JP2000159501A - Hydrogen-containing gas-producing apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hydrogen-containing gas-producing apparatus enabling miniaturization, capable of making the apparatus inexpensive and reducing hydrogen-containing gas production cost. SOLUTION: This hydrogen-containing gas producing apparatus is obtained by integrally forming, in unit state, a steam-generating part 2 for evaporating water by heating, a reforming treatment part 3 for carrying out reforming reaction of steam generated in the steam generating part 2 with a hydrocarbon- based raw fuel gas and producing a gas containing hydrogen gas and a heating part H for heating the reforming treatment part 3 and the steam generating part 2.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hydrogen-containing gas generator for producing a gas containing hydrogen gas by subjecting a hydrocarbon-based fuel gas and steam to a reforming reaction.

[0002]

2. Description of the Related Art In such a hydrogen-containing gas generator, steam and a hydrocarbon-based raw fuel gas are supplied.
A reforming unit is provided to generate a hydrogen-containing gas containing hydrogen gas by performing a reforming reaction. However, since the reforming reaction between steam and the raw fuel gas in the reforming unit is an endothermic reaction, A heating section for heating the reforming section is provided to give reaction heat. Conventionally, a steam generator for generating steam for the reforming reaction is provided separately from the reforming section and the heating section, and steam is supplied from the steam generating apparatus to the reforming section. The generator and the reforming section were connected by a steam supply pipeline.

[0003]

However, conventionally, there have been the following various problems due to the fact that the steam generator is provided separately from the reforming section and the heating section. That is, there is a problem that the external shape becomes large. In addition, the manufacturing process of the hydrogen-containing gas generator becomes complicated, so that there is a problem that the price of the device increases. In addition, since the heat loss is increased due to the large surface area, it is necessary to increase the amount of energy input to the heating unit, and there has been a problem that the cost of producing a hydrogen-containing gas increases.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a hydrogen-containing gas generating apparatus which can be reduced in size and cost and can reduce the cost of producing the hydrogen-containing gas. is there.

[0005]

According to a first aspect of the present invention, there is provided a steam generator for evaporating water by heating, and a steam and hydrocarbon-based raw fuel gas generated in the steam generator. Is supplied, a reforming section for generating a hydrogen-containing gas by reforming them, and a heating section for heating the reforming section and the steam generating section are integrally formed as a unit. I have. Then, in the steam generating section, water is evaporated by heating by the heating section to generate steam, and in the reforming section, the raw fuel gas and the steam generated in the steam generating section are supplied. The heating by the heating unit causes a reforming reaction to generate a hydrogen-containing gas. In other words, the hydrogen-containing gas generator is unitized in a state in which it has a function of generating steam used for the reforming reaction and a function of generating a hydrogen-containing gas by performing a reforming reaction between the steam and the raw fuel gas. The hydrogen-containing gas is generated by supplying water and the raw fuel gas to the hydrogen-containing gas generator integrally formed in such a unit shape.

Therefore, by integrally forming the hydrogen-containing gas generator in a unit shape, the outer shape of the hydrogen-containing gas generator can be made smaller than before. In addition, since the manufacturing process of the hydrogen-containing gas generator is simplified, the cost of the apparatus can be reduced as compared with the related art. Also, since the surface area is smaller than before, heat radiation loss can be suppressed, and the amount of energy input to the heating unit can be reduced accordingly,
The cost of producing a hydrogen-containing gas can be reduced.

According to the characteristic structure of the second aspect, the raw fuel gas supplied to the reforming processing unit is integrated with a desulfurizing unit for desulfurizing the raw fuel gas. That is, if the raw fuel gas contains sulfur and it is necessary to remove the sulfur, a desulfurization unit is provided. Conventionally, the desulfurization unit was provided separately from the reforming unit and the steam generator. On the other hand, according to the characteristic configuration of the second aspect, in the hydrogen-containing gas generator having the desulfurization unit for desulfurizing the raw fuel gas, the hydrogen-containing gas generator can be integrated with the desulfurization unit also provided. In addition, miniaturization can be further promoted.
Further, since the manufacturing process of the hydrogen-containing gas generator is further simplified, the cost of the apparatus can be further reduced. Further, since the heat dissipation loss can be further suppressed by further reducing the surface area, the reduction of the hydrogen-containing gas production cost can be further promoted.

According to a third aspect of the present invention, there is provided a raw fuel gas passage for guiding the raw fuel gas to the desulfurizing section, and a desulfurizing gas for guiding the desulfurizing gas discharged from the desulfurizing section to the reforming section. A flow section, an upstream reforming gas flow section provided to heat the desulfurization processing gas flow section and guiding the reforming gas discharged from the reforming section; The upstream reforming gas flow section is provided so as to heat the flow section, and the downstream reforming gas flow section through which the reforming gas flows after flowing through the upstream reforming gas flow section is integrated. Is formed. In other words, in order to improve the thermal efficiency when generating the hydrogen-containing gas, the heat for the desulfurization treatment gas is used to heat the desulfurization treatment gas to be reformed after the desulfurization treatment with the high-temperature reforming treatment gas after the reforming treatment. There is a case where a heat exchanger for raw fuel gas that heats a raw fuel gas to be desulfurized by a reforming gas passed through the heat exchanger for gas desulfurization is provided.

Conventionally, a heat exchanger for a desulfurization gas and a heat exchanger for a raw fuel gas are provided separately from a reforming section, a steam generator and a desulfurizing section.
Heat exchanger for desulfurization gas and heat exchanger for raw fuel gas,
The pipes are connected so that the gas to be treated flows through a predetermined path. On the other hand, according to the characteristic configuration of the third aspect, the hydrogen-containing gas generator is provided with a raw fuel gas passage, a desulfurization treatment gas passage, an upstream reforming gas passage, and a downstream side. With the reforming gas flow passage provided, they are integrated, and the respective gas flow passages are used to form a desulfurization treatment gas heat exchanger and a raw fuel gas heat exchanger. .

