 61. (See Equations (5) and (6) above).

Source gas:

Amount of isobutane: 2000 cm ³ Zmin (gas)

Air volume: 16000 cmVmin (gas)

Water volume: 1 2 cmVmin (liquid)

As a result, the following reformed gas was obtained.

Reformed gas:

The amount of hydrogen: 14300 cm ³ / min

Methane amount: 300 cmVmin

Amount of carbon dioxide: 4200 cmVmin

Amount of carbon monoxide: 3400 cmVm i n

Nitrogen content: 1 2700 cm ³ / min

Subsequently, about 90% of carbon monoxide is changed to hydrogen and carbon dioxide by causing the reaction of the following equation (7) using the CO shift catalyst 63 (see Fig. 2). By causing the reaction of equation (8) shown below (see Fig. 2), the concentration of carbon oxide is reduced to about 10 ppm. _{_{CO + H 2 0 → C0 2}} + H 2 (7)

2CO + 0 ₂ → 2C0 ₂ (8)

In step ST04, when the temperature of the reforming catalyst 61 of the reformer body 11 reaches 200 ° C, the supply of fuel to the burner 31 is stopped, and the heating of the small reformer 12 is stopped. Close the valves 32, 33, 34, 46 to stop the supply of hydrocarbons, air and water to the small reformer 12. Then, the supply of the generated gas from the small reformer 12 to the reformer main body 11 is stopped.

As described above, the type and amount of the reforming catalyst in the reformer main body 11 and the small reformer 12 in the first embodiment, and the temperature rise time of the reforming catalyst are shown in the following table as Example 1. Summarized.

That is, in Example 1, in the small reformer catalyst, the type was Ru (supported on alumina), the amount was 50 cm ³ , and the temperature rising time from normal temperature to 200 ° C was 5 seconds, and the temperature was 200 ° C. The catalytic combustion time up to 600 ° C is 5 seconds. Reformer Te body catalyst smell, the type is one in P t (supported on alumina), its amount as 200 cm ^3, the heating time from room temperature to 200 ° C 1 5 seconds, from 200 ° C 700 The heating time to ° C is 20 seconds. The total time from the start of heating the small reformer to the time when the temperature of the reformer body catalyst reached 700 ° C, that is, the startup time was 45 seconds.

5A and 5B are cross-sectional views of relevant parts showing a comparative example of heating of the reforming catalyst. FIG. 5A shows Comparative Example 1, and FIG. 5B shows Comparative Example 2.

In Comparative Example 1 shown in FIG. 5A, a 500 W electric heater 102 is provided inside the reformer main body 101, and the temperature of the reforming catalyst 61 is raised from room temperature to 200 ° C. by the electric heater 102. When the reforming catalyst 61 reaches 200 ° C, the reformer body 1 01 supplies isobutylene Tan 2000 CMVM in and air 60000 cm ³ / mi n, thereby raising the temperature of the Aratameshitsusawa medium 61 to 700 ° C.

In Comparative Example 1, as shown in the above-mentioned table, a small reformer was not used, and one type of the reformer main body catalyst (reforming catalyst 61) was used, and Pt (supported on alumina) was used. as the amount 200 cm ^3, the heating time from room temperature to 200 ° C 1 40 seconds, 2 00 ° Atsushi Nobori time from C to 700 ° C is 20 seconds. The total time from the start of heating of the reformer body catalyst by the electric heater 202 until the temperature of the reformer body catalyst reached 700 ° C was 160 seconds.

In Comparative Example 2 shown in FIG. 5B, a 2 kW burner 105 is provided inside the reformer main body 104, and the reformer catalyst 61 is heated from room temperature to 200 ° C. by the burner 105. Raise the temperature.

When the reforming catalyst 61 reaches 200 ° C, the reformer body 1 04 supplies isobutane 200 0 CMVM in and air 60000 cm ³ / m η, raise the temperature of the reforming catalyst 61 to 7 00 ° C.

In Comparative Example 2, as shown in the above-mentioned table, a small reformer was not used, and the type of the reformer main body catalyst (reformation catalyst 61) was one type of Pt (supported on alumina). Assuming that the volume was 200 cm ³ , the heating time from normal temperature to 200 ° C was 60 seconds, and the heating time from 200 ° C to 700 ° C was 30 seconds. Modification by burner 105 The total time from the start of the heating of the main body catalyst until the temperature of the reformer main body catalyst reached 700 ° C was 90 seconds.

FIGS. 6, 7, 8, and 9 show a second embodiment, a third embodiment, a fourth embodiment, and a fifth embodiment of the reforming catalyst of the reformer body according to the present invention.

