JPH10106606A - Hydrogen manufacturing device, and manufacture thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hydrogen manufacturing device and a method thereof capable of compact device designing and capable of being operated without supplying steam. SOLUTION: Fuel from a fuel pump and air from an air blast machine 3 are fed to a device main body 1 each at a specified flow rate. The fed fuel and air are mixed in an inlet mixing layer 10, partial oxidization reaction and complete combustion reaction are achieved in an oxidization layer 20, and a high-temperature gas including carbon monoxide, carbon dioxide, and steam is obtained. This gas is mixed while passing through an intermediate mixing layer 30, and the temperature is lowered. In a conversion reaction layer 40, while the gas temperature is gradually lowered, carbon monoxide and steam in the gas conversely react with each other, and carbon dioxide and hydrogen are generated. Then, hydrogen-rich gas is generated and fed to a fuel cell 101.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a hydrogen production apparatus and a hydrogen production method for producing a hydrogen-rich gas by reforming a hydrocarbon-based fuel such as natural gas, methanol, and naphtha.

[0002]

2. Description of the Related Art As a hydrogen producing apparatus for supplying hydrogen to a fuel cell or the like, a fuel such as natural gas, methanol, naphtha or methane is mixed with steam to produce a hydrogen-rich gas with a reforming catalyst. A so-called steam reforming system for reforming is widely used. This steam reforming reaction is usually carried out at a high temperature of about 750 to 800 ° C. in a reformer equipped with a catalyst, and is represented by the following reaction formula 1 in the case of methane.

[0003]

Embedded image The reformed gas generated by such a steam reforming reaction contains carbon monoxide to some extent. However, since carbon monoxide causes deterioration of the electrode catalyst of the fuel cell, the conversion reaction catalyst layer is further added. In many cases, carbon monoxide in the reformed gas is converted into carbon dioxide by the reaction shown below through a CO converter having the following formula, and then supplied to the fuel cell. Usually, the CO converter is used to convert the catalyst layer for the conversion reaction to 200 to 300.
Operate while maintaining the temperature at about ° C.

[0004]

Embedded image By the way, for such a hydrogen production device, it is convenient to use it at home or carry it outdoors.
The compactness of the device is often required. As a conventional relatively compact hydrogen production apparatus, for example, as disclosed in JP-A-2-264903 and JP-A-5-186201, a double cylindrical tube is filled with a reforming catalyst. A method is known in which fuel and steam are fed into the reaction layer while the reaction layer is heated by a burner and reformed.

Further, as disclosed in Japanese Patent Application Laid-Open No. 7-335238, first, a raw material is mixed with air and partially oxidized using a catalyst for partial oxidation. A device for mixing with steam supplied from a steam reformer using a reforming catalyst has also been developed. In this device, the heat generated by the partial oxidation reaction is transferred to the reforming catalyst and used for the reforming reaction. I have.

[0006]

However, such a steam reforming type hydrogen production apparatus requires a large amount of a steam reforming catalyst due to the slow steam reforming reaction. There is a problem that this hinders the downsizing of the device. In addition, since the above-described steam reforming type hydrogen production apparatus is designed to operate while being supplied with steam from the outside, there is also a problem that it cannot be operated without a steam supply source such as a boiler. .

To solve such a problem, it is conceivable to attach a small boiler to the hydrogen production apparatus, but this hinders the downsizing of the apparatus. In view of such problems, the present invention enables a compact device design,
An object of the present invention is to provide a hydrogen production apparatus and a hydrogen production method that can be operated without receiving supply of steam.

[0008]

In order to achieve the above object, a hydrogen production apparatus according to the present invention comprises a mixing section for mixing fuel and air to produce a mixed gas, and a mixing section for producing a mixed gas. An oxidizing unit that partially oxidizes part of the fuel contained in the gas and oxidizes another part to complete combustion, and carbon monoxide generated by the partial oxidation contained in the mixed gas is mixed in the mixed gas. And a conversion reaction section for converting carbon dioxide and hydrogen by water generated by the complete combustion contained in the fuel cell.

In the hydrogen production apparatus, the fuel and air are mixed in the mixing section to generate a mixed gas, and in the oxidizing section, a part of the fuel contained in the mixed gas is partially oxidized and another part is mixed. Is oxidized to complete combustion.
Then, the fuel is partially oxidized to generate carbon monoxide and hydrogen, and is completely burned to generate carbon dioxide and water.