Therefore, in a hydrogen-containing gas generator having a function of preheating a desulfurization gas or raw fuel gas by a reforming gas, a function of preheating a desulfurization gas or raw fuel gas by a reforming gas is also provided. Since they can be integrated in a state, size reduction can be further promoted.
Further, since the manufacturing process of the hydrogen-containing gas generator is further simplified, the cost of the apparatus can be further reduced. Further, since the heat dissipation loss can be further suppressed by further reducing the surface area, the reduction of the hydrogen-containing gas production cost can be further promoted.

According to a fourth aspect of the present invention, the heating section is provided to heat the reforming section, and heats the combustion section for burning the combustion gas and the steam generation section. A heating exhaust gas flowing portion through which the combustion exhaust gas from the combustion portion flows. In other words, water evaporates at a temperature lower than the temperature at which the raw fuel gas and water vapor undergo a reforming reaction, and only one combustion unit for burning the combustion gas is provided. The reforming section that requires heating is heated, and the steam generation section is heated by the heating exhaust gas flow section through which the combustion exhaust gas from the combustion section flows. Therefore, for example, it is possible to reduce the size and cost as compared with a case where a combustion section is provided for each of the reforming section and the steam generation section.

According to a fifth aspect of the present invention, a shift processing section for shifting carbon monoxide gas in a reforming gas discharged from the reforming section to carbon dioxide gas, and the shift processing section The cooling exhaust gas flowing through the heating exhaust gas flowing portion is provided, and the cooled exhaust gas flows through the exhaust gas flowing through the heating exhaust gas flowing portion. ing. That is, the reforming gas discharged from the reforming section contains carbon monoxide gas in addition to hydrogen gas. On the other hand, such a hydrogen-containing gas generator may be used in a fuel cell power generation facility. The fuel cell power generation equipment is configured to supply a hydrogen-containing gas and an oxygen-containing gas and generate power by an electrochemical reaction between hydrogen in the hydrogen-containing gas and oxygen in the oxygen-containing gas. In some cases, an electrode catalyst poisoned by carbon monoxide gas is used in the fuel cell power generation equipment. In this case, the carbon monoxide content in the hydrogen-containing gas supplied for the power generation reaction is reduced as much as possible. It is necessary to provide a shift processing unit that shifts carbon monoxide gas in the reforming process gas to carbon dioxide gas. Further, since the metamorphic reaction is an exothermic reaction, a cooling function for cooling the metamorphic treatment section is provided.

Conventionally, the metamorphic treatment section and the cooling means for cooling the same have been provided separately from the reforming treatment section and the steam generator. On the other hand, according to the characteristic configuration of the fifth aspect, in the hydrogen-containing gas generation device including the shift processing unit, the hydrogen conversion gas generating unit can be integrated with the shift processing unit and the function of cooling the same. Therefore, miniaturization can be further promoted. Further, since the manufacturing process of the hydrogen-containing gas generator is further simplified, the cost of the apparatus can be further reduced. Further, since the combustion exhaust gas discharged from the combustion section is used as the cooling medium for cooling the shift conversion section, the cost of producing hydrogen-containing gas can be reduced as compared with the case where a dedicated cooling medium is used. Can be planned.

According to a sixth aspect of the present invention, there is provided a selective oxidizing section for oxidizing carbon monoxide gas in the shift processing gas discharged from the shift converting section, and cooling the selective oxidizing section. In addition, it is formed integrally with the downstream cooling exhaust gas flow portion through which the combustion exhaust gas flowing through the upstream cooling exhaust gas flow portion flows. That is, the carbon monoxide gas that has not been subjected to the metamorphic treatment remains in the metamorphic treatment gas discharged from the metamorphic treatment section. On the other hand, when such a hydrogen-containing gas generator is used in a fuel cell power generation facility, in order to minimize the effect of poisoning of the electrode catalyst, the residual gas in the metamorphic processing gas discharged from the metamorphic processing section is reduced. In some cases, a selective oxidation unit for oxidizing carbon oxide gas is provided. Also, since the oxidation reaction is exothermic,
A function of cooling the selective oxidation unit is also provided.

Conventionally, a selective oxidizing section and a cooling means for cooling the selective oxidizing section are provided separately from the reforming section, the steam generator and the shift processing section. On the other hand, according to the characteristic configuration of the sixth aspect, in the hydrogen-containing gas generating apparatus including the selective oxidizing section, the hydrogen-containing gas generating apparatus can be integrated with the selective oxidizing section and the function of cooling the selective oxidizing section. Therefore, miniaturization can be further promoted. In addition, since the manufacturing process of the hydrogen-containing gas generator is further simplified,
It is possible to further promote a reduction in the price of the device.
Further, since the combustion exhaust gas discharged from the combustion unit is used as a cooling medium for cooling the selective oxidation unit, the cost of producing a hydrogen-containing gas can be reduced as compared with the case where a dedicated cooling medium is used. Can be planned.

According to the seventh aspect of the present invention, the steam generation section, the reforming section, the combustion section, and the exhaust gas flow section for heating are formed so that the outer shape becomes a flat plate shape,
On one plate surface side of the combustion unit, a reforming treatment unit is provided in a state in which the thickness direction of the plate-like shape is aligned with the thickness direction of the combustion unit, and combustion is performed on the other plate surface side of the combustion unit. In the direction away from the section, the heat insulating section, the exhaust gas flow section for heating, and the steam generating section are arranged side by side in the stated order with the thickness direction of each plate-like shape being along the thickness direction of the combustion section. ing. Therefore, miniaturization can be further promoted. Further, by arranging the both sides of the combustion section between the reforming section and the heat insulating section, most of the heat generated in the combustion section can be transferred to the reforming section as much as possible, so that high-temperature heating can be achieved. The required reforming treatment section can be efficiently heated, and heat radiation from the combustion section can be suppressed as much as possible. Therefore, the input energy amount can be reduced as much as possible, so that the cost of producing the hydrogen-containing gas can be reduced as much as possible.