In Example 2 shown in FIG. 6, the small reformer 12 of Example 1 (see FIG. 3) was used, and as the reforming catalyst of the reformer main body 11, each particle was a spherical particle having an outer diameter of about 3 mm. A catalyst in which platinum is supported on alumina that has been modified, that is, a reforming catalyst 61 (not hatched in the figure), and a catalyst in which ruthenium is supported on ruthenium in a spherical alumina having an outer diameter of about 3 mm, that is, a reforming catalyst The reforming space 58 is filled with a mixture of the catalyst 85 (hatched) and the catalyst 85 (hatched).

Using the reformer main body 11 of the second embodiment, the start-up time was measured in the same manner as in the first embodiment.

First, after going through steps ST01 to ST03 in Fig. 4 in the small reformer 12, the gas and air generated in the small reformer 12 6800 cm ³ / min are transferred to the reformer body 11. Supply and raise the temperature of the reforming catalysts 61 and 85 to 200 ° C.

Next, the following raw material gas is supplied to the reformer main body 11, and the temperature of the reforming catalysts 61 and 85 is raised to 700 ° C.

Source gas:

Amount of isobutane: 2000 cm ³ / min (gas)

Air volume: 60000 cm ³ / min (gas)

When the temperature of the reforming catalysts 61 and 85 reaches 700 ° C, the following raw material gas is further supplied to the reformer body 11 to perform the combined reforming reaction.

Source gas:

Amount of isobutane: 2000 cm ³ / min (gas)

Air volume: 1 6000 crnVmin (gas)

Volume of 7_K: 1 2 cm ³ / min (liquid)

As a result, the following reformed gas was obtained.

Reformed gas:

The amount of hydrogen: 1 5000 cm ³ / min Methane amount: 200 cm ³ Zmi n

Amount of carbon dioxide: 4200 cmVmin

—Amount of carbon oxide: 3500cm ³ / min

Nitrogen content: 1 2700 c rr ^ Zm i n

Subsequently, a reaction using a CO shift catalyst and a reaction using a CO removal catalyst are caused.

In Example 2, as shown in the above-mentioned table, in the small reformer catalyst, the type, the amount, the heating time from normal temperature to 200 ° C, and the catalytic combustion time from 200 ° C to 600 ° C were as follows. Same as Example 1. In the reformer body catalyst, that type two types, Pt were mixed with (supported on alumina) Ru and (supported on alumina), the amount Pt is 20 cm ^3, Li is 2000171 ^3, 200 ° C from room temperature The temperature rise time is up to 20 seconds, and the temperature rise time from 200 ° C to 700 ° C is 25 seconds.After the small reformer starts heating, the catalyst in the reformer reaches 700 ° C. Total time to 55 seconds

In the third embodiment shown in FIG. 7, the small reformer 12 of the first embodiment (see FIG. 3) is used, and the reforming catalyst 61 supporting platinum is used as the reforming catalyst of the reformer body 11. An example is shown in which the reforming space 58 is filled with the reforming catalyst 85 carrying ruthenium so as to be on the upstream side of the flow and downstream of the gas flow.

Using the reformer main body 11 of the third embodiment, the startup time was measured in the same manner as in the first embodiment.

First, after going through steps ST01 to ST03 shown in FIG. 4 in the small reformer 12, the gas and air 6800 cm ³ / min generated in the small reformer 12 are transferred to the reformer body 11. Supply and raise the temperature of the reforming catalysts 61 and 85 to 200 ° C.

Next, the following raw material gases are supplied to the reformer main body 11 to raise the temperature of the reforming catalysts 61 and 85 to 700 ° C.

Source gas:

Amount of isobutane: 2000 cms / min (gas)

Air volume: 60000 cm ³ / min (gas)

When the temperature of the reforming catalysts 61 and 85 reaches 700 ° C, the reformer body 11 The raw material gas shown is supplied to cause a combined reforming reaction.

Source gas:

Amount of isobutane: 2000 cm ³ Zm in (gas)

Air volume: 1 6000 cm ³ Zm in (gas)

Water volume: 1 2 cmVmin (liquid)

As a result, the following reformed gas was obtained.

Reformed gas:

Amount of hydrogen: 15000 cmVm n

Methane amount: 200 cmVm n

Amount of carbon dioxide 4200 cmVm n

Amount of carbon monoxide 3500 cmVm n

Nitrogen content: 1 2700 cmVm n

In Example 3, as shown in the table above, in the small reformer catalyst, its type, its amount, and normal temperature to 200. The temperature rise time up to C and the catalyst combustion time from 200 ° C to 600 ° C are the same as those in Example 1, and two types of the reformer main body catalyst were used. And Ru (supported on alumina) are arranged such that Pt is on the upstream side and Ru is on the downstream side. The amount of Pt is 50 cm ³ , the Ru is 200 cm \ The heating time from normal temperature to 200 ° C is 20 seconds, and the heating time from 200 ° C to 700 ° C is 20 seconds. The total time from the start of heating the small reformer to the temperature of the reformer's main catalyst reaching 700 ° C was 50 seconds.