Taking the case where the fuel is methane as an example, partial oxidation is mainly a reaction represented by the following formula (3), and complete combustion is a reaction represented by the following formula (4).

[0011]

Embedded image

[0012]

Embedded image In the partial oxidation, in addition to the reaction formula of the above chemical formula 3,
The reaction represented by the following reaction formula 5 also occurs to some extent.

[0013]

Embedded image The mixed gas oxidized in the oxidizing section contains carbon monoxide, water, hydrogen, and carbon dioxide. Next, in the conversion reaction section, carbon monoxide and water contained in the mixed gas from the oxidation section undergo a conversion reaction as shown in the above reaction formula 2 to produce carbon dioxide and hydrogen. Is done.

As described above, in the present hydrogen production apparatus, a hydrogen-rich gas having a low carbon monoxide content can be produced by supplying only fuel and air without receiving supply of steam or water from the outside. Generated. Further, since the conversion reaction section can be heated by the heat generated in the oxidizing section, there is no need to provide a separate heating means such as a burner.

Although such an oxidizing section can be realized by using a catalyst for partial oxidation, the amount of the catalyst can be considerably smaller than when a catalyst for steam reforming is used. The size can be reduced. Here, the oxidizing section is mainly a partial oxidation reaction with respect to the fuel in one of the mixed gas divided by the gas dividing means and the gas dividing means which divides the mixed gas from the mixing section at a predetermined ratio. It can also be composed of a partial oxidation reaction layer for oxidizing and a combustion reaction layer for oxidizing mainly the complete combustion with respect to the fuel in the other mixed gas divided by the gas dividing means.

In this case, the ratio between the partial oxidation performed in the partial oxidation reaction layer and the complete combustion performed in the combustion reaction layer can be adjusted by adjusting the ratio of bisecting the mixed gas by the gas dividing means. Therefore, with this adjustment,
The ratio of carbon monoxide and water in the gas introduced into the conversion reaction section can be set to a ratio suitable for the conversion reaction (a ratio suitable for reducing the concentration of carbon monoxide).

The mixing section is provided with first mixing means for mixing fuel and air at a first ratio and second mixing means for mixing at a second ratio, and the oxidizing section is provided with a first mixing means. A partial oxidation reaction layer that oxidizes the mixed gas mixed by the means mainly based on a partial oxidation reaction, and a combustion that performs an oxidation mainly completed combustion on the mixed gas mixed by the second mixing means A reaction layer can also be provided.

In this case, the fuel and air mixed at the first ratio in the first mixing means are sent to the partial oxidation reaction layer, and the fuel and air mixed at the second ratio in the second mixing means. Is sent to the combustion reaction layer. Therefore,
Fuel and air can be supplied to the partial oxidation reaction layer at a ratio suitable for the partial oxidation reaction, and fuel and air can be supplied to the combustion reaction layer at a ratio suitable for the reaction. The ratio between partial oxidation performed in the partial oxidation reaction layer and complete combustion performed in the combustion reaction layer can also be adjusted.

Further, if the conversion reaction section is provided with a catalyst layer for the conversion reaction and a means for adjusting the amount of heat radiation from the inlet to the outlet of the catalyst layer is provided, Temperature distribution from the inlet to the outlet of the catalyst layer can be adjusted to a state suitable for the conversion reaction. In order to achieve the above object, the hydrogen production method of the present invention includes a mixing step of mixing fuel and air to generate a mixed gas, and a mixed gas generated in the mixing step.
An oxidation step in which part of the fuel contained in the mixed gas is partially oxidized and another part is oxidized so as to be completely burned, and carbon monoxide generated by the partial oxidation contained in the mixed gas is mixed. And a conversion reaction step of converting carbon dioxide and hydrogen by water generated by complete combustion contained in the gas.

[0020]

Embodiments of the present invention will be described below with reference to the drawings. (First Embodiment) [Description of Overall Configuration of Hydrogen Production Apparatus] FIG. 1 is a perspective view of a hydrogen production apparatus according to an embodiment of the present invention. Also,
FIG. 2 is a schematic cross-sectional view of an apparatus main body of the hydrogen production apparatus, in which gas flows are indicated by arrows.