Incidentally, when a desulfurization unit is provided,
Forming it in a flat plate shape and providing the plate shape in a state where the thickness direction of the plate shape is in line with the thickness direction of the combustion part can further promote downsizing. Further, in the configuration including the upstream-side reforming gas passage, the downstream-side reforming gas passage, the raw fuel gas passage, and the desulfurization treatment gas passage, they are formed into a flat plate shape. In addition to the above, when the plate-like shapes are provided in a state where the thickness direction of each plate-like shape is aligned with the thickness direction of the combustion part, the miniaturization can be further promoted. Further, in the configuration including the metamorphic treatment section and the upstream-side exhaust gas passage section for cooling, while forming them into a flat plate shape, the thickness direction of each plate shape is set to the thickness direction of the combustion section. If the device is provided along the direction, size reduction can be further promoted. In the configuration including the selective oxidizing section and the downstream-side exhaust gas passage section for cooling, they are formed so as to have a flat plate shape, and the thickness direction of each plate shape is set in the thickness direction of the combustion section. If the device is provided along the direction, size reduction can be further promoted.

[0018]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS [First Embodiment] A first embodiment of the present invention will be described below with reference to FIGS. 1 to 5, FIG. 9 and FIG. As shown in FIGS. 1 and 9, the hydrogen-containing gas generator P includes a desulfurization unit 1 for desulfurizing a raw fuel gas such as natural gas, and a steam generation unit 2 for heating supplied water to generate steam. And a reforming process using a mixed gas of the raw fuel gas desulfurized in the desulfurization unit 1 and the steam generated in the steam generation unit 2 as a gas to be reformed, and contains hydrogen gas and carbon monoxide gas. A reforming section 3 for generating a reforming gas, the reforming section 3 and the steam generating section 2
A heating section H for heating the gas, a conversion processing section 5 for performing a conversion reaction of carbon monoxide gas in the reforming processing gas discharged from the reforming processing section 3 with water vapor to convert the carbon monoxide gas into carbon dioxide gas, The apparatus is provided with a selective oxidizing unit 6 for oxidizing carbon monoxide gas remaining in the shift processing gas discharged from the processing unit 5.

The heating section H is provided so as to heat the reforming section 3 and to burn a combustion gas, and the heating section H is provided so as to heat the steam generating section 2. And a heating exhaust gas passage 12 through which exhaust gas flows.

The hydrogen-containing gas generator P further includes a raw fuel gas passage 7 for supplying the raw fuel gas to the desulfurization unit 1, a desulfurized raw fuel gas desulfurized in the desulfurization unit 1, and a steam generation unit. A steam mixing section 8 for mixing the steam generated in Step 2 with the steam generated in Step 2, and a reformed gas passage for supplying the mixed gas mixed in the steam mixing section 8 to the reforming section 3 as a gas to be reformed. (Corresponding to a desulfurization process gas passage) 9, an upstream reforming process gas provided to heat the reformed gas passage 9 to guide the reforming gas discharged from the reforming unit 3 The downstream reforming is provided so as to heat the flow passage 10f and the raw fuel gas flow passage 7, and guides the reforming gas after flowing through the upstream reforming gas flow passage 10f to the shift processing unit 5. The conversion gas discharged from the processing gas passage 10b and the conversion unit 5
Air mixing unit 1 for mixing a small amount of air for selective oxidation
1. The metamorphic treatment section 5 is provided so as to cool, and cools the upstream-side cooling exhaust gas passage 13f through which the combustion exhaust gas flows after flowing through the heating exhaust gas passage 12, and the selective oxidation section 6. And a downstream cooling exhaust gas passage 13b through which the combustion exhaust gas flowing through the upstream cooling exhaust gas passage 13f flows. Further, the hydrogen-containing gas generator P is provided with a heat insulating section 16 for suppressing heat radiation from the combustion section 4 to the outside.

As shown in FIGS. 1 and 2, in the present invention, the hydrogen-containing gas generator P includes a desulfurization section 1, a steam generation section 2, a reforming section 3, a combustion section 4, a shift processing section 5, Selective oxidation unit 6, raw fuel gas passage 7, steam mixing unit 8, gas to be reformed 9, passage 10f for upstream reforming gas, passage 10b for downstream reforming gas, air Mixing part 11, exhaust gas passage for heating 12, exhaust gas passage for upstream cooling 13
f, Downstream cooling exhaust gas passage 13b and heat insulating portion 16
Are integrally formed in a unit shape, and formed as a single body.

Furthermore, a desulfurization section 1, a steam generation section 2, a reforming section 3, a combustion section 4, a shift processing section 5, a selective oxidizing section 6, a raw fuel gas flow path 7, a reformed gas flow path 9 An upstream reforming gas passage 10f, a downstream reforming gas passage 10b,
Exhaust gas passage 12 for heating, exhaust gas passage 1 for upstream cooling
3f, downstream exhaust gas passage 13b for cooling, and heat insulating portion 16
Each of them is formed in a flat shape, and each of the flat portions and each of the flow paths are juxtaposed in the thickness direction to form a compact as a whole.