In Example 4 shown in FIG. 8, the small reformer 12 of Example 1 (see FIG. 3) was used, and the reforming catalyst 85 supporting ruthenium was used as the reforming catalyst of the reformer body 11. An example is shown in which the reforming catalyst 61 carrying platinum is filled in the reforming space 58 so as to be on the upstream side of the flow and on the downstream side of the gas flow.

Using the reformer main body 11 of the fourth embodiment, the startup time was measured in the same manner as in the first embodiment.

First, the small reformer 12 goes through steps ST 0 "! ~ ST 03 in Fig. 4 The gas and air generated at the die reformer 12 and 6800 cm ³ / min are supplied to the reformer body 11 to raise the temperature of the reforming catalysts 61 and 85 to 200 ° C.

Source gas:

The amount of isobutane: 2000 cmVmin (gas)

Air volume: 60000 cmVmin (gas)

When the temperature of the reforming catalysts 61 and 85 reaches 700 ° C, the following raw material gas is supplied to the reformer body 11 to perform the combined reforming reaction.

Source gas:

The amount of isobutane: 2000 cmVmin (gas)

Air volume: 1 6000 cm ³ / min (gas)

Water volume: 1 2 cm ³ / min (liquid)

As a result, the following reformed gas was obtained.

Reformed gas:

The amount of hydrogen: 1 5000 cm ³ / min

Methane amount: 200 cm ³ / min

Amount of carbon dioxide: 4200 cm ³ / min

—Amount of carbon oxide: 3500 cmVmin

Nitrogen amount: 1 2700cm ³ / min

Then, the reaction with the CO shift catalyst and the reaction with the CO removal catalyst

In Example 4, as shown in the above-described table, in the small reformer catalyst, the type, the amount, and the heating time from normal temperature to 200 ° C. were 200. The catalyst combustion time from C to 600 ° C is the same as in Example 1. In the reformer main body catalyst, there are two types, and Pt (supported on alumina) and Ru (supported on alumina) are arranged so as to be Ru on the upstream side and Pt on the downstream side. The amounts are 200 cm3 for Ru and 50 cm3 for Pt. From room temperature to 200. The heating time to C is 25 seconds, and the heating time from 200 ° C to 700 ° C is 20 seconds. After starting heating of the small reformer, the reformer body The total time for the catalyst to reach 700 ° C was 55 seconds.

In the fifth embodiment shown in FIG. 9, the small reformer 12 of the first embodiment (see FIG. 3) is used, and the reforming catalyst 61 supporting platinum is used as the reforming catalyst of the reformer body 11. In the upstream side of the flow, the reforming catalyst 85 carrying ruthenium was filled into the reforming space 58 so as to be on the downstream side of the gas flow, and the catalyst 87 carrying platinum on ø3 spherical alumina was filled. An example in which an annular external heater 88 is provided on the outer periphery of the cylindrical container 51 on the side of the reforming space 58 is shown.

The start-up time was measured in the same manner as in Example 1 using the reformer main body 11 and the external heater 88 of Example 5.

First, after going through steps ST 01 to ST 03 in Fig. 4 in the small reformer 12, the gas and air generated in the small reformer 12 6800 cm ³ / min are transferred to the reformer body 11. Then, the temperature of the reforming catalysts 61 and 85 is raised to 200 ° C.

Next, the following raw material gas is supplied to the reformer main body 11, and the following heating gas is supplied to the external heater 88 to raise the temperature of the reforming catalysts 61 and 85 to 700 ° C.

Raw material gas supplied to the reformer body 1 1:

Amount of isobutane: 1 500 cm ³ min (gas)

Air volume: 46400 cm ³ min (gas)

Heating gas supplied to the external heater 88:

Amount of isobutane: 500 cm ³ Zmin (gas)

Air volume: 1 5500 cm ³ Zmin (gas)

When the temperature of the reforming catalysts 61 and 85 reaches 700 ° C., the following raw material gas is further supplied to the reformer main body 11 to cause a steam reforming reaction.

Source gas:

Amount of isobutane: 1 500 c nr ^ Zmin (gas)

Water volume: 15 cm ³ / min (liquid)

As a result, the following reformed gas was obtained.