This hydrogen production apparatus converts fuel supplied from a fuel tank 100 into a hydrogen-rich gas and supplies it to a fuel cell 101. The apparatus main body 1 mixes the gas and performs a catalytic reaction. A fuel pump 2 for feeding fuel from the fuel tank 100 to the apparatus main body 1, and a blower 3 for sending air to the apparatus main body 1. Here, a case in which city gas containing methane as a main component is supplied from the fuel tank 100 will be described.
The operation can be performed by supplying a hydrocarbon-based fuel such as naphtha, or by supplying methanol or the like by vaporizing a liquid fuel.

The apparatus main body 1 mixes the gas from the inlet mixed layer 10 for mixing the fuel and air, the oxidized layer 20 for oxidizing the mixed gas so that partial oxidation and complete combustion are performed, and the mixed gas. It is composed of an intermediate mixed layer 30 and a conversion reaction layer 40 for converting carbon monoxide generated by partial oxidation with water generated by complete combustion. Inlet mixed layer 10, oxide layer 20, intermediate mixed layer 30, conversion reaction layer 4
Numerals 0 are provided in this order in the cylindrical container 4, and between adjacent layers, a mesh-like partition plate 5 through which gas can flow is provided.
It is divided by 6,7.

The inlet mixed layer 10 is formed by filling a filler 11 into a cylindrical space sandwiched between an end face 4a on the inlet side of the cylindrical container 4 and the partition plate 5, and a fuel pump is provided at the center of the end face 4a. A fuel port 12, which is an inlet of fuel from the blower 2, and an air port 13, which is an inlet of air from the blower 3, are attached.
The filler 11 is for uniformly mixing the gas, and specific examples thereof include a metal (or ceramic) sphere (2 to 3 mm in diameter) as shown in FIG. And those obtained by laminating circular metal nets and forming them into a columnar shape.

The fuel supplied from the fuel port 12 and the air supplied from the air port 13 are mixed in the inlet mixing layer 10 and sent to the oxide layer 20. The oxidation layer 20 has a structure in which an oxidation catalyst layer 21 formed by filling an oxidation reaction catalyst in a cylindrical space sandwiched between the partition plate 5 and the partition plate 6 is formed. Specific examples of the oxidation reaction catalyst for forming the oxidation catalyst layer 21 include a catalyst in which a platinum-based catalyst such as platinum, palladium, ruthenium, and rhodium is supported on a porous alumina formed in a honeycomb shape, and a tablet-shaped catalyst. And spherical ones.

The mixed gas of the fuel and the air passing therethrough is mainly subjected to both partial oxidation as shown in the above chemical formula 3 and complete combustion as shown in the above chemical formula 4, and a part thereof is converted into the above-mentioned gas. The partial oxidation shown in FIG. 5 is performed. Since both the partial oxidation and the complete combustion are exothermic reactions, after the mixed gas has passed through the oxide layer 20, hydrogen, carbon monoxide,
A high-temperature gas containing carbon dioxide and water vapor is sent to the intermediate mixed layer 30.

In the oxidized layer 20, the gas temperature rises due to the heat generated by the partial oxidation reaction and the complete combustion reaction, whereby the temperature of the oxidized layer 20 becomes 600 to 700 ° C.
The flow rate and the like of the mixed gas fed into the oxide layer 20 are set to be approximately the same. The intermediate mixed layer 30 includes the partition plate 6
A filler 31 similar to the above-described filler 11 is filled in a columnar space sandwiched between the partition member 7 and the partition member 7.

The intermediate mixed layer 30 is mixed with the gas from the oxide layer 20 to make it uniform. In addition, since the temperature of the gas from the oxide layer 20 is too high to directly lead to the conversion reaction layer 40, the intermediate mixed layer 30 also serves to lower the temperature of the gas to a temperature suitable for the conversion reaction layer 40. Although not shown, a radiating fin or the like may be provided around the intermediate mixed layer 30 in order to adjust the temperature of the gas entering the conversion reaction layer 40.

The reaction layer 40 has a structure in which a conversion reaction catalyst is filled in a columnar space sandwiched between the partition plate 7 and the end face 4b of the cylindrical container 4 to form a conversion reaction catalyst layer 41. A gas outlet 14 for sending a hydrogen-rich gas to the fuel cell 101 is attached to the center of the end face 4b. The catalyst forming the conversion reaction catalyst layer 41 is a conversion reaction catalyst conventionally used in a CO converter combined with a steam reformer, and specific examples thereof include tablet-shaped copper-zinc. System catalysts.