More specifically, a plurality of vertical partition walls 18 are arranged inside a rectangular parallelepiped box-shaped casing 17 at intervals in the horizontal direction with their respective planes directed up and down. Then, a plurality of flat spaces are formed in the casing 17 side by side in the horizontal direction with the flat directions of the flat spaces facing up and down. Then, a combustion chamber 4r constituting the combustion unit 4 is formed using the flat space in the middle part of the flat space arrangement direction, and the flat space arranged on one side is used to sequentially move in the direction away from the combustion chamber 4r. , A reforming processing chamber 3 r constituting the reforming processing section 3, an upstream reforming processing gas passage 10
f, gas passage 9 to be reformed, desulfurization chamber 1 constituting desulfurization unit 1
r, raw fuel gas passage 7, downstream reforming gas passage 1
0b, the upstream-side exhaust gas passage 13f for cooling, the metamorphic treatment section 5
, A downstream exhaust gas passage 13b for cooling is formed, and the flat space at the end is used to form the metamorphic processing chamber 5r below and the selective oxidation unit 6 above. The selective oxidation chambers 6r are respectively formed. In addition, using a flat space arranged on the other side of the combustion chamber 4r, a heat insulating material chamber 16r, a heating exhaust gas passage 12, a steam generation section 2, Are formed, respectively.

The raw fuel gas passage 7, the reformed gas passage 9, the upstream reforming gas passage 10f, the downstream reforming gas passage 10b, the heating exhaust gas passage 12, Upstream cooling exhaust gas passage 13f, downstream cooling exhaust gas passage 1
In a flat space used as each gas passage of 3b, a plurality of round rods 30 are arranged side by side in a staggered manner at intervals in the vertical direction, with the longitudinal direction of each flat space being horizontal. The gas flows in the vertical direction while meandering. The flow path of the gas flowing through each flat space is made longer so that heat can be exchanged efficiently between adjacent flat spaces.

Further, the upper part of the flat space is formed by using a plurality of horizontal partition walls 19 whose surfaces are oriented in the horizontal direction so as to perform various processes such as desulfurization and reforming while allowing gas to flow in a desired route. Or flat spaces used for different applications are connected to each other at the top and bottom, and flat spaces used for the same application that are separated from each other at a position where there is a flat space used for other applications And communicate. To be more specific, based on the gas flow path, the raw fuel gas flow path 7 uses two flat spaces, and one raw space from the raw fuel gas supply port 20 formed on the upper surface of the casing 17. The raw fuel gas supplied to the flat space flows downward through the flat space, makes a U-turn at the lower end, flows into the adjacent flat space, flows upward through the flat space, and flows into the outflow chamber 1r from above. It is formed to flow in.

The outflow chamber 1r uses one flat space,
It is formed so that the raw fuel gas flows downward. The reformed gas passage 9 uses one flat space adjacent to the raw fuel gas passage 7 in the outflow chamber 1r,
The lower end thereof is connected to the outflow chamber 1r so that the gas to be reformed flows upward. In addition, at the communication place between the outflow chamber 1r and the gas passage 9 to be reformed, a water vapor discharge pipe 31 having a cylindrical shape and having a large number of water vapor discharge holes formed along the longitudinal direction.
Is disposed along the flattening direction of the flat space with its longitudinal direction being horizontal, and a steam pipe 27 described later is connected to the steam jetting pipe 31. Then, the desulfurization raw fuel gas flowing out of the desulfurization chamber 1r and the steam spouting from the steam jetting pipe 31 are mixed at the continuous passage, and the reformed gas which is a mixed gas of the desulfurization raw fuel gas and the steam is mixed. Is passed through the gas passage 9 to be reformed. Therefore, the outflow chamber 1r
A steam mixing section 8 is formed at a location where the gas flows through the passage 9 and the gas passage 9 to be reformed.

Two flat spaces adjacent to the side of the reformed gas passage 9 opposite to the outflow chamber 1r are used as the upstream reformed gas passage 10f, and the upstream reformed gas passage 10f is used as the upstream reformed gas passage 10f. A flat space adjacent to the flat space used for the flow path 10f is used as the reforming processing chamber 3r. The upper end of the flat space used for the reformed gas passage 9 and the upper end of the flat space used for the reforming chamber 3r are placed above the two flat spaces used for the upstream reforming gas passage 10f. The gas to be reformed flows into the reforming processing chamber 3r from the upper portion thereof and communicates therewith.
r is made to flow downward.

The upstream reforming gas passage 10f is formed by using the two flat spaces adjacent to the reforming chamber 3r, and the downstream reforming gas passage 10b is formed by the raw fuel gas. It is formed using a flat space adjacent to the flow passage 7 on the side opposite to the outflow chamber 1r side. That is, the upper ends of the two flat spaces adjacent to the reforming chamber 3r communicate with each other, and the lower end of the flat space on the reforming chamber 3r side and the lower end of the reforming chamber 3r among the two flat spaces. To form an upstream reforming gas passage 10f. Further, the lower end of the flat space opposite to the reforming chamber 3r side of the two flat spaces and the lower end of the flat space adjacent to the raw fuel gas passage 7 are connected to the reformed gas passage. 9. The upstream reforming gas passage 10f and the downstream reforming gas passage 10b are connected to communicate with each other below the outflow chamber 1r and the raw fuel gas passage 7. . Then, the reforming gas flowing into the adjacent flat space from the lower end of the reforming chamber 3r flows upward through the flat space, makes a U-turn at the upper end, flows into the adjacent flat space, and the flattened space. The space flows downward, and further flows into the lower end of the flat space adjacent to the raw fuel gas flow passage 7 to flow upward through the flat space.