Reformed gas:

Amount of hydrogen: 1 5200 cm3Zmin Methane amount: 200 cm 3 / min

Amount of carbon dioxide: 260 mcm / min

Amount of carbon monoxide: 3500 cm3 / min

Subsequently, a reaction by the CO conversion catalyst and a reaction by the CO removal catalyst are caused,

In Example 5, as shown in the above-mentioned table, in the small reformer catalyst, the type, the amount, the heating time from normal temperature to 200 ° C., and the temperature from 200 ° C. to 600 ° C. The catalytic combustion time up to is the same as in Example 1. In the reformer main body catalyst, there are two types, and Pt (supported on alumina) and Ru (supported on alumina) are arranged so that Pt is on the upstream side and Ru is on the downstream side. The amount P t is 2 0 cm ^3, R u is 2 0 0 cm ^3. Using an external heater 88, the heating time from normal temperature to 200 ° C is 20 seconds, and from 200 ° C to 700 ° C. The heating time to C was 40 seconds. The total time from the start of heating of the small reformer to the temperature of the reformer body catalyst reaching 700 ° C was 70 seconds.

The heating time of the external heater 88 from 200 ° C to 700 ° C is 25 seconds.

/ <— O

As described above, first, in the present invention, the reforming catalyst 61 is housed in the cylindrical container 51, and the reforming catalyst 61 is raised to a reforming temperature of about 700 ° C. In a hydrogen generator 10 that reforms to hydrogen by contacting a raw material gas consisting of hydrocarbons or aliphatic alcohols, a combustion catalyst that promotes the reaction between hydrogen and oxygen is used as a reforming catalyst 61 to generate hydrogen. When the device 10 is started, the reforming catalyst 61 is supplied with hydrogen and air to the reforming catalyst 61 by the small reformer 12, the air supply valve 15, and the piping 18, so that the reforming catalyst 61 is heated to the reforming temperature. It is characterized in that the temperature can be raised up to the maximum.

Further, as described in FIGS. 1, 6, 7, and 8, the reforming catalysts 61 and 85 are housed in the cylindrical container 51, and these reforming catalysts 61 and 85 are stored in the cylindrical container 51. In the hydrogen generator 10 which raises the reforming temperature to about 0 ° C and makes it contact with a raw material gas consisting of hydrocarbons or aliphatic alcohols, the reforming catalyst 85 A reforming catalyst 61 composed of a combustion catalyst is provided in a mixed or upper and lower layer. When the hydrogen generator 10 is started, a small reformer 12 and a valve 1 for supplying air to the reforming catalyst 61 are provided. Five One

-19-By supplying hydrogen and air via the pipe 18 and the reforming catalysts 61 and 85, the temperature can be raised to the reforming temperature.

As described above, a combustion catalyst that promotes the reaction between hydrogen and oxygen is used as the reforming catalyst 61, or a reforming catalyst 61 composed of a combustion catalyst is mixed with or provided in the reforming catalyst 85, and the reforming catalyst 6 Hydrogen and air are supplied to 1 through a small reformer 12, a valve 15, and a pipe 18, so that the hydrogen is catalyzed and the reforming catalysts 61, 85 are heated to the reforming temperature. I do. The time required to raise the temperature to the reforming temperature with a large amount of heat generated by catalytic combustion is reduced, and the startup time of the hydrogen generator can be reduced. In addition, a special heating device is not required for raising the temperature of the reforming catalysts 61 and 85, and the hydrogen generator 10 can be reduced in size.

If platinum is used as the combustion catalyst, hydrogen can be catalytically burned from room temperature, and the time for raising the temperature of the reforming catalysts 61 and 85 can be further reduced.

As the reforming catalyst to be filled in the reformer body, one containing platinum is desirable, and one carrying platinum, one carrying platinum and a metal belonging to Group VIII to Group 10 (Fe, C o, Ni, Ru, Pd, etc.).

The reforming raw material may be LPG, casserole fuel, city gas, naphtha, gasoline, light oil, kerosene and other light hydrocarbons. Further, the aliphatic alcohol is not particularly limited, and includes methanol and ethanol.

Next, a hydrogen generator according to a sixth embodiment of the present invention will be described with reference to FIGS.

The hydrogen generator 110 of the sixth embodiment shown in FIG. 10 includes a reformer main body 111 and a small reformer 112. The small reformer 112 is an external hydrogen supply means for supplying hydrogen to the reformer main body 111 for catalytic combustion. The small reformer 1 1 2 is smaller than the reformer body 1 1 1.

The reformer main body 111 includes a reforming section 111A and a heating section, which is a heater for heating the reforming section 111A by being attached above the reforming section 111A. It consists of 1 1 1 B.

The reforming section 111A has a reforming catalyst described later therein. Hydrocarbon, air and water, which are raw material gases, are supplied from outside via the pipes 117, 118, 119, and the valves 114, 115, 116 from the reforming unit 111A. Supplied to Hydrogen after reforming And other gases are exhausted from gas outlets 126.

The heating unit 111B has a combustion catalyst that promotes the reaction between hydrogen and oxygen. The heating section 111B is connected to the small reformer 112. The temperature of the reforming catalyst in the reforming section 111A and the temperature of the combustion catalyst in the heating section 111B are measured by a temperature measuring device 122.