Normally, the volume of the conversion reaction catalyst layer 41 is
The volume may be set to about 10 times the volume of the oxidation catalyst layer 21.
Further, the temperature of the conversion reaction layer 40 is about 300 ° C. on the inlet side,
It is desirable to form a temperature gradient at about 200 ° C. at the outlet side. In the present embodiment, fins 42 are attached to the cylindrical container 4 around the conversion reaction layer 40 to adjust the temperature. Have been.

By forming such a temperature gradient, the conversion reaction represented by the above formula (2) quickly reaches equilibrium on the inlet side at a relatively high temperature (300 ° C.), and the outlet at a relatively low temperature (200 ° C.) On the side, the carbon monoxide concentration in the gas is reduced to a low level because the equilibrium of the conversion reaction of the above formula (2) moves to the right. When the 3 kW class fuel cell 101 is operated using the hydrogen production apparatus described above, the consumption of city gas is about 2 Nm ³ / h. In this case, the volume of the oxidation catalyst layer 21 of the apparatus main body 1 is 150 c
c and the volume of the conversion reaction catalyst layer 41 may be set to about 1500 cc.

On the other hand, when the same fuel cell is operated by using a conventional steam reforming type hydrogen production apparatus having a steam reforming catalyst layer and a conversion reaction catalyst layer, the set volume of the conversion reaction catalyst layer is However, since it is necessary to set the volume of the steam reforming catalyst layer to about 3 to 10 times the oxidation catalyst layer 21, it is difficult to reduce the size as compared with the hydrogen production apparatus of the present embodiment. It can be said that.

[Explanation of Operation and Operation Method of Hydrogen Production Apparatus] In the hydrogen production apparatus having such a configuration, during operation, fuel is supplied from the fuel pump 2 and air is supplied from the blower 3 at predetermined flow rates. Feed it into the main body 1. As shown in FIG. 2, the supplied fuel and air are mixed in the inlet mixing layer 10, and a partial oxidation reaction and a complete combustion reaction are performed in the oxidation layer 20, and hydrogen, carbon monoxide, carbon dioxide, and water vapor are formed. At a high temperature (750-800 ° C.). This gas is mixed while passing through the intermediate mixed layer 30, and the temperature also decreases. In the conversion reaction layer 40, while the temperature of the gas gradually decreases, carbon monoxide and water vapor in the gas undergo a conversion reaction to produce carbon dioxide and hydrogen. Then, the gas is supplied to the fuel cell 101 as a hydrogen-rich gas having a low carbon monoxide concentration.

The fuel cell 101 generates power using the hydrogen-rich gas. Here, the setting of the reaction conditions in the oxide layer 20 will be described. Since the ratio of carbon monoxide and water introduced into the conversion reaction layer 40 depends on the ratio between the partial oxidation reaction and the complete combustion reaction that occur in the oxide layer 20, the reaction conditions in the oxide layer 20 are suitable for the conversion reaction. The ratio may be set so that the partial oxidation reaction and the complete combustion reaction occur so as to achieve the above ratio.

As a method of setting these conditions, the oxide layer 20
The ratio at which the partial oxidation reaction and the complete combustion reaction take place in the above depends on conditions such as the ratio of fuel and air fed into the oxide layer 20 and the flow rate, or the temperature of the oxide layer 20. The optimum conditions may be determined experimentally by changing these conditions in various ways and set to the optimum conditions.

This ratio can be obtained as follows by a simple calculation, assuming that the fuel consists only of methane. As shown in the chemical formula 2, in the conversion reaction in the conversion reaction layer 40, 1 mol of water is added to 1 mol of carbon monoxide.
Since ol is required, the simple calculation may be set so that 1 mol of water is generated for 1 mol of carbon monoxide in the oxide layer 20.