The upstream reforming gas passage 10f and the gas passage 9 to be reformed are arranged adjacent to each other, and the vertical partition wall 18 separating them serves as a heat transfer plate. The heat of the reforming gas flowing through the gas passage 10f is given to the gas to be reformed flowing through the gas passage 9 to preheat the gas to be reformed. Thus, the upstream reforming gas passage 10f and the reformed gas passage 9 provide
A heat exchange unit 14 for the gas to be reformed is configured. In addition, the downstream reforming gas passage 10b and the raw fuel gas passage 7 are arranged adjacent to each other, and the vertical partition wall 18 separating them functions as a heat transfer plate, so that the downstream reforming gas passage is formed. Channel 10
The heat of the reforming gas flowing through b is given to the raw fuel gas flowing through the raw fuel gas passage 7 to preheat the raw fuel gas. Therefore, the downstream reforming gas passage 10
b and the raw fuel gas passage 7 constitute a raw fuel gas heat exchange section 15.

The flat space used for the upstream cooling exhaust gas passage 13f is closed at the top and bottom, and the downstream reforming gas passage 1f is closed.
0b and the upper end of the flat space used as the shift treatment chamber 5r are connected to the upstream cooling exhaust gas passage 13
It is communicated above f. Further, the lower end of the flat space used for the downstream side exhaust gas passage 13b for cooling is closed, and the upper end is opened on the upper surface of the casing 17, so that the exhaust gas outlet 23 is formed.
Is formed. Further, the lower ends of the flat spaces used as the shift processing chamber 5r communicate with each other below the downstream cooling exhaust gas passage 13b. A space is formed between the lower metamorphic treatment chamber 5r and the upper selective oxidation chamber 6r, and an air ejection tube 21 having a cylindrical shape and a large number of ejection holes formed along the longitudinal direction is formed in the space. It is disposed along the flat direction of the flat space with the longitudinal direction being horizontal. The air mixing section 11 is formed in the space so that air is blown from the air blowing pipe 21 into the space.

The downstream reforming gas passage 10b
Reforming gas flowing into the metamorphic processing chamber 5r from the upper end of the
It flows downward through the metamorphic processing chamber 5r, flows into the other metamorphic processing chamber 5r from the lower end thereof, flows through the metamorphic processing chamber 5r upward, is subjected to the metamorphic processing in the flow process, and has an air mixing unit. 11 to flow out. Then, the shift gas is mixed with a small amount of air jetted from the air jet pipe 21 in the air mixing section 11, flows into the lower end of the selective oxidation chamber 6r, and flows upward through the selective oxidation chamber 6r to be selected. It is oxidized. The gas subjected to the selective oxidation treatment in the selective oxidation chamber 6r is led out of the apparatus from a fuel gas discharge pipe 22 disposed above the selective oxidation chamber 6r.

The heat insulating section 16 is provided in the heat insulating chamber 16r.
6i. In addition, the steam generation unit 2
The steam generation chamber 2r is filled with stainless wool 2w formed to allow gas flow.
Using two horizontal partition walls 19, the upper end of the flat space used for the heat insulating material chamber 16r is partitioned, and the upper end of the flat space used for the combustion chamber 4r and the upper end of the flat space used for the heating exhaust gas passage 12 are insulated. Communicating above the material chamber 16r, and
A steam filling chamber 24 communicating with the upper end of the flat space used for the steam generating chamber 2r is formed. In addition, an exhaust gas discharge pipe 32 is provided below the flat space used for the heating exhaust gas passage 12, and an exhaust gas ejection pipe 33 is provided below the flat space used for the upstream cooling exhaust gas passage 13f. The exhaust gas discharge pipe 32 and the exhaust gas ejection pipe 33 are connected by a combustion exhaust gas pipe 25. Further, an exhaust gas discharge pipe 34 is provided above the flat space used for the upstream-side cooling exhaust gas passage 13f.
The exhaust gas discharge pipe 35 is disposed below the flat space used for the downstream-side cooling exhaust gas passage 13b, and the exhaust gas discharge pipe 34 and the exhaust gas discharge pipe 35 are connected by the combustion exhaust gas pipe 26. I have. Further, a water vapor discharge pipe 36 is provided in the water vapor filling chamber 24, and the water vapor discharge pipe 36 and the water vapor discharge pipe 31 of the water vapor mixing section 8 are connected by the water vapor pipe 27.

When the combustion gas such as natural gas is burned with air in the combustion chamber 4r, the combustion exhaust gas discharged from the combustion chamber 4r flows through the heating exhaust gas passage 12, the upstream cooling exhaust gas passage. Path 13f, downstream side exhaust gas passage 13 for cooling
b flows sequentially and is discharged from the exhaust gas discharge port 23.
In the heating exhaust gas passage 12, the heat of the combustion exhaust gas flowing therethrough is transferred through the vertical partition wall 18 to the steam generation chamber 2r, thereby heating the steam generation chamber 2r and heating the steam generation chamber 2r. In the exhaust gas passages 13f and 13b, the reaction heat generated from the shift treatment chamber 5r and the selective oxidation chamber 6 is transmitted through the vertical partition wall 18 to the combustion exhaust gas, and the reaction shift chamber 5r and the selective oxidation chamber 6 are cooled. It is configured to cool. In the steam generation chamber 2r, water supplied from the lower water supply port 29 evaporates to generate steam, and the steam is supplied to the steam filling chamber 24 and the steam discharge pipe 3.
6. The steam is supplied to the steam mixing section 8 through the steam pipe 27. In the steam generation chamber 2r, steam is efficiently generated by the excellent heat transfer effect of the stainless wool 2w filled therein.

That is, the reforming unit 3 is disposed on one of the plate surfaces of the combustion unit 4 in a direction away from the combustion unit 4.
Upstream reforming gas passage 10f, reformed gas passage 9, desulfurization unit 1, raw fuel gas passage 7, downstream reforming gas passage 10b, upstream cooling exhaust gas passage The path 13f, the metamorphic treatment section 5, the downstream cooling exhaust gas passage 13b, and the selective oxidizing section 6 are arranged in the stated order in a state where the thickness direction of each plate-like shape is aligned with the thickness direction of the combustion section 4. It is set up. Further, on the other plate surface side of the combustion unit 4, the heat insulation unit 16, the exhaust gas passage for heating 12, and the steam generation unit 2 are arranged in the thickness direction of the respective plate-like shapes in a direction away from the combustion unit 4. Are arranged side by side in the order of description in a state of being arranged along the thickness direction of the combustion part 4.