The small reformer 1 12 includes a burner 13 1 and a cross-shaped container 17 2 having a reforming catalyst 17 6 shown in FIG. 13 inside. The burner 13 1 is a small heater for heating the reforming catalyst 1 76. Hydrocarbons, air and water are supplied externally to the small reformer 1 12 via pipes 13 6, 13 7, 13 8 having valves 13 2, 13 3, 13 4 respectively. . The temperature of the reforming catalyst in the small reformer 12 is measured by a temperature measuring device 41. The reformed hydrogen and other gases are taken out to the connecting pipe 144 as an outlet, and supplied to the heating section 111B of the reformer main body 111 via the valve 146.

The first bypass pipe 1 36 a branches off from the upstream side of the valve 13 2 of the pipe 13 6, and the tip is downstream from the valve 14 6 of the connection pipe 14 4 via the valve 13 2 a And supplies hydrocarbons directly to the heating section 111B.

The second bypass pipe 1 3 7a branches off from the upstream side of the valve 1 3 3 of the pipe 1 3 7, and its tip is below the connecting pipe 1 4 4 of the valve 1 4 6 via the valve 13 3a. It is connected to the flow side and supplies air to the heating unit 111B.

The second bypass pipe 1337a and the valve 1333a constitute external air supply means.

As shown in FIG. 11, the reforming section 1 11 A of the reformer main body 1 1 1 has a cylindrical container 15 1, and is mounted on the upper portion of the cylindrical container 15 1 with a space therebetween. A lash ring provided in a gas dispersion chamber 1 56 formed between the perforated plate 15 2 and the lower perforated plate 15 3, the upper end plate 15 4 of the cylindrical container 15 1, and the upper perforated plate 15 2 (Granules, wire mesh, etc.) 1'57, reforming space 58 formed between upper perforated plate 152, lower perforated plate 153, reforming catalyst 161, filled in lower perforated plate CO conversion catalysts 16 3 (upper conversion catalyst 16 3 a and lower conversion catalyst 16 3) provided in order from top to bottom via space 16 2 in the cylindrical vessel 15 1 below 15 3 b) and a CO removal catalyst 1 64. The cylindrical container 15 1 is made of, for example, Japanese Industrial Standard SU S316 stainless steel plate having an inner diameter of 12 Omm, an outer diameter of 124 mm, and a thickness of 2 mm, and the upper head plate 154 and the lower head plate 1 of the same material. Corrosion-resistant and heat-resistant sealed container closed with 67.

The lash ring 157 is a member for preventing the gas flow in the gas dispersion chamber 156 from being biased.

The reforming catalyst 161 is, for example, one in which each particle carries ruthenium (Ru) on spherical alumina having an outer diameter of about 3 mm.

As for the CO shift catalyst 163, the upper shift catalyst 163a is suitable for iron-chromium (Fe-Cr) based catalyst, and the lower shift catalyst 163b is suitable for copper-zinc (Cu-Zn) based catalyst. .

As the CO removal catalyst 164, a ruthenium-based catalyst is desirable. 'Piping 1 1 1, 1 1 8 and 1 1 9 are attached to the upper head plate 1 54. The gas outlet 126 is attached to the lower end plate 167 of the cylindrical container 151.

The temperature measuring device 122 includes a sensor 168 inserted in the reforming catalyst 161, a sensor 166 inserted in the combustion catalyst 171 described below, and signals based on these sensors 166 and 168. And a temperature display section 169 for calculating and displaying the temperature. The tip 166a of the sensor 166 and the tip 168a of the sensor 168 are a temperature measuring portion, and the tip 168a is located at the center of the reforming space 158.

The heating unit 1 1 1B is composed of an annular container 170 mounted on the upper part of a cylindrical container 151 and a combustion catalyst 171 filled in the annular container 170, and is connected to the annular container 170. 1 Connect 44.

The combustion catalyst 171 is, for example, one in which each particle carries white gold (Pt) on spherical alumina having an outer diameter of about 3 mm, and its amount is 200 cm ³ .

Thus, by using platinum as the combustion catalyst 171, the reaction between hydrogen and oxygen is promoted, and hydrogen can be catalytically combusted from normal temperature. In addition, 170a is a heating unit gas outlet serving as an outlet of the gas in the heating unit 111B.

The tip 166a of the sensor 166 of the temperature measuring device 122 is located at the center of the cross section of the annular container 170.

As shown in FIG. 12, the reformer main body 1 1 1 An annular vessel 170 of heating section 1 11 B is placed outside of 1 and the combustion catalyst 17 1 is filled in this annular vessel 170 to form a reforming catalyst of the reforming section 1 11 A. The structure is such that 16 1 can be heated by the heating section 11 1 B combustion catalyst 17 1.