Accordingly, if only the partial oxidation reaction of the chemical formula 3 and the complete combustion of the chemical formula 4 are performed in the oxide layer 20, 2 mol of the 3 mol of methane treated in the oxide layer 20 Partial oxidation reaction takes place,
l should be adjusted so that the complete combustion of Chemical Formula 4 is performed. In addition, when the partial oxidation reaction of the chemical formula 3 and the complete combustion of the chemical formula 4 are performed at such a ratio, methane and oxygen are consumed in the oxidized layer 20 in an equimolar amount. The volume ratio between methane and air fed into the layer 10 may be set to about 1: 5.

However, experimentally, a better result is obtained by using excess air (about twice as much as the simple calculated value) than the simple calculated value. (Embodiment 2) FIG. 3 is a perspective view of a hydrogen production apparatus according to the present embodiment. The hydrogen production apparatus according to the present embodiment also converts the fuel supplied from the fuel tank 100 into a hydrogen-rich gas and supplies the same to the fuel cell 101, as in the first embodiment. And a fuel pump 202 that feeds the fuel in the fuel tank 100 to the device main body 201.

The apparatus main body 201 includes an ejector type mixer 210 for mixing air (fuel gas) supplied from the fuel pump 202 at a predetermined ratio, and a mixer 210.
And a square-shaped catalyst layer 220 that performs a catalytic reaction on the mixed gas mixed in the above. The oxidizing section 220a and the intermediate mixing section 2 are formed in the catalyst layer 220 from the gas inlet side to the gas outlet side.
20b and three parts of the conversion reaction section 220c. The oxidizing section 220a, the intermediate mixing section 220b, and the conversion reaction section 220c have functions similar to those of the oxide layer 20, the intermediate mixing layer 30, and the conversion reaction layer 40 of the first embodiment.

The mixer 210 is mounted on the inlet side of the catalyst layer 220 (on the oxidizing section 220a side). Mixer 210
Although the internal structure is not shown, a suction chamber is provided inside the mixer 210, and the fuel gas fed from the fuel pump 202 is supplied to a nozzle at the tip of a fuel injection pipe 211 (this nozzle is disposed in the suction chamber. ), And with this injection, outside air is taken in from the air intake 212 and drawn into the suction chamber, where it is mixed with fuel gas.

Further, inside the mixer 210, there is provided an air amount adjusting mechanism (not shown) for adjusting the ratio of the air intake amount to the fuel gas injection amount. Specifically, this air amount adjusting mechanism is provided with a damper for adjusting the degree of opening of the passage in the air flow passage from the air intake 212 to the suction chamber, or moves the position of the nozzle in the suction chamber. It can be realized by providing means.

Since an ejector having such an air amount adjusting function is widely used in a general gas burner, a detailed description thereof will be omitted. The catalyst layer 220 has a structure in which a rectangular shaped outer case 221 is filled with a catalyst molded body 230, and the outer case 22
1 includes a case body 221a having an open upper surface, and a lid 221b covering the opening.

The catalyst formed body 230 includes the catalysts 232a, 23
A plurality of corrugated plates 231 on which 2c are disposed are formed by being vertically stacked. Each corrugated plate 231
, A tablet-shaped oxidation reaction catalyst 232a (platinum-based catalyst) is provided in a region corresponding to the oxidizing section 220a, and no catalyst is provided in a region corresponding to the intermediate mixing section 220b. A conversion reaction catalyst 232 formed in a tablet shape is provided in an area corresponding to the reaction section 220c.
c is provided. Then, the oxidized portions 220a,
The intermediate mixing section 220b and the conversion reaction section 220c are formed by such a catalyst arrangement.

The oxidation reaction catalyst 23 used here
The catalyst 2a and the conversion reaction catalyst 232c are the same as the tablet-shaped catalyst described in the first embodiment. The temperature from the inlet side to the outlet side of the conversion reaction section 220c is set to 300, similar to the conversion reaction layer 40 of the first embodiment.
It is preferable to adjust the temperature to 200 ° C. to 200 ° C., and although not shown in FIG.
May be provided on the outer case 221 around the fin.

In the hydrogen production apparatus having such a configuration,
During operation, fuel is supplied from the fuel pump 202 to the mixer 210 at a predetermined flow rate. In the mixer 210, air is taken in at a predetermined ratio with respect to the fed fuel by an air amount adjusting mechanism. Thus, the mixer 210
The fuel and air taken in are mixed by the mixer 210,
Oxidizing section 220a, intermediate mixing section 220b, conversion reaction section 22
By sequentially passing through Oc, a catalytic reaction is performed in the same manner as in the first embodiment, and the gas is converted into a hydrogen-rich gas having a low carbon monoxide concentration and sent to the fuel cell 101.