In other words, in arranging the components constituting the hydrogen-containing gas generator P side by side, the combustion section 4 and the reforming section 3 requiring the highest temperature heating are arranged at a substantially central portion in the direction of the side by side. By arranging the respective parts on both sides thereof in the order of decreasing temperature substantially, and by arranging the metamorphic processing unit 5 and the selective oxidation unit 6 which require cooling at the end in the juxtaposition direction, Each component can be controlled to an appropriate temperature while suppressing heat radiation loss as much as possible, thereby reducing the production cost of the hydrogen-containing gas.

The desulfurization section 1 is constituted by filling a large number of porous ceramic particles 1h holding a desulfurization catalyst into a desulfurization chamber 1r.

Referring to FIGS. 3 to 5, the reforming section 3
And the combustion unit 4 will be described. The reforming processing unit 3
A flat reforming honeycomb body 3h holding ruthenium as a reforming catalyst is provided in a flat reforming chamber 3r. The reforming honeycomb body 3h is configured to allow the reformed gas to flow from the reformed gas supply port 3i to the reforming gas outlet 3o in a multi-path manner. And
In a state where the reforming chamber 3r is externally heated by the combustion unit 4, the gas to be reformed is caused to flow from the reforming gas supply port 3i to the reforming gas outlet 3o in the reforming chamber 3r. It is configured to perform a reforming process. When natural gas containing methane gas as a main component is a raw fuel gas, a reforming reaction between methane gas and water vapor is carried out according to the following reaction formula to produce a reformed gas containing hydrogen gas and carbon monoxide gas. Generate.

[0038]

Embedded image CH ₄ + H ₂ O → CO + 3H ₂

The reforming honeycomb body 3h is formed in such a manner that both sides of a corrugated sheet w having a sine waveform are sandwiched between two flat plates b so that a large number of elongated flow paths c flow. They are formed side by side in the road width direction. The corrugated plate w and the flat plate b are formed of a thin stainless steel plate. Ruthenium as a reforming catalyst is held on both sides of the corrugated sheet w and on both sides of each plate b. The reforming honeycomb body 3h is in a state where one opening end of the elongated flow path c is located on the side of the reforming target gas supply port 3i and the other opening end is located on the side of the reforming gas outlet 3o. And is provided in the reforming processing chamber 3r.

The combustion section 4 includes a flat combustion chamber 4r provided along the reforming processing chamber 3r, and a burner 4b provided to burn combustion gas in the combustion chamber 4r. It is. The burner 4b has a large number of flame ports 4s arranged in the flat direction of the flat combustion chamber 4r, and is configured to form a flame along the flat direction of the flat combustion chamber 4r.

The metamorphic treatment section 5 is constituted by filling a large number of porous ceramic particles 5h holding a metamorphic catalyst of iron oxide or copper zinc in a metamorphic treatment chamber 5r. The shift processing unit 5 shifts the carbon monoxide gas to carbon dioxide gas by causing a shift reaction between carbon monoxide gas and steam in the reforming process gas according to the following reaction formula.

[0042]

## STR2 ## CO + H ₂ O → CO ₂ + H ₂

The selective oxidizing section 6 is constituted by filling a large number of porous ceramic particles 6h holding a carbon monoxide selective oxidizing catalyst in a selective oxidizing chamber 6r.

Next, a fuel cell power generation facility using the hydrogen-containing gas generator P having the above-described configuration will be described with reference to FIG. A fuel cell power generation unit G configured to supply a fuel gas containing hydrogen gas and an oxygen-containing gas containing oxygen gas to generate power;
A hydrogen-containing gas generator P that generates a fuel gas to be supplied to the fuel cell power generation unit G using a hydrocarbon-based raw fuel gas such as natural gas, and supplies air as an oxygen-containing gas to the fuel cell power generation unit G. It is provided with a blower B. The hydrogen-containing gas led out from the fuel gas discharge pipe 22 of the hydrogen-containing gas generator P is used as the fuel gas, and the fuel cell power generation unit G
To be supplied. The blower B is also connected to an air ejection pipe 21 so as to supply air for carbon monoxide gas oxidation to the selective oxidation section 6.

Although the description of the fuel cell power generation section G is omitted, a plurality of cells having an oxygen electrode on one side of the electrolyte layer and a fuel electrode on the other side are provided, and an oxygen electrode is provided on the oxygen electrode of each cell. The gas is configured to supply the fuel gas to the fuel electrode, and an electrochemical reaction is caused by hydrogen and oxygen in each cell to generate power. The fuel cell power generation section G is a polymer type using a polymer membrane as an electrolyte.

[Second Embodiment] Hereinafter, FIGS. 6 to 10
A second embodiment of the present invention will be described based on FIG. In the second embodiment, the reforming section 3 has the same configuration as the above-described first embodiment, but the combustion section 4 has a different configuration from the first embodiment. The combustion section 4 will be described with reference to FIGS. The combustion unit 4 includes the reforming processing chamber 3r
The combustion catalyst is held in a flat combustion chamber 4r adjacent to the combustion chamber 4b, and the combustion gas flows from the combustion gas supply port 4i of the combustion chamber 4r to the combustion exhaust gas discharge port 4o in a multi-path manner. Composed flat plate-shaped honeycomb honeycomb body for combustion 4h
It is provided with.