The gas supplied from the small reformer 1 1 2 (see Fig. 10), the first bypass pipe 13 6 a and the second bypass pipe 13 7 a to the heating section 11 1 B is connected to the connecting pipe 14 4 flows into the annular container 170, flows in contact with the combustion catalyst 171, as shown by the arrow, and flows out from the heating section gas outlet 170a.

As shown in Fig. 13, the small reformer 1 1 and 2 consist of a cruciform container 1 72 and a cruciform box 1 It consists of a lashing ring 174, a reforming catalyst 176, and a lashing ring 177, which are arranged in 2. The lashing ring 174 is placed on the front side 173 side of the cross-shaped container 172 where the pipes 136, 137, 138 are to be mounted. The reforming catalyst 176 is arranged on the downstream side of the gas flow with respect to the lashing ring 174, and is arranged long so as to be orthogonal to the gas flow. The lashing ring 177 is disposed downstream of the gas flow with respect to the reforming catalyst 176. Reference numeral 1778 denotes a rear side provided on the cross-shaped container 172 for mounting the connection pipe 144 shown in FIG.

The lashing rings 174 and 177 are members for preventing the gas flow in the cross-shaped container 172 from being biased.

The reforming catalyst 176 is, for example, one in which each particle carries ruthenium on spherical alumina having an outer diameter of about 3 mm, and the amount thereof is 50 cm ³ .

The temperature measuring device 14 1 comprises a sensor 18 1 inserted into the reforming catalyst 17 6, and a temperature display section 18 2 for calculating and displaying a temperature based on a signal from the sensor 18 1. . The tip 18 1 a of the sensor 18 1 is a temperature measuring portion and is located at the center of the reforming catalyst 17 6.

The operation of the hydrogen generator 110 according to the sixth embodiment described above will be described based on the flowcharts shown in FIGS. 10, 11, 12, 13, and 14.

ST 2 1: Small reformer 1 1 2, more specifically, reforming catalyst 1 76 (see Fig. 13) with a 2 kW burner 1 3 1 (see Fig. 10) 200. Heat to C and raise the temperature. This temperature of 200 ° C. is the oxidation activation temperature of the reforming catalyst 176, and the reaction is promoted above this temperature. Proceed.

ST22: Open the valve 136 of the pipe 136 and the valve 133 of the pipe 137 shown in Fig. 10, supply the raw material gas shown below to the small reformer 112, and set the reforming catalyst 176 to 600 ° Raise the temperature to C.

Source gas:

The amount of isobutane: 500 cmVmin (gas)

Air volume: 1 5600 cm ³ Zm in (gas)

ST 23: When the temperature of the reforming catalyst 176 reaches 600 ° C., the valve 134 of the pipe 138 shown in FIG. 10 is also opened, and the following raw material gas is supplied to the small reformer 112.

Source gas:

Amount of isobutane: 500 cm ³ / "min (gas)

Air volume: 4800 cm ³ Zm in (gas)

Water volume: 3 cm ³ / min (liquid)

As a result, the following product gas was obtained.

Generated gas:

The amount of hydrogen: 2800 cm ³ Zmin

Methane amount: 200 cm ³ / min

Amount of carbon dioxide: 1 200 cm ³ / min

Amount of carbon monoxide: S OOcmaZmi n

Nitrogen amount: 3800 cmn

ST 24: The gas (hydrogen, methane, carbon dioxide, carbon monoxide and nitrogen) generated by the small reformer 112 and air 6800 cmVmin are connected to the valve 146 of the connecting pipe 144 (see Fig. 10) and the second bypass. Open the valve 133a of the pipe 137a and supply it to the heating section 111B, perform catalytic combustion in the heating section 111B, and raise the combustion catalyst 171 (see Fig. 11) to 200 ° C. Let warm. This temperature of 200 ° C. is the oxidation activation temperature of the combustion catalyst 171, and the reaction is promoted above this temperature.

ST 25: Open the valve 1 32a of the 1st bypass pipe 1 36a and the valve 1 33a of the second bypass pipe 1 37a, and supply the following raw material gas to the heating section 1 1 1B. Then, the temperature of the combustion catalyst 171 is increased to 800 ° C. At this time, the temperature of the reforming catalyst 161 in the reforming section 111 A rises to 700 ° C, which is a reforming temperature required for reforming.

Source gas:

Amount of isobutane: 2000 cm ³ / min (gas)

Air volume: 60000 cm ³ / min (gas)

ST 26: When the temperature of the combustion catalyst 171 reaches 800 ° C (the temperature of the reforming catalyst 161 reaches 700 ° C), the valves 1 14 of the pipe 1 17 and the valve 1 of the pipe 1 19 shown in Fig. 11 16 is opened and the following raw material gas is supplied to the reforming section 111A to cause the reforming catalyst 161 to perform the steam reforming reaction (see the above-mentioned equations (1) and (2)).