(Embodiment 3) FIG. 4 is a schematic sectional view of a main body of a hydrogen production apparatus according to the present embodiment. The same components as those in the first embodiment are denoted by the same reference numerals in the drawings, and description thereof will be omitted. The device main body 301 has the same configuration as the device main body 1 of the first embodiment, but in the present embodiment,
The oxide layer 320 is divided by a partition plate 302 into a partial oxide layer 321 and a complete combustion layer 322, and the gas mixed in the inlet mixed layer 10 is mixed at a predetermined ratio with the partial oxidation layer 321 and the complete combustion layer. 322.

The basic structure of the partial oxidation layer 321 and the complete combustion layer 322 is the same as that of the oxide layer 20 of the first embodiment, and the platinum-based catalyst described in the first embodiment is used. The type of catalyst used and the set temperature of each layer are selected so that the partial oxidation reaction mainly occurs in the partial oxidation layer 321 and the complete combustion mainly occurs in the complete combustion layer 322.

Specific methods for selecting the type of catalyst include:
What is used for the partial oxidation layer 321 may be an experiment with each of the platinum-based catalysts described above, and an appropriate one for the partial oxidation reaction may be selected. On the other hand, the one used for the complete combustion layer 322 may be one selected from the above platinum-based catalysts suitable for complete combustion by experiments, or a nickel-based catalyst suitable for complete combustion may be used. .

As for the set temperature of each layer, partial oxidation is likely to occur at a relatively low temperature and complete combustion is likely to occur at a relatively high temperature, so that the partial oxidation layer 321 has a lower temperature than the complete combustion layer 322. Set as follows. The normal set temperature of each layer is such that the partial oxide layer 321
0 ° C., and the temperature of the complete combustion layer 322 is 700 to 800 ° C. In order to set the temperature of the partial oxidation layer 321 lower than the temperature of the complete combustion layer 322 in this embodiment,
A fin 323 is attached to the outside of the partial oxide layer 321 of the cylindrical container as shown in FIG.

As for the above-mentioned predetermined ratio (the ratio of the partial oxidation layer 321 and the complete combustion layer 322), various ratios may be changed to carry out experiments, and the optimum ratio may be obtained from the results. Similar to the calculation in 1, the simple calculation assuming that the fuel consists only of methane is 3 m
of methane, 2 mol is formed by partial oxidation layer 321
Of the complete combustion layer 322
It is sufficient to set so that the complete combustion of Chemical Formula 4 is performed.

In the hydrogen production apparatus having such a configuration,
During operation, fuel and air are fed into the apparatus main body 1 at predetermined flow rates, respectively, as in the first embodiment. The fed fuel and air are mixed in the inlet mixing layer 10 and separated into a partial oxidation layer 321 and a complete combustion layer 322 at a predetermined ratio. Then, in the partial oxidation layer 321, a high-temperature gas containing hydrogen and carbon monoxide is mainly generated by the partial oxidation reaction, and a high-temperature gas containing carbon dioxide and water vapor is generated in the complete combustion layer 322 by a complete combustion reaction. Is done.

In the intermediate mixed layer 30, the gas from the partial oxidation layer 321 and the gas from the complete combustion layer 322 are mixed, and at the same time, the temperature is lowered and flows into the conversion reaction layer 40. Then, a conversion reaction is performed in the conversion reaction layer 40, and a hydrogen-rich gas having a low carbon monoxide concentration is generated and sent to the fuel cell 101. Thus, in the present embodiment, the oxide layer 3
20 is a partial oxidation layer 321 mainly performing a partial oxidation reaction
And a complete combustion layer 322 that mainly performs complete combustion. By adjusting the ratio of bisecting the mixed gas, partial oxidation performed in the partial oxidation reaction layer and complete combustion performed in the combustion reaction layer are performed. Can be adjusted, whereby the ratio of carbon monoxide and water introduced into the conversion reaction layer 40 can be adjusted.