The honeycomb-shaped body for combustion 4h has the same configuration as the honeycomb-shaped body for reforming 3h, and is formed on both sides of the corrugated sheet w and both sides of each flat plate b forming the honeycomb-shaped body for combustion 4h. Platinum as a catalyst is retained. The honeycomb-shaped body for combustion 4h is placed in a combustion chamber in a state where one opening end of the elongated flow path c is located on the combustion gas supply port 4i side and the other opening end is located on the combustion exhaust gas discharge port 4o side. 4r, a combustion gas supply pipe 4p having a plurality of discharge holes 4s formed in the combustion gas supply port 4i along the longitudinal direction.
Are arranged such that the longitudinal direction thereof is along the flat direction of the combustion chamber 4r. Then, the combustion gas ejected and supplied from the combustion gas ejection pipe 4p is caused to flow in a multi-path manner to the combustion exhaust gas discharge port 4o by using a plurality of elongated flow paths c of the combustion honeycomb body 4h. In the flowing process, the catalyst is burned by the action of the combustion catalyst without a flame.

The thickness of the combustion section 4 can be further reduced by forming the combustion section 4 using the honeycomb-shaped body for combustion 4h instead of the burner 4b in the first embodiment. Then, as shown in FIG. 6, using the thus configured combustion unit 4, as in the first embodiment,
The hydrogen-containing gas generator P is configured. Since the thickness of the combustion part 4 is reduced, the hydrogen-containing gas generator P can be formed more compact.

[Another Embodiment] Next, another embodiment will be described. (A) In the above embodiment, the hydrogen-containing gas generator P is connected to the steam generator 2, the reformer 3, and the heater H
The case where the desulfurization unit 1, the shift treatment unit and the selective oxidation unit 6 are added to form a single unit is illustrated. Instead, some or all of the desulfurization unit 1, the shift conversion unit 5, and the selective oxidation unit 6 are provided separately from the integrated steam generation unit 2, the reforming unit 3, and the heating unit H. May be. When the metamorphic treatment section 5 and the selective oxidation section 6 are provided separately, the cooling exhaust gas flow sections 13f and 13
b is also provided separately from the integrated steam generator 2, reformer 3, and heater H. In addition, the separate parts are connected to each other by a conduit for guiding gas. For example, when the desulfurization unit 1 is provided separately, at least the reformed gas passage 9, the upstream reformed gas passage 10f, and the downstream reformed gas passage 10b are formed by pipes. Will do.

(B) The selective oxidizing section 6 is omitted when the hydrogen-containing gas to be used may contain carbon monoxide gas, or when it is not necessary to reduce the content of carbon monoxide gas very much. Alternatively, both the conversion unit 5 and the selective oxidation unit 6 can be omitted. Further, two metamorphic processing units 5 may be provided as one.

(C) As in the above embodiment, when forming the hydrogen-containing gas generator P as a single unit,
Desulfurization section 1, steam generation section 2, reforming section 3, combustion section 4,
Metamorphic processing unit 5, selective oxidizing unit 6, raw fuel gas passage 7, steam mixing unit 8, reformed gas passage 9, respective reforming gas passages 10f, 10b, air mixing unit 11, heating The arrangement of the exhaust gas passage 12 for cooling, the exhaust gas passages 13 f and 13 b for cooling, and the heat insulating portion 16 can be changed as appropriate. For example, the order of arrangement in the horizontal direction may be changed. Further, they may be arranged in a plurality of rows in the horizontal direction, or may be arranged in a plurality of rows in the horizontal direction. Also, they may be arranged vertically.

(D) In the above embodiment, the desulfurization section 1, the steam generation section 2, the reforming section 3, the combustion section 4, the shift processing section 5, the selective oxidation section 6, the raw fuel gas passage 7, The reformed gas passage 9, each reforming gas passage 10 f, 10 b,
Exhaust gas passage 12 for heating, exhaust gas passage 13 for each cooling
Although the case where the gas flow direction in each part and each gas flow path of f and 13b is the vertical direction has been exemplified, the gas flow direction in each part and each gas flow path can be appropriately changed. It may be set in the horizontal direction.

(E) As the desulfurization catalyst holder for holding the desulfurization catalyst, a honeycomb-shaped body formed in the same manner as the reforming honeycomb-shaped body 3h instead of the porous granular body 1h exemplified in the above embodiment is used. May be applied. Further, as the shift catalyst holding body for holding the shift catalyst, a honeycomb-shaped body formed in the same manner as the reforming honeycomb body 3h may be applied instead of the porous granular body 5h exemplified in the above embodiment. good. Further, the carbon monoxide selective oxidation catalyst holding member for holding the carbon monoxide selective oxidation catalyst was formed in the same manner as the reforming honeycomb-shaped body 3h instead of the porous granular material 6h exemplified in the above embodiment. A honeycomb-shaped body may be applied. When a honeycomb-shaped body is used instead of the porous granular material as a catalyst holding body for holding each catalyst of the desulfurization catalyst, the shift conversion catalyst, and the carbon monoxide selective oxidation catalyst, the desulfurization section 1, the shift conversion section 5, the selective oxidation section, Since each section of the section 7 can be made thinner, the hydrogen-containing gas generator P can be formed more compactly.

(F) As the reforming catalyst holding body for holding the reforming catalyst, a porous granular material may be used instead of the reforming honeycomb body 3h exemplified in the above embodiment.

(G) The reforming honeycomb-shaped body 3h and the combustion honeycomb-shaped body 4h have various configurations other than those exemplified in the above embodiment, provided that the gas can flow in a multi-path manner. Is possible. For example, instead of the corrugated sheet w having a sine waveform, a corrugated sheet w having a rectangular waveform or a sawtooth waveform may be used. Alternatively, a plurality of corrugated sheets w may be arranged in the thickness direction, and a plurality of elongated flow paths c may be formed side by side in the thickness direction of the corrugated sheet w. Further, instead of the corrugated plate w, an uneven plate provided with a large number of pillar-shaped or conical-shaped protrusions scattered may be used.