Source gas:

Amount of isobutane: 1 500 cmVmin (gas)

Water volume: 15 cm ³ / min (liquid)

At this time, the valves 132, 133 and 134 are closed to stop the supply of hydrocarbons, air and water to the small reformer 112, and the small reformer 112 and the reformer 111 are closed. The valve 146 is closed to stop the supply of product gas to A, and the supply of fuel to the burner 131 is stopped.

As a result, the following reformed gas was obtained.

Reformed gas:

The amount of the hydrogen: 1 5200 cm ³ / min

Methane amount: 200 cm ³ / min

Amount of carbon dioxide: 2600 cm ³ / min

—Amount of carbon oxide: 3500 cm ³ / min

Thereafter, the reaction of the equation (7) shown in the description of the first embodiment is continuously caused by the CO shift catalyst 163 (see FIG. 11), whereby about 90% of the carbon monoxide is converted to hydrogen and hydrogen dioxide. The carbon monoxide concentration is reduced to about 10 ppm by causing the reaction of Eq. (8) described in the first embodiment with the CO removal catalyst 164 (see Fig. 11). .

The heating of the small reformer 112 by the burner 131 starts, and the time required for the temperature of the reforming catalyst 176 to rise from room temperature to 200 ° C is 5 seconds, as shown in FIG. The time required for 6 to rise from 200 ° C to 600 ° C is 5 seconds, and the time required for the heating catalyst 1 1 1 B of the combustion catalyst 17 1 to rise from room temperature to 200 ° C is 15 Second, the time required for the combustion catalyst 17 1 to rise from 200 ° C to 800 ° C is 30 seconds, and the total of the above times is 55 seconds. This is from the start of the start of the small reformer 12 in the hydrogen generator 110 of the sixth embodiment until the reforming temperature at which the hydrogen can be generated in the reformer body 111 reaches 700 ° C. The so-called startup time.

FIGS. 15A and 15B show Comparative Example 1 and Comparative Example 2 with respect to the hydrogen generator according to the sixth embodiment including a heating unit. The same members as those of the hydrogen generator of the sixth embodiment shown in FIGS. 10 and 11 are denoted by the same reference numerals, and detailed description thereof will be omitted. The temperature measuring device 122 shown in FIG. 11 was omitted.

The hydrogen generator 200 of Comparative Example 1 shown in FIG. 15A includes a reforming section 111 A, a heating section 111 B, and an electric heater 200 for heating the heating section 111 B. The compact reformer 112 of the hydrogen generator 110 of the sixth embodiment shown in FIG. 10 is not provided. Reference numeral 202 denotes a pipe for supplying a raw material gas described later to the heating unit 111B, and reference numeral 203 denotes a valve interposed in the pipe 202.

The hydrogen generator 2 10 of Comparative Example 2 shown in FIG. 15B includes a reforming section 1 1 1 A, a heating section 1 1 1 B, and a burner 2 1 1, which heats the heating section 1 1 1 B. 2 1 1

Next, regarding the operations of Comparative Example 1 and Comparative Example 2 described above, the flow chart of Comparative Example 1 shown in FIGS. 15A, 15B and 16 and the comparison shown in FIG. An explanation will be given based on the flowchart of Example 2.

ST 31 1: Heating section 1 1 1B, specifically combustion catalyst 17 1 (see Fig. 15A), is heated to 200 ° C with a 500 W electric heater 201 to raise the temperature.

ST32: Open the valve 203 of the pipe 202, supply the following raw material gas to the heating unit 111B, and raise the temperature of the combustion catalyst 171 to 800 ° C. At this time, the temperature of the reforming catalyst 161 in the reforming section 111A rises to 700 ° C., which is the reforming temperature required for reforming.

Source gas:

Amount of isobutane: 2000 cm ³ / min (gas)

Air volume: 600 000 cm ³ / min (gas) S T33: When the temperature of the combustion catalyst 171 reaches 800 ° C (the temperature of the reforming catalyst 161 reaches 700.C), open the valves 1, 1, 1, and 1, and reform the section 1 1 1 A Hydrogen, methane, carbon dioxide, and carbon monoxide were produced by supplying isobutane and water to a steam reforming reaction.

The heating of the heating unit 1 11 B by the electric heater 201 is started, and the time for the temperature of the combustion catalyst 17 1 to rise from room temperature to 200 ° C is 200 seconds, and the time for the combustion catalyst 1 71 is 200 to 800 ° C. The time required to raise the temperature is 30 seconds, and the total of the above times is 230 seconds. This is the start-up time of the hydrogen generator 200 of Comparative Example 1.