In the apparatus main body 301 of the present embodiment, the mixed gas contains the partial oxidation layer 321 and the complete combustion layer 32.
The predetermined ratio, which is divided into two, is fixed, but the ratio can be easily changed by providing a damper between the inlet mixed layer 10 and the oxide layer 320 for adjusting the gas flow rate. That is, the ratio of the gas divided into the partial oxidation layer 321 and the complete combustion layer 322 can be adjusted so as to adapt to changes in the operating conditions.

(Embodiment 4) FIG. 5 is a schematic sectional view of a main body of a hydrogen production apparatus according to the present embodiment. The same components as those in the first embodiment are denoted by the same reference numerals in the drawings, and description thereof will be omitted. The device main body 401 has the same configuration as the device main body 1 of the first embodiment, but in the present embodiment,
The inlet mixed layer 410 and the oxide layer 320 are separated by the partition plate 402, and the inlet mixed layer 410 is divided into the first mixed layer 41.
1 and the second mixed layer 412, and the oxide layer 420
It is divided into a partial oxidation layer 421 and a complete combustion layer 422.

The inlet mixed layer 410 has basically the same structure as that of the inlet mixed layer 10 of the first embodiment.
A predetermined amount of fuel and a predetermined amount of air are separately fed into the first mixed layer 411 and the second mixed layer 412 divided by the second section. The configuration of the partial oxidation layer 421 and the complete combustion layer 422 is the same as that of the partial oxidation layer 321 of the third embodiment.
And the complete combustion layer 322, and
Fins 423 are attached to the outside of 1, and the temperature is set so that the partial oxidation reaction easily occurs in the partial oxidation layer 421 and the complete combustion occurs in the complete combustion layer 422.

The fuel and air sent to the first mixed layer 411 are mixed here, and then sent to the partial oxidation layer 421, where the partial oxidation reaction is mainly performed, whereby the high temperature containing hydrogen and carbon monoxide is contained. Gas is generated. On the other hand, the fuel and the air sent to the second mixed layer 412 are mixed here and then sent to the complete combustion layer 422, where a complete combustion reaction is mainly performed, so that a high-temperature gas containing carbon dioxide and water vapor is emitted. Is generated.

In the intermediate mixed layer 30, the gas from the partial oxidation layer 421 and the gas from the complete combustion layer 422 are mixed, and at the same time, the temperature decreases and flows into the conversion reaction layer 40. Then, in the conversion reaction layer 40, a hydrogen-rich gas having a low carbon monoxide concentration is generated by the conversion reaction and sent to the fuel cell 101. First mixed layer 411 and second mixed layer 4
As for the amounts of fuel and air to be fed into the fuel cell 12, the optimum flow rate may be determined from the results of experimentally varying the flow rates and set based on the optimum flow rate. A simple calculation of the ratio of the quantities can also be made.

In the partial oxidation layer 421, 2 mol of methane undergoes a partial oxidation reaction with 1 mol of oxygen (corresponding to about 5 mol in the air) according to the chemical formula 3, and in the complete combustion layer 422, 1 mol of methane converts 2 mol of oxygen (by air) according to the chemical formula 4. About 10
mol), the first mixed layer 411 contains 2 mol of methane and 5 mol of methane.
A considerable amount of air may be sent to the second mixed layer 412 with 1 mol of methane and 10 mol of air.

As described above, in the present embodiment, oxide layer 420 is divided into partial oxide layer 421 mainly performing a partial oxidation reaction and complete combustion layer 422 mainly performing a complete combustion. 421 and complete combustion layer 42
The amounts of the fuel and the air introduced into the fuel cell 2 and the fuel cell 2 can also be set independently of each other. Therefore, fuel and air are supplied at a ratio suitable for the partial oxidation reaction to the partial oxidation layer 421, and fuel and air are supplied at a ratio suitable for the complete combustion to the complete combustion layer 422. be able to. (Other Matters) In the first, third, and fourth embodiments, the example in which the fins are provided to adjust the temperature of the conversion reaction layer and the partial oxidation reaction layer has been described. The temperature may be adjusted by arranging a pipe for air introduced into the mixed layer around the conversion reaction layer or the partial oxidation reaction layer in a coil shape. In this case,
The air introduced into the inlet mixed layer is preheated when passing through the piping.

[0059]

As described above, the hydrogen production apparatus according to the present invention comprises a mixing section for mixing fuel and air to generate a mixed gas, and a fuel mixture contained in the mixed gas. An oxidizing part that partially oxidizes and oxidizes another part to complete combustion, and carbon monoxide generated by the partial oxidation contained in the mixed gas by the complete combustion contained in the mixed gas Since it is configured to include a conversion reaction section that converts carbon dioxide and hydrogen with the generated water, the apparatus can be made compact and can be operated without receiving a supply of steam.

Further, in the hydrogen production method of the present invention, a mixing step of mixing a fuel and air to generate a mixed gas, and a step of mixing the mixed gas generated in the mixing step with a part of the fuel contained in the mixed gas Is partially oxidized and another part is oxidized so as to be completely burned, and carbon monoxide generated by the partial oxidation contained in the mixed gas is converted into water generated by the complete combustion contained in the mixed gas. A similar effect can be obtained by a configuration comprising a conversion reaction step of converting carbon dioxide and hydrogen into carbon dioxide and hydrogen.

The hydrogen production apparatus and the hydrogen production method of the present invention are of great practical value, especially for supplying hydrogen to a portable fuel cell.

[Brief description of the drawings]

FIG. 1 is a perspective view of a hydrogen production apparatus according to a first embodiment.

FIG. 2 is a schematic sectional view of an apparatus main body of the hydrogen production apparatus shown in FIG.

FIG. 3 is a perspective view of a hydrogen production apparatus according to a second embodiment.

FIG. 4 is a schematic sectional view of a main body of the hydrogen production apparatus according to Embodiment 3.

FIG. 5 is a schematic sectional view of a main body of the hydrogen production apparatus according to Embodiment 4.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Device main body 2 Fuel pump 3 Blower 4 Cylindrical container 10 Inlet mixed layer 20 Oxidation layer 30 Intermediate mixed layer 40 Conversion reaction layer 42 Fin 100 Fuel tank 101 Fuel cell 201 Device main body 202 Fuel pump 210 Mixer 220 Catalyst layer 220a Oxidation part 220b Intermediate mixing section 220c Conversion reaction section 301 Device body 320 Oxidation layer 321 Partial oxidation layer 322 Complete combustion layer 401 Device body 410 Inlet mixture layer 411 First mixture layer 412 Second mixture layer 420 Oxide layer 421 Partial oxidation layer 422 Complete combustion layer

Claims (5)

[Claims] A mixing unit that mixes fuel and air to generate a mixed gas; and a mixed gas that is generated in the mixing unit is partially oxidized while another part of the fuel contained in the mixed gas is partially oxidized. Oxidation part that oxidizes partly to complete combustion, and converts carbon monoxide generated by partial oxidation contained in the mixed gas into carbon dioxide and hydrogen by water generated by complete combustion contained in the mixed gas And a conversion reaction section. 2. The oxidizing unit includes: a gas dividing unit that divides the mixed gas from the mixing unit into two at a predetermined ratio; and a partial oxidation unit that divides the fuel in one of the mixed gases divided by the gas dividing unit. A partial oxidation reaction layer that oxidizes mainly by reaction; and a combustion reaction layer that oxidizes mainly fuel by complete combustion with respect to the fuel in the other mixed gas divided by the gas dividing means. The hydrogen production apparatus according to claim 1, wherein: 3. The mixing unit includes a first mixing unit that mixes fuel and air at a first ratio, and a second mixing unit that mixes fuel and air at a second ratio. A partial oxidation reaction layer that performs an oxidation mainly based on a partial oxidation reaction on the mixed gas mixed by the mixing means, and an oxidation mainly based on complete combustion on the mixed gas mixed by the second mixing means. The hydrogen production apparatus according to claim 1, further comprising a combustion reaction layer for performing the reaction. 4. The conversion reaction section includes a catalyst layer for a conversion reaction, and a heat radiation amount adjusting means for adjusting a heat radiation amount from an inlet to an outlet of the catalyst layer. The hydrogen production apparatus according to any one of claims 1 to 3. 5. A mixing step of mixing a fuel and air to generate a mixed gas, and separating the mixed gas generated in the mixing step while partially oxidizing a fuel contained in the mixed gas. An oxidation step in which part of the gas is oxidized to complete combustion, and carbon monoxide generated by the partial oxidation contained in the mixed gas is converted to carbon dioxide and hydrogen by water generated by the complete combustion contained in the mixed gas And a conversion reaction step.