(H) The reforming catalyst is not limited to the ruthenium exemplified in the above embodiment, but various catalysts such as nickel and platinum can be used. The combustion catalyst is not limited to platinum exemplified in the above-described second embodiment, and various catalysts such as platinum rhodium can be used.

(I) As in the above embodiment, when the hydrogen-containing gas generator according to the present invention is used in a fuel cell power generation facility, the combustion gas to be burned in the combustion unit 4 is the fuel gas power generation unit G The discharged fuel gas may be used. (V) The hydrogen-containing gas generator according to the present invention can be used in various types of fuel cell power generation equipment such as a phosphoric acid type and a solid electrolyte type in addition to the polymer type fuel cell power generation equipment exemplified in the above embodiment. Can be. Further, the present invention is not limited to fuel cell power generation equipment, and can be used for various purposes.

[Brief description of the drawings]

FIG. 1 is a longitudinal sectional view of a hydrogen-containing gas generator according to a first embodiment of the present invention.

FIG. 2 is a view taken in the direction of the arrow II in FIG.

FIG. 3 is a longitudinal sectional view of a reforming section and a combustion section according to the first embodiment of the present invention.

FIG. 4 is a cross-sectional view of a reforming section and a combustion section according to the first embodiment of the present invention.

FIG. 5 is a perspective view of a reforming honeycomb body.

FIG. 6 is a longitudinal sectional view of a hydrogen-containing gas generator according to a second embodiment of the present invention.

FIG. 7 is a longitudinal sectional view of a reforming section and a combustion section according to a second embodiment of the present invention.

FIG. 8 is a cross-sectional view of a reforming section and a combustion section according to a second embodiment of the present invention.

FIG. 9 is a block diagram of a hydrogen-containing gas generator according to an embodiment of the present invention.

FIG. 10 is a block diagram illustrating a schematic configuration of a fuel cell power generation facility according to an embodiment of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Desulfurization part 2 Steam generation part 3 Reforming part 4 Combustion part 5 Metamorphosis processing part 6 Selective oxidation part 7 Raw fuel gas passage part 9 Desulfurization treatment gas passage part 10b Downstream reforming treatment gas passage part 10f Upstream side Reforming gas flow section 12 Exhaust gas flow section for heating 13b Downstream exhaust gas flow section for cooling 13f Upstream exhaust gas flow section for cooling H Heating section

Continuation of the front page (72) Seisaku Higashiguchi 4-1-2, Hiranocho, Chuo-ku, Osaka-shi, Osaka Prefecture Inside Osaka Gas Co., Ltd. (72) Masafumi Tachimori 4-chome, Hiranocho, Chuo-ku, Osaka-shi, Osaka No. 2 Osaka Gas Co., Ltd. F-term (reference) 4G040 EA03 EA06 EB01 EB12 EB44 EC08 5H027 BA01 BA16 BA17

Claims (7)

[Claims] 1. A steam generating section for evaporating water by heating, a steam generated by the steam generating section and a hydrocarbon-based raw fuel gas are supplied, and a reforming reaction is performed to convert the hydrogen gas into a hydrogen gas. A hydrogen-containing gas generator, wherein a reforming section for generating a contained gas, and a heating section for heating the reforming section and the steam generating section are integrally formed in a unit. 2. The hydrogen-containing gas generation apparatus according to claim 1, wherein a desulfurization section for desulfurizing the raw fuel gas supplied to the reforming section is integrated. 3. A raw fuel gas passage for guiding raw fuel gas to the desulfurization unit, a desulfurization gas passage for guiding desulfurization gas discharged from the desulfurization unit to the reforming unit, and desulfurization thereof. An upstream reforming gas flow section, which is provided to heat the processing gas flow section and guides the reforming gas discharged from the reforming section, and heats the raw fuel gas flow section. Is formed integrally with the downstream reforming gas flow portion through which the reforming gas flows after flowing through the upstream reforming gas flow portion. The hydrogen-containing gas generator according to claim 2, wherein 4. The combustion section, wherein the heating section is provided to heat the reforming section, and is provided to heat a combustion gas, and the steam section is provided to heat the steam generation section. The hydrogen-containing gas generating apparatus according to any one of claims 1 to 3, further comprising a heating exhaust gas flowing portion through which combustion exhaust gas flows. 5. A shift processing unit for shifting carbon monoxide gas in the reforming gas discharged from the reforming unit to carbon dioxide gas, and provided to cool the shift unit. The hydrogen-containing gas generator according to claim 4, wherein the hydrogen-containing gas generator is integrally formed with an upstream-side cooling exhaust gas flow portion through which the combustion exhaust gas flowing through the heating exhaust gas flow portion flows. . 6. A selective oxidizing section for oxidizing carbon monoxide gas in a shift processing gas discharged from the shift processing section, and provided to cool the selective oxidizing section, wherein the exhaust gas for upstream cooling is provided. 6. The hydrogen-containing gas generator according to claim 5, wherein the hydrogen-containing gas generator is integrally formed with a downstream-side exhaust gas flow portion for cooling, through which the combustion exhaust gas flowing through the flow portion flows. 7. The steam generation section, the reforming section, the combustion section, and the heating exhaust gas passage section are formed such that the outer shape is a flat plate-like shape, and one of the combustion sections is formed. On the plate surface side, the reforming processing unit is provided in a state where the thickness direction of the plate shape is aligned with the thickness direction of the combustion unit, and the combustion unit is provided on the other plate surface side of the combustion unit. In a direction away from the heat insulation section, the exhaust gas flow section for heating,
The hydrogen according to any one of claims 4 to 6, wherein the steam generating sections are arranged in the stated order in a state where the thickness direction of each plate-like shape is along the thickness direction of the combustion section. Included gas generator.