S T41: Heating section 1 1 1B, specifically combustion catalyst 1 71 (see Fig. 15 B), is heated to 200 ° C by 2 kW burners 21 1 and 21 1 and heated.

ST42: Open the valve 203 of the pipe 202, supply the following raw material gas to the heating unit 111B, and raise the temperature of the combustion catalyst 71 to 800 ° C. At this time, the temperature of the reforming catalyst 161 in the reforming section 111 A rises to 700 ° C, which is the temperature required for reforming.

Source gas:

Amount of isobutane: 2000 cm ³ Zmin (gas)

Air volume: 60000 cmVm i n (gas)

ST 43: When the temperature of the combustion catalyst 1 71 reaches 800 ° C (the temperature of the reforming catalyst 1 61 reaches 700 ° C), open the valves 1 1 4 and 1 16 to make the reforming section 1 1 1 A Hydrogen, methane, carbon dioxide, and carbon monoxide were produced by supplying isoptan and water to the reactor and performing a steam reforming reaction.

As shown in Fig. 17, the heating section 11 1 B is started to be heated by the burners 2 11 1 and 21 1 shown in Fig. The time required for the combustion catalyst 17 1 to rise from 200 ° C to 800 ° C is 50 seconds, and the total time is 170 seconds. This is the start-up time of the hydrogen generator 210 of Comparative Example 2.

As described above, the reforming raw materials used in the sixth embodiment include the first to fifth embodiments. Similarly, light hydrocarbons such as LPG, fuel for cooking stoves, city gas, naphtha, gasoline, light oil, and kerosene may be used. Further, the aliphatic alcohol is not particularly limited, and includes methanol and ethanol.

Further, as the reforming catalyst for reforming hydrocarbons, those containing metals of Groups 8 to 10 (Fe, Co, Ni, RUPd, Pt, etc.) are desirable. A catalyst supporting u or Rh or a Ni-containing catalyst is particularly desirable. Industrial applicability

As the reforming catalyst housed in the reformer body, a catalyst having at least a reforming catalyst function and a combustion catalyst function is used, and hydrogen and air are supplied to the catalyst to cause catalytic combustion of hydrogen. The temperature of the reforming catalyst can be raised to the reforming temperature, and the startup time of the hydrogen generator can be shortened. Furthermore, since a special heating device is not required for raising the temperature of the reforming catalyst, the size of the hydrogen generator can be reduced, which is useful for putting a fuel cell into practical use.

Claims

The scope of the claims

1. A hydrogen generating apparatus that raises the reforming catalyst to a reforming temperature of about 700 ° C. and makes the reforming catalyst come into contact with a raw material gas composed of hydrocarbons or aliphatic alcohols to reform hydrogen. So,

A reforming catalyst comprising a combustion catalyst that promotes a reaction between hydrogen and oxygen, or a mixture of the reforming catalyst and the combustion catalyst or a juxtaposition of the reforming catalyst;

A cylindrical container for storing the reforming catalyst;

External hydrogen supply means for supplying hydrogen to the cylindrical container to perform catalytic combustion; external air supply means for supplying air to the cylindrical container;

A hydrogen generator, comprising: raising the temperature of the reforming catalyst to a reforming temperature.

2. The hydrogen generation according to claim 1, wherein the combustion catalyst is platinum.

3. The hydrogen generator according to claim 1, wherein the reforming catalyst includes at least a catalyst in which platinum having the function of a reforming catalyst and a combustion catalyst is supported on the surface of an alumina carrier.

4. The external hydrogen supply means is a small-sized hydrogen generator that contains a reforming catalyst in a small container smaller than the cylindrical container and includes a small heater that raises the temperature of the reforming catalyst to a reforming temperature. The hydrogen generator according to claim 1, wherein:

5. A hydrogen generating apparatus that raises the reforming catalyst to a reforming temperature of about 700 ° C. and makes the reforming catalyst come into contact with a raw material gas composed of hydrocarbons or aliphatic alcohols to reform hydrogen. So,

A cylindrical container containing the reforming catalyst;

A heater attached to the cylindrical container and containing a combustion catalyst for promoting a reaction between hydrogen and oxygen; External hydrogen supply means for supplying hydrogen to the heater to perform catalytic combustion; external air supply means for supplying air to the heater;

Wherein the temperature of the reforming catalyst is raised to a reforming temperature by the heater.

6. The hydrogen generation according to claim 5, wherein the combustion catalyst is platinum.

7. The external hydrogen supply means is a small hydrogen generator that includes a small heater that stores the reforming catalyst in a small container smaller than the cylindrical container and raises the temperature of the reforming catalyst to the activation start temperature. The hydrogen generator according to claim 5, wherein: