JP2002326805A - Reformer and fuel cell system including the same - Google Patents

Abstract

(57) [PROBLEMS] To improve the thermal efficiency of a reformer and reduce the energy required for hydrogen production in the reformer. SOLUTION: In the reformer (30) of the fuel cell system,
A first heat recovery device (40) and a second heat recovery device (43) are provided.
The first heat recovery device (40) has a first flow path (41) connected to the source gas passage (23), and a second flow path (42) connected to the reformer (31) in the internal gas passage (24). ) And the transformer (34). The first heat recovery device (40) recovers the heat of the gas discharged from the reformer (31) into the raw material gas. Second heat recovery unit (4
In 3), the first flow path (44) is connected to the combustion air passage (26), and the second flow path (45) is connected to the combustion exhaust gas passage (28).
Connected to. The second heat recovery device (43) recovers heat of the combustion exhaust gas into air supplied to the combustor (36).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a reformer for producing hydrogen from a raw material gas containing a hydrocarbon-based raw fuel, and a fuel for generating electricity by supplying hydrogen produced by the reformer to a fuel cell. It relates to a battery system.

[0002]

2. Description of the Related Art Conventionally, as disclosed in Japanese Patent Application Laid-Open No. 1-186570, a reformer for producing hydrogen from a hydrocarbon-based raw fuel has been known. In this reformer, hydrogen is generated from a hydrocarbon-based raw fuel by a steam reforming reaction and a partial oxidation reaction. The reaction equations of the steam reforming reaction and the partial oxidation reaction are as follows.

[0003] _{C n H m + nH 2 O} → nCO + (n + m / 2) H 2 ... steam reforming reaction _{C n H m + n / 2O} 2 → nCO + m / 2H 2 ... partial oxidation reaction the reformer fuel In many cases, a fuel cell system is configured in combination with a battery. In this case, the reformed gas mainly composed of hydrogen obtained in the reformer is supplied to the fuel electrode of the fuel cell. Air is supplied to the air electrode of the fuel cell. Fuel cells use hydrogen supplied to the fuel electrode as fuel,
Electric power is generated using oxygen in the air supplied to the air electrode as an oxidant.

[0004]

However, in the above-mentioned conventional reformer, no consideration has been given to heat recovery from the high-temperature gas, despite the fact that a relatively high-temperature gas flows out of the reformer. Was. For this reason, the conventional reformer has a problem that the energy required for producing hydrogen in the reformer increases due to low thermal efficiency.

[0005] This problem will be specifically described. The reaction temperature of the steam reforming reaction and the partial oxidation reaction in the reformer is as high as about 600 to 800 ° C., and the reformed gas obtained by these reactions is also sent out from the reformer in a relatively high temperature state. On the other hand, the operating temperature of the fuel cell may be lower than the reaction temperature of the steam reforming reaction or the like. For example, a solid polymer electrolyte type fuel cell has an operating temperature of about 80 to 90 ° C. Therefore, in such a case,
The reformed gas from the reformer must be supplied to the fuel cell after being cooled, and the heat loss from the reformed gas causes heat loss.

[0006] The steam reforming reaction performed in the reformer is an endothermic reaction, and fuel or the like must be burned to supply the reaction heat. Therefore, high-temperature combustion exhaust gas generated by combustion of fuel or the like is discharged from the reformer. At that time, if the combustion exhaust gas is simply exhausted, the heat held by the combustion exhaust gas will be wasted and the heat loss will also occur.

[0007] The present invention has been made in view of the above, and an object of the present invention is to increase the thermal efficiency of a reformer and reduce the energy required for producing hydrogen in the reformer. .

[0008]

According to a first aspect of the present invention, there is provided a reformer in which a raw material gas containing a hydrocarbon-based raw fuel is supplied to produce hydrogen by a partial oxidation reaction and a steam reforming reaction. Combustion in which a combustion oxidant containing oxygen and a heating fuel are supplied to supply a reaction heat of a steam reforming reaction to the reforming unit (31). And a reformer for producing a reformed gas mainly composed of hydrogen from the raw material gas. And a first heating means (40) for heating the raw material gas by the reacted gas flowing out of the reforming section (31).
And second heating means (4) for heating the combustion oxidant with the combustion exhaust gas discharged from the combustion section (36).
3) is provided.

A second solution taken by the present invention is a reforming section (31) in which a raw material gas containing a hydrocarbon-based raw fuel is supplied to generate hydrogen by a partial oxidation reaction and a steam reforming reaction.
And a combustion unit (36) that is supplied with a combustion oxidant containing oxygen and a heating fuel and burns the heating fuel to supply reaction heat of the steam reforming reaction to the reforming unit (31). And a reformer that generates a reformed gas mainly composed of hydrogen from the raw material gas. Then, the combustion section (3
A first heating means (40) for heating the raw material gas by the combustion exhaust gas discharged from (6);
A second heating means (43) for heating the combustion oxidant with the reacted gas flowing out from 1) is provided.

According to a third aspect of the present invention, in the first or second aspect, the fuel electrode (12) of the fuel cell (10) to which the reformed gas generated by the reformer is supplied. )
Is supplied to the combustion section (36) as fuel for heating, discharged from the fuel electrode.

A fourth solution taken by the present invention is the first or second solution, wherein the reforming section (31) includes a first reaction section (32) in which a partial oxidation reaction is performed; And a second reaction section (33) in which a steam reforming reaction is performed.

According to a fifth aspect of the present invention, in the fourth aspect of the present invention, the reforming section (31) is configured to remove the reacted gas flowing out of the first reaction section (32) into the second reaction section. (33).

According to a sixth aspect of the present invention, in the fourth aspect, the first reaction section (32) is formed in a honeycomb shape having a catalyst exhibiting an activity in a partial oxidation reaction. And a second reaction section (33).
Is filled with a large number of catalyst packings (38) having a catalyst exhibiting activity in a steam reforming reaction.

According to a seventh aspect of the present invention, in the first or the second aspect, the reforming section (31) is provided so as to surround a combustion section (36). Department (36)
It is formed integrally with.

According to an eighth aspect of the present invention, in the above fourth aspect, the reforming section (31) includes a combustion section (36).
A second reaction part (33) is provided so as to surround the periphery of the first reaction part, and a first reaction part (32) is provided so as to surround the periphery of the second reaction part (33). Is formed.

According to a ninth aspect of the present invention, in the above-mentioned seventh or eighth aspect of the present invention, there is provided a conversion section for supplying hydrogen after reaction from a reforming section (31) to generate hydrogen by a shift reaction. (34) is provided so as to surround the reforming section (31).

According to a tenth aspect of the present invention, in the first or the second aspect, the conversion section is provided with a gas after the reaction from the reforming section (31) to generate hydrogen by a shift reaction. (34) heat recovery through which a heat medium flows to absorb heat radiated from at least one or all of the combustion unit (36), the reforming unit (31), and the shift unit (34). Aisle (5
2,55, ...).

According to an eleventh aspect of the present invention, in the tenth aspect, the heat medium flowing through the heat recovery passages (52, 55,...) Is supplied to the reforming section (31). It is a gas.

According to a twelfth aspect of the present invention, in accordance with the tenth aspect, the heat medium flowing through the heat recovery passages (52, 55,...) Is supplied to the combustion section (36). It is an oxidizing agent.

According to a thirteenth aspect of the present invention, there is provided a fuel cell system, comprising:
And a fuel cell (1) to which the reformed gas generated by the reformer (30) is supplied.
0).

-Operation- In each of the first and second solving means, the reforming unit (30) is provided with the reforming unit (31) and the combustion unit (36). Reforming unit (3
In 1), a source gas is supplied. This source gas contains
Contains hydrocarbon-based raw fuels. Examples of the hydrocarbon-based raw fuel include methane (CH ₄ ) and propane (C ₃ H).
₈ ). On the other hand, the fuel for heating and the oxidizing agent for combustion are supplied to the combustion section (36). The oxidizing agent for combustion contains oxygen. As the oxidizing agent for combustion,
An example is air.

In the reforming section (31), a partial oxidation reaction and a steam reforming reaction are performed, and H ₂ (hydrogen) is generated from the raw material gas. Here, the steam reforming reaction in the reforming section (31) is an endothermic reaction. Therefore, in order to perform the steam reforming reaction in the reforming section (31), the reaction heat of the steam reforming reaction is reduced by the reforming section (3).
Need to supply to 1). Therefore, the combustion unit (36) supplies the reaction heat of the steam reforming reaction to the reforming unit (31). That is, the combustion unit (36) burns the supplied heating fuel, and supplies the combustion heat to the reforming unit (31).

In the first solution, the first heating means (40) for heating the raw material gas is provided in the reformer (30). The first heating means (40) uses the gas flowing out of the reforming section (31) to heat the raw material gas.
That is, by providing the first heating means (40), the heat held by the gas flowing out of the reforming section (31) is recovered by the raw material gas and sent back to the reforming section (31). Here, a mixture of raw fuel and air may be supplied as a raw material gas to the reforming section (31). In such a case, the first heating means (40) may heat one of the raw fuel and the air before mixing, or may heat a mixture of the raw fuel and the air. That is, the first heating means (40) may be any device that uses the heat of the gas flowing out of the reforming section (31) to heat the raw material gas.

In the present solution, a second heating means (43) for heating the oxidizing agent for combustion is provided in the reformer (30). The second heating means (43) uses combustion exhaust gas discharged from the combustion section (36) to heat the oxidizing agent for combustion. That is, by providing the second heating means (43), heat held by the combustion exhaust gas discharged from the combustion section (36) is recovered by the oxidizing agent for combustion and sent back to the combustion section (36). The second heating means (43) only needs to heat at least the oxidizing agent for combustion, and may, for example, heat both the oxidizing agent for combustion and the fuel for heating.

In the second solution, the first heating means (40) for heating the raw material gas is provided in the reformer (30). The first heating means (40) uses combustion exhaust gas discharged from the combustion section (36) to heat the raw material gas. That is, by providing the first heating means (40), the heat held by the combustion exhaust gas discharged from the combustion section (36) is recovered by the raw material gas and sent back to the reforming section (31). Here, a mixture of raw fuel and air may be supplied as a raw material gas to the reforming section (31). In such a case, the first heating means (40) may heat one of the raw fuel and the air before mixing, or may heat a mixture of the raw fuel and the air. That is, the first heating means (40) may be any device that uses the heat of the combustion exhaust gas from the combustion section (36) to heat the raw material gas.

Further, in the present solution, a second heating means (43) for heating the oxidizing agent for combustion is provided in the reformer (30). The second heating means (43) uses gas flowing out of the reforming section (31) to heat the oxidizing agent for combustion. That is, by providing the second heating means (43),
The heat held by the gas flowing out of the reforming section (31) is recovered by the oxidizing agent for combustion and sent back to the combustion section (36). still,
The second heating means (43) only needs to heat at least the oxidizing agent for combustion, and may, for example, heat both the oxidizing agent for combustion and the fuel for heating.

In the third solution, the reformer (30)
Is supplied to the fuel electrode (12) of the fuel cell (10). Air is supplied to the air electrode (11) of the fuel cell (10). The fuel cell (10) generates power using hydrogen in the reformed gas as a fuel and oxygen in the air as an oxidant. Fuel electrode exhaust gas is discharged from the fuel electrode (12) of the fuel cell (10). Hydrogen not used for power generation remains in the fuel electrode exhaust gas. Therefore, in this solution, the fuel electrode exhaust gas containing hydrogen is supplied to the combustion unit (36) as heating fuel. Combustion unit (36)
Then, the hydrogen in the fuel electrode exhaust gas burns, and the heat of combustion is supplied to the reforming section (31).

In the fourth solution, the first reaction section (3
2) and the second reaction section (33) are provided in the reforming section (31).
You. In the first reaction section (32), a partial oxidation reaction is performed,
Fuel and O _Two(Oxygen) reacts to produce hydrogen. 2nd anti
In the reaction section (33), a steam reforming reaction is performed, and the raw fuel and H
_TwoO (steam) reacts to generate hydrogen. In addition, the first counter
In the reaction part (32), only the partial oxidation reaction needs to be performed
However, a partial oxidation reaction may be mainly performed. As well
In the second reaction section (33), only the steam reforming reaction
It is not necessary to carry out
Just do it.

In the fifth solution, in the reforming section (31), the first reaction section (32) is arranged on the upstream side, and the second reaction section (33) is arranged on the downstream side. The raw material gas is first introduced into the first reaction section (32) of the reforming section (31). In the first reaction section (32), a partial oxidation reaction, which is an exothermic reaction, is performed to generate hydrogen. The reacted gas that has exited from the first reaction section (32) is subsequently introduced into the second reaction section (33). In the second reaction section (33), a steam reforming reaction, which is an endothermic reaction, is performed to generate hydrogen.

Since the partial oxidation reaction is an exothermic reaction, the temperature of the reacted gas flowing out of the first reaction section (32) is high. The first reaction section (3) is connected to the second reaction section (33).
The hot gas from 2) is introduced. Then, in the second reaction section (33), heat held by the introduced gas is used as reaction heat of the steam reforming reaction.

In the sixth solution, a honeycomb member (37) formed in a honeycomb shape is provided in the first reaction section (32). The honeycomb member (37) is provided with a catalyst exhibiting activity in the partial oxidation reaction, for example, a Rh (rhodium) -based catalyst. The raw material gas introduced into the first reaction section (32)
It flows through the honeycomb member (37). At that time, the raw material gas comes into contact with the catalyst of the honeycomb member (37), and a partial oxidation reaction is performed to generate hydrogen.

In the present solution, a large number of catalyst packings (38) are filled in the second reaction section (33). The catalyst packing (38) is provided with a catalyst exhibiting activity in the steam reforming reaction, for example, a Ru (ruthenium) catalyst or a Ni (nickel) catalyst. From the first reaction section (32) to the second reaction section (33)
The gas sent to the reactor is filled with a large amount of catalyst
8) Flow through the gap. At that time, the gas introduced into the second reaction section (33) comes into contact with the catalyst of each catalyst packing (38), and a steam reforming reaction is performed to generate hydrogen.

In the seventh solution, the reforming section (31) and the combustion section (36) are formed integrally. At this time, the reforming section (31) is provided so as to surround the combustion section (36). That is, in the present solution, the periphery of the combustion section (36) is surrounded by the reforming section (31).

[0034] In the eighth solution, the first reaction section (32) and the second reaction section (33) of the reforming section (31) and the combustion section (36).
Are integrally formed. At that time, the second reaction section (33) is provided so as to surround the combustion section (36), and the first reaction section (32) is provided so as to surround the second reaction section (33). That is, in this solution, the periphery of the combustion section (36) is surrounded by the second reaction section (33), and the periphery of the second reaction section (33) is further surrounded by the first reaction section (32).

According to the ninth solution, the reacted gas exiting from the reforming section (31) is sent to the shift section (34). The gas sent to the shift section (34) contains the hydrogen and carbon monoxide produced by the reaction in the shift section (31) together with the reforming section (3
Water vapor not used in 1) remains. Metamorphic department (3
In 4), a shift reaction (carbon monoxide conversion reaction) is performed, and hydrogen is generated and carbon monoxide is reduced at the same time.

In the present solution, the shift section (34) is provided so as to surround the reforming section (31). Here, generally, the reaction temperature of the shift reaction (about 200 to 400 ° C.)
Is the reaction temperature of the partial oxidation reaction or the steam reforming reaction (600
(About 700 ° C.). That is, in the present solution, the periphery of the reforming section (31) is surrounded by the shift section (34) having a lower temperature than the reforming section (31).

In the present solution, it is not necessary that the reformed portion (31) and the metamorphic portion (34) around the reformed portion are brought into close contact with each other to form them integrally. That is, the reforming section (31) and the metamorphic section (3
If the temperature difference in 4) is large, the reforming section (31)
The amount of heat transfer to 4) may be excessive. Therefore, in such a case, a certain interval may be provided between the reforming section (31) and the shift section (34). Further, between the reforming section (31) and the shift section (34), a heat insulating material or the like may be provided as a member for adjusting the amount of heat transferred from the reforming section (31) to the shift section (34).

[0038] In the tenth solving means, the conversion section (34)
And the heat recovery passages (52, 55, ...) are provided in the reformer (30). The operation of the transformation unit (34) is the same as that of the ninth solving means. On the other hand, the heat medium flows through the heat recovery passages (52, 55,...). The heat medium flowing through the heat recovery passages (52, 55,...) Absorbs heat radiated from the combustion section (36), the reforming section (31), and the shift section (34). That is, the heat recovery passage (52, 55,
...) may recover heat from any one of the combustion unit (36), the reforming unit (31), and the shift unit (34),
Further, heat recovery may be performed from any two of the combustion section (36), the reforming section (31), and the shift section (34), and furthermore, the combustion section (36) and the reforming section ( Heat recovery from all of 31) and the metamorphic section (34) may be performed.

In the eleventh solution, the raw material gas flows through the heat recovery passages (52, 55,...) As a heat medium. That is, in the heat recovery passages (52, 55,...), Heat radiated from the combustion section (36), the reforming section (31), and the shift section (34) is recovered into the raw material gas. The raw material gas having absorbed heat in the heat recovery passages (52, 55, ...) is thereafter supplied to the reforming section (31).

In the twelfth solution, the oxidizing agent for combustion flows through the heat recovery passages (52, 55,...) As a heat medium. That is, in the heat recovery passages (52, 55,...), Heat radiated from the combustion section (36), the reforming section (31), and the shift section (34) is recovered by the oxidizing agent for combustion. The oxidizing agent for combustion that has absorbed heat in the heat recovery passages (52, 55, ...) is thereafter supplied to the combustion section (36).

In the thirteenth solution, the reformer (3
0) and the fuel cell (10) constitute a fuel cell system. The reformed gas mainly composed of hydrogen generated by the reformer (30) is supplied to the fuel electrode (12) of the fuel cell (10). Air is supplied to the air electrode (11) of the fuel cell (10). The fuel cell (10) generates power using hydrogen in the reformed gas as a fuel and oxygen in the air as an oxidant.

[0042]

According to the present invention, the first reformer (30) has
Since the heating means (40) and the second heating means (43) are provided, the heat generated by the reacted gas from the reforming section (31) and the combustion exhaust gas from the combustion section (36) is transferred to the reforming section. The raw material gas supplied to (31) and the oxidizing agent for combustion supplied to the combustion section (36) can be recovered. In other words, the heat that had been conventionally released from the reformer (30) to the outside can be recovered into the raw material gas or the oxidizing agent for combustion and returned to the reformer (30). Therefore, according to the present invention, the heat loss from the reformer (30) can be reduced, the thermal efficiency of the reformer (30) can be increased, and the energy required for operation of the reformer (30) can be reduced. .

In the third solution, the fuel cell (10)
The fuel electrode exhaust gas discharged from is used as fuel for heating. Therefore, in order to supply the reaction heat of the steam reforming reaction, it is possible to effectively use the hydrogen remaining in the fuel electrode exhaust gas.

In the fourth solution, a first reaction section (32) and a second reaction section (33) are provided in the reforming section (31), and the partial oxidation reaction and the steam reforming reaction are performed in separate reaction sections (31). 32,33). For this reason, the reaction conditions such as temperature
It is possible to set individually for the reaction section (32) and the second reaction section (33). Specifically, the reaction conditions of the first reaction section (32) are set to conditions suitable for the partial oxidation reaction, and the second reaction section (3
The reaction condition 3) can be made suitable for the steam reforming reaction. Therefore, according to the present solution, the partial oxidation reaction and the steam reforming reaction in the reforming section (31) can be performed under optimal conditions for each reaction, and the amount of hydrogen generated in the reforming section (31) can be reduced. Can be increased.

In the fifth solution, first, a partial oxidation reaction is performed in the first reaction section (32), and then a steam reforming reaction is performed in the second reaction section (33). Therefore, the heat of the partial oxidation reaction, which is an exothermic reaction, can be used as the heat of the steam reforming reaction, which is an endothermic reaction. As a result, the amount of heat to be supplied to the reforming section (31) as the reaction heat of the steam reforming reaction can be reduced, and the energy required for operating the reformer (30) can be further reduced.

In the sixth solution, the first reaction section (3
2) A honeycomb member (37) is provided, and the honeycomb member (3) is provided.
7) so that the source gas flows through. For this reason,
According to this solution, the pressure loss of the gas when passing through the first reaction section (32) can be reduced. Furthermore, in this solution, a large number of catalyst packings (38) are provided in the second reaction section (33).
To form a packed layer having excellent heat transfer performance. Therefore, it is possible to efficiently supply the heat supplied from the combustion unit (36) to the flowing gas and the catalyst of the catalyst packing (38), and to reliably perform the steam reforming reaction to increase the amount of generated hydrogen. it can.

In the seventh and eighth solutions, the reforming section (31) is provided so as to surround the combustion section (36) in which the heating fuel burns. Therefore, the combustion heat of the heating fuel radiated from the combustion section (36) can be efficiently supplied to the reforming section (31) around the combustion section (36). That is, it is possible to increase the proportion of the combustion heat of the heating fuel combusted in the combustion unit (36) that is effectively used as the reaction heat of the steam reforming reaction. Supply can be reduced. Therefore, according to these solutions, the energy required for operating the reformer (30) can be further reduced.

In the eighth solution, the combustion section (36) is arranged inside the second reaction section (33) where the steam reforming reaction, which is an endothermic reaction, is performed, and the exothermic reaction section is provided outside the combustion section (36). A first reaction section (32) for performing an oxidation reaction is arranged. Therefore, the combustion heat of the heating fuel can be efficiently supplied from the combustion section (36) to the second reaction section (33), and the reaction heat of the partial oxidation reaction can be further transmitted from the first reaction section (32). Can also be supplied efficiently. Therefore, according to the present solution, the supply amount of the heating fuel to the combustion section (36) can be further reduced,
Energy required for operation of the reformer (30) can be further reduced.

[0049] In the ninth solution, the reforming section (31) is surrounded by a shift section (34) whose temperature is lower than that of the reforming section (31). Therefore, the periphery of the reforming section (31) can be thermally insulated by the shift section (34), and heat loss from the reforming section (31) can be reduced. Therefore, according to the present solution, the reforming section (31) can be insulated using the shift section (34) for generating hydrogen, and the heat loss from the reformer (30) can be reduced. As a result, the thermal efficiency of the reformer (30) can be improved.

According to the tenth, eleventh, and twelfth solving means, the combustion section (36), the reforming section (31), and the shift section (34).
The heat radiated from the reformer (30) can be recovered to the heat medium, and the heat loss from the reformer (30) can be further reduced. In particular, according to the eleventh solution, the heat radiated from the combustion unit (36) or the like can be used to preheat the raw material gas supplied to the reforming unit (31). Further, according to the twelfth solution, in order to preheat the oxidizing agent supplied to the combustion section (36), heat radiated from the combustion section (36) or the like can be used.

According to the thirteenth solution, a fuel cell system with high power generation efficiency can be realized by combining the reformer (30) and the fuel cell (10) according to the present invention.

[0052]

Embodiment 1 Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. As shown in FIG. 1, the first embodiment is a fuel cell system including a fuel cell main body (10) and a reformer (30).

The fuel cell body (10) is of a solid polymer electrolyte type. The fuel cell body (10) is provided with an air electrode (cathode) (11), which is a catalyst electrode, and a fuel electrode (anode) (12), which is also a catalyst electrode. The air electrode (11) of the fuel cell body (10) is connected to an air supply passage (20) on the inlet side, and is connected to an air electrode exhaust passage (13) on the outlet side. On the other hand, the fuel electrode (12) of the fuel cell body (10) has a reformed gas passage (25) connected to the inlet side, and a fuel electrode exhaust passage (14) connected to the outlet side.

The air supply passage (20) has a start end open to the outside and an end end connected to the air electrode (11) of the fuel cell body (10). This air supply passage (20)
Air taken from outside is supplied to the cathode (11). The air supply passage (20) is provided with a first branch passage (21) and a second branch passage (22).

The cathode exhaust passage (13) has a start end connected to the cathode (11) of the fuel cell body (10), and an end open to the outside. On the other hand, the fuel electrode exhaust passage (14) has a start end at the fuel electrode (1
2), the end of which is connected to an off-gas burner (not shown).

The reformer (30) is configured to generate a reformed gas containing hydrogen as a main component from the raw fuel and supply the obtained reformed gas to the fuel cell body (10). . The reformer (30) includes a humidifier (39), a reformer (31),
Transformer (34), selective oxidation reactor (35), and combustor (3
6) is provided. The reformer (30) is provided with a first heat recovery device (40) and a second heat recovery device (43).

A raw material gas passage (23) is connected to the inlet side of the reformer (31). The raw material gas passage (23)
This is for supplying a raw material gas, which is a mixture of a hydrocarbon-based raw fuel, oxygen, and steam, to the reformer (31).
At the beginning of the raw material gas passage (23), natural gas mainly containing methane (CH ₄ ) as a raw fuel is introduced.
The source gas passage (23) is provided with a humidifier (39) and a first heat recovery unit (40) in order along the flow of the source gas. The humidifier (39) in the source gas passage (23)
The first branch passage (21) of the air supply passage (20) is connected to the upstream of the air supply passage.

The beginning of the internal gas passage (24) is connected to the outlet side of the reformer (31). Internal gas passage (2
4) is provided with a first heat recovery unit (40) and a transformer (34) in order. The end of the internal gas passage (24) is connected to the inlet side of the selective oxidation reactor (35). Further, a portion of the internal gas passage (24) between the shift converter (34) and the selective oxidation reactor (35) is provided with the second air supply passage (20).
The branch passage (22) is connected.

At the outlet side of the selective oxidation reactor (35),
The starting end of the reformed gas passage (25) is connected. The reformed gas discharged from the selective oxidation reactor (35) is sent to the fuel electrode (12) of the fuel cell body (10) through the reformed gas passage (25).

A heating fuel passage (27), a combustion air passage (26), and a combustion exhaust gas passage (28) are connected to the combustor (36). The heating fuel passage (27) is for supplying natural gas to the combustor (36) as heating fuel. The combustion air passage (26) is for supplying air as a combustion oxidant to the combustor (36). The flue gas passage (28) is for exhausting flue gas generated in the combustor (36) to the outside. A second heat recovery unit (43) is provided in the combustion air passage (26) and the combustion exhaust gas passage (28).

The humidifier (39) is for supplying steam to the raw material gas. Specifically, this humidifier (3
9) is configured to supply steam required for the reaction performed in the reformer (31) and the shift converter (34) to the raw material gas.

The reformer (31) constitutes a reforming section. In this reformer (31), in order along the flow of gas,
A first reactor (32) as a first reaction section and a second reactor (33) as a second reaction section are provided. That is, the first
A second reactor (33) is arranged downstream of the reactor (32).

As shown in FIG. 2, the first reactor (32)
Is provided with a honeycomb member (37) formed in a honeycomb shape. The honeycomb member (37) has a large number of gas passages therethrough. Further, a catalyst exhibiting activity for the partial oxidation reaction is attached to the surface of the honeycomb member (37) by a binder or the like. Examples of the catalyst exhibiting activity in the partial oxidation reaction include Rh (rhodium) -based catalysts. In the first reactor (32), the raw material gas contacts the catalyst while flowing through the honeycomb member (37), and hydrogen is generated by a partial oxidation reaction.

The second reactor (33) is filled with a large number of granular catalyst packings (38). A catalyst exhibiting activity in the steam reforming reaction is attached to the surface of each catalyst packing (38) by a binder or the like. Examples of the catalyst exhibiting activity in the steam reforming reaction include a Ru (ruthenium) catalyst and a Ni (nickel) catalyst. In the second reactor (33),
The gas comes into contact with the catalyst while flowing through the gap between the charged catalyst packings (38), and hydrogen is generated by the steam reforming reaction.

The first heat recovery unit (40) is formed with a first flow path (41) and a second flow path (42) (FIG. 1).
reference). The first flow path (41) of the first heat recovery device (40) is connected to the raw material gas passage (23). This first flow path (41)
, A raw material gas flowing from the humidifier (39) to the reformer (31) is introduced. On the other hand, the second flow path (42) of the first heat recovery device (40) is connected between the reformer (31) and the shift converter (34) in the internal gas passage (24). This second
The gas after the reaction sent from the reformer (31) is introduced into the flow path (42).

The first heat recovery unit (40) is connected to the first flow path (4
It is configured to exchange heat between the source gas of 1) and the gas in the second flow path (42). That is, the first heat recovery unit (40)
Constitutes first heating means for heating the raw material gas sent to the reformer (31) by the gas after the reaction that has come out of the reformer (31).

The transformer (34) forms a transformer. The shift converter (34) includes a catalyst that exhibits an activity in a shift reaction (a shift reaction for carbon monoxide). Here, the gas sent from the second reactor (33) of the reformer (31) to the shift converter (34) contains not only hydrogen but also carbon monoxide and steam. Then, in the shift converter (34), carbon monoxide in the gas reacts with water vapor to generate hydrogen.

The selective oxidation reactor (35) is provided with a catalyst exhibiting activity in the selective CO oxidation reaction. In the selective oxidation reactor (35), carbon monoxide contained in the gas fed into is selectively oxidized, and the amount of carbon monoxide in the gas is reduced. The gas discharged from the selective oxidation reactor (35) is used as a reformed gas as fuel gas (12) in the fuel cell body (10).
Supplied to

The combustor (36) constitutes a combustion section. The combustor (36) is configured to burn the natural gas supplied as the heating fuel, and to supply the combustion heat to the second reactor (33) of the reformer (31).

In the second heat recovery unit (43), a first flow path (44) and a second flow path (45) are defined. Second
The first flow path (44) of the heat recovery device (43) is connected to the combustion air passage (26). Air supplied to the combustor (36) as a combustion oxidant is introduced into the first flow path (44). On the other hand, the second flow path (45) of the second heat recovery device (43)
Is connected to the flue gas passage (28). This second
The combustion exhaust gas discharged from the combustor (36) is introduced into the flow path (45).

The second heat recovery unit (43) is connected to the first flow path (4
It is configured to exchange heat between the air of 4) and the combustion exhaust gas of the second flow path (45). In other words, the second heat recovery unit (4
3) constitutes second heating means for heating the air sent to the combustor (36) by the combustion exhaust gas from the combustor (36).

-Operation- An operation of the fuel cell system will be described.

Air is supplied to the natural gas flowing through the source gas passage (23) as the source gas through the first branch passage (21) of the air supply passage (20). Subsequently, steam is applied to the raw material gas in the humidifier (39). The raw material gas that has become a mixture of natural gas, air, and steam flows into the first flow path (41) of the first heat recovery device (40). In the first flow path (41) of the first heat recovery unit (40), the source gas is heated by exchanging heat with the gas in the second flow path (42). The raw material gas preheated by the first heat recovery device (40) is sent to the first reactor (32) of the reformer (31).

In the first reactor (32) of the reformer (31), a partial oxidation reaction is performed to generate hydrogen and carbon monoxide.
The reaction formula of the partial oxidation reaction is as shown below. CH ₄ + / O ₂ → CO + 2H ₂ ... Partial oxidation reaction Since this partial oxidation reaction is an exothermic reaction, the temperature of the gas increases in the first reactor (32) due to the heat of the partial oxidation reaction. The gas after the reaction in the first reactor (32) is subsequently sent to the second reactor (33).

In the second reactor (33) of the reformer (31), a steam reforming reaction is performed to generate hydrogen and carbon monoxide. The reaction formula of the steam reforming reaction is as shown below. CH ₄ + H ₂ O → CO + 3H ₂ … Steam reforming reaction Since this steam reforming reaction is an endothermic reaction, it is necessary to supply the reaction heat to perform the steam reforming reaction in the second reactor (33). is there. Thus, the heat of the steam reforming reaction is supplied to the reformer (31) by the combustor (36). Further, the reaction heat of the partial oxidation reaction imparted to the gas in the first reactor (32) is also used as the reaction heat of the steam reforming reaction in the second reactor (33). The reacted gas exiting the second reactor (33) flows into the second flow path (42) of the first heat recovery device (40).

As described above, the first heat recovery unit (40)
The raw material gas flows in the flow path (41). This source gas is almost at room temperature. On the other hand, the second heat recovery unit (40)
In the flow path (42), the reacted gas that has flowed out of the second reactor (33) flows. The temperature of this gas is between about 600 ° C. and 800
It is about ° C. In the first heat recovery unit (40), the raw material gas flowing through the first flow path (41) exchanges heat with the reacted gas flowing through the second flow path (42). Then, in the first heat recovery unit (40), the source gas in the first flow path (41) absorbs heat from the gas in the second flow path (42).

The gas flowing out of the second flow path (42) of the first heat recovery unit (40) is introduced into the transformer (34). The gas introduced into the shift converter (34) contains hydrogen and carbon monoxide, and the steam supplied by the humidifier (39) remains. In the shift converter (34), a shift reaction is performed, and the amount of hydrogen increases while the amount of carbon monoxide decreases. The reaction formula of the shift reaction is as shown below. CO + H ₂ O → CO ₂ + H ₂ … shift reaction

The gas flowing out of the converter (34) is introduced into the selective oxidation reactor (35) after being mixed with the air supplied through the second branch passage (22) of the air supply passage (20). Here, the gas flowing out of the converter (34) is mainly composed of hydrogen, but still contains carbon monoxide. This carbon monoxide becomes a catalyst poison for the fuel electrode (12). Therefore, the selective oxidation reactor (35) further reduces carbon monoxide in the gas by the CO selective oxidation reaction. The reaction formula of the CO selective oxidation reaction is as shown below. CO + 1 / 2O ₂ → CO ₂ … CO selective oxidation reaction Then, the gas mainly composed of hydrogen, whose carbon monoxide has been reduced by the selective oxidation reactor (35), is converted as a reformed gas into the fuel cell body (1).
0) is supplied to the fuel electrode (12).

In the fuel cell body (10), reformed gas is supplied to the fuel electrode (12), and air is supplied to the air electrode (11). The fuel cell body (10) generates power using hydrogen in the reformed gas as fuel and oxygen in the air as an oxidant. Specifically, in the fuel cell body (10), the following cell reactions are performed on the electrode surfaces of the fuel electrode (12) and the air electrode (11). Fuel electrode: 2H ₂ → 4H ⁺ + 4e ⁻ Air electrode: O ₂ + 4H ⁺ + 4e ⁻ → 2H ₂ O By this battery reaction, the chemical energy of the combustion reaction of hydrogen contained in the reformed gas is converted into electric energy.

From the fuel cell main body (10), air electrode exhaust gas and fuel electrode exhaust gas are discharged as cell exhaust gas. The air electrode exhaust gas discharged from the air electrode (11) of the fuel cell body (10) is exhausted outdoors. The fuel electrode exhaust gas discharged from the fuel electrode (12) of the fuel cell body (10) is introduced into an off-gas burner (not shown). In the off-gas burner, hydrogen remaining in the fuel electrode exhaust gas burns.

The air taken into the combustion air passage (26) flows into the first flow path (44) of the second heat recovery device (43).
In the first flow path (44) of the second heat recovery device (43), air is
It is heated by exchanging heat with the combustion exhaust gas in the flow path (45). Second
The air preheated by the heat recovery device (43) is supplied to the combustor (36). Natural gas is supplied to the combustor (36) through the heating fuel passage (27). In the combustor (36), the introduced natural gas burns. The heat of combustion generated in the combustor (36) is supplied to the second reactor (33) of the reformer (31) as reaction heat of the steam reforming reaction. Further, the flue gas generated by the combustion of the natural gas is sent from the combustor (36) to the second flow path (45) of the second heat recovery unit (43).

As described above, the first heat recovery unit (43)
In the flow path (44), air at substantially normal temperature flows. On the other hand, in the second flow path (45) of the second heat recovery unit (43), the combustor (36)
The flue gas discharged from the tank is distributed. The temperature of the combustion exhaust gas is about 800 ° C. to 1000 ° C. In the second heat recovery device (43), the air flowing through the first flow path (44) exchanges heat with the combustion exhaust gas flowing through the second flow path (45). Then, in the second heat recovery unit (43), the air in the first flow path (44) absorbs heat from the combustion exhaust gas in the second flow path (45).

-Effects of First Embodiment- In the first embodiment, since the first heat recovery unit (40) is provided, the heat held by the reacted gas sent from the reformer (31) is From this, the raw material gas supplied to the reformer (31) can be recovered. Furthermore, in the second embodiment, since the second heat recovery unit (43) is provided, the heat held by the combustion exhaust gas discharged from the combustor (36) is supplied to the air supplied to the combustor (36). Can be recovered. That is, the heat that has been conventionally released from the reformer (30) to the outside can be recovered to the raw material gas or air as the oxidizing agent for combustion and returned to the reformer (30) again. Therefore,
According to the first embodiment, the heat radiation loss from the reformer (30) can be reduced, the thermal efficiency of the reformer (30) can be increased, and the energy required for operation of the reformer (30) can be reduced. .

In the first embodiment, the first reactor (32) and the second reactor (33) are provided in the reformer (31), and the partial oxidation reaction and the steam reforming reaction are performed in different reactors. (32, 33). For this reason, reaction conditions such as temperature,
It becomes possible to set individually in the first reactor (32) and the second reactor (33). That is, the reaction conditions of the first reactor (32) are set to conditions suitable for the partial oxidation reaction, and the second reactor (33)
Can be set to conditions suitable for the steam reforming reaction. Therefore, according to the first embodiment, the reformer (31)
The partial oxidation reaction and the steam reforming reaction in the above can be performed under optimal conditions for each reaction, and the amount of hydrogen generated in the reformer (31) can be increased.

In the first embodiment, first, a partial oxidation reaction is performed in the first reactor (32), and then a steam reforming reaction is performed in the second reactor (33). Therefore, the heat of the partial oxidation reaction, which is an exothermic reaction, can be used as the heat of the steam reforming reaction, which is an endothermic reaction. As a result, the amount of heat to be supplied to the second reactor (33) of the reformer (31) as the reaction heat of the steam reforming reaction can be reduced, and the energy required for operating the reformer (30) can be further reduced. Can be.

In the first embodiment, the first reactor (32) is provided with the honeycomb member (37), and the raw material gas flows through the honeycomb member (37). Therefore, according to the first embodiment, the pressure loss of the raw material gas when passing through the first reactor (32) can be reduced. Furthermore, in Embodiment 1, a large number of catalyst packings (38) are placed in the second reactor (33).
To form a packed layer having excellent heat transfer performance. For this reason, the heat supplied from the combustor (36) can be efficiently supplied to the flowing gas and the catalyst of the catalyst packing (38), and the steam reforming reaction can be reliably performed to increase the amount of hydrogen generated. it can.

[0087]

Embodiment 2 Embodiment 2 of the present invention is the same as Embodiment 1 except that the reformer (31), the combustor (36),
The heat recovery unit (40) and the second heat recovery unit (43) are integrated. Here, parts of the second embodiment that are different from the first embodiment will be described.

As shown in FIG. 3, the combustor (36) is formed in a hollow cylindrical shape. A first combustion gas passage (60) and a second combustion gas passage (61) are defined inside the combustor (36). The first combustion gas passage (60) extends up and down along the central axis of the combustor (36). On the other hand, the second
The combustion gas passage (61) is formed in a cylindrical shape along the outside of the first combustion gas passage (60). The second combustion gas passage (61) communicates with the upper end of the first combustion gas passage (60) at the upper end. Further, a fuel nozzle (62) protrudes from the lower end of the first combustion gas passage (60). The fuel nozzle (62) is connected to the heating fuel passage (27), and blows out natural gas supplied as heating fuel into the first combustion gas passage (60).

Around the combustor (36), the first reforming side passageway (7) is positioned such that the central axis thereof coincides with that of the combustor (36).
1) and a second reforming-side passage (72) are defined.
The first reforming side passage (71) and the second reforming side passage (72) are provided with a reformer (31) and a first heat recovery unit (40).

The second reforming side passage (72) is provided with a combustor (3
It is formed in a cylindrical shape that is longer than 6). The second reforming side passage (72) is provided such that its lower half is in close contact with the outer periphery of the combustor (36). That is, the second reforming side passage (72) is arranged so as to surround the outside of the combustor (36). The upper end of the second reforming side passage (72) has an internal gas passage (24) extending toward the transformer (34).
Are connected (see FIG. 1).

The first reforming side passage (71) is formed in a cylindrical shape slightly shorter than the second reforming side passage (72).
The first reforming side passage (71) is provided so as to be in close contact with the outside of the second reforming side passage (72). That is, the first reforming side passage (71) is disposed so as to surround the outside of the second reforming side passage (72). In addition, at the upper end of the first reforming side passage (71), the raw material gas passage (2) extending from the humidifier (39) is provided.
3) is connected (see FIG. 1). Further, the lower end of the first reforming side passage (71) communicates with the lower end of the second reforming side passage (72).

A honeycomb member is provided below the first reforming side passage (71). The lower half of the first reforming side passage (71) constitutes a first reactor (32) of a reformer (31) in which a partial oxidation reaction is performed. On the other hand, the second
The lower part of the reforming side passage (72) is filled with a large number of catalyst fillers. The lower half of the second reforming side passage (72) forms a second reactor (33) of the reformer (31) in which the steam reforming reaction is performed. As described above, in the second embodiment, the reformer (31) is provided so as to surround the combustor (36).

The first heat recovery unit (40) includes a reformer (31)
Above the first reforming side passageway (71) and the second reforming side passageway (7).
It is arranged across 2). Specifically, the first flow path (41) of the first heat recovery unit (40) is provided above the first reactor (32) in the first reforming side passage (71). The second flow path (42) of the first heat recovery unit (40) is connected to the second reforming side passage (7).
It is provided above the second reactor (33) in 2).

Around the first reforming-side passage (71) and the second reforming-side passage (72), the first combustion chamber is positioned such that the center axes of the two reforming-side passages (71, 72) coincide with each other. A side passage (63) and a second combustion side passage (66) are defined. A second heat recovery unit (43) is provided in the first combustion side passage (63) and the second combustion side passage (66).

The second combustion side passage (66) is formed in a bottomed cylindrical shape and is provided so as to surround the first and second reforming side passages (71, 72). Specifically, the second combustion side passage (66) is constituted by a cylindrical portion (67) and a bottom portion (68). The cylindrical portion (67) of the second combustion side passage (66) is formed in a vertically extending cylindrical shape, and is arranged so as to surround the side of the first reforming side passage (71). Also,
The cylindrical portion (67) of the second combustion side passage (66) has a larger diameter than the first reforming side passage (71).
A gap of a predetermined width is formed between the reforming side passage (71). A bottom portion (68) of the second combustion side passage (66) is formed in a flat plate shape and a donut shape, and communicates with a lower end portion of the cylindrical portion (67) at an outer peripheral portion thereof.

The bottom portion (68) of the second combustion side passage (66)
The inner peripheral portion communicates with the lower end portion of the second combustion gas passage (61) in the combustor (36). On the other hand, a combustion exhaust gas passage (28) is connected to the upper end of the cylindrical portion (67) of the second combustion side passage (66).

The first combustion side passage (63) is formed in a cylindrical shape with a bottom and is provided so as to surround the second combustion side passage (66). Specifically, the first combustion side passage (63)
Is composed of a cylindrical portion (64) and a bottom portion (65). The cylindrical portion (64) of the first combustion side passage (63) is formed in a vertically extending cylindrical shape, and is provided in close contact with the outside of the cylindrical portion (67) of the second combustion side passage (66). First
A bottom portion (65) of the combustion side passage (63) is formed in a flat plate shape and a donut shape, and a cylindrical portion (64) is formed on an outer peripheral portion thereof.
Communicates with the lower end. Also, the first combustion side passage (63)
Of the second combustion side passageway (66).
8) Closely attached to the lower side.

The bottom part (65) of the first combustion side passage (63)
The inner peripheral portion communicates with the lower end of the first combustion gas passage (60) in the combustor (36). On the other hand, a combustion air passage (26) is connected to the upper end of the cylindrical portion (64) of the first combustion side passage (63).

The second heat recovery unit (43) is disposed across the first combustion side passage (63) and the second combustion side passage (66). The first flow path (44) of the second heat recovery unit (43) is provided in a cylindrical portion (64) of the first combustion side passage (63). Second
The second flow path (45) of the heat recovery device (43) is provided in a cylindrical portion (67) of the second combustion side passage (66).

The combustor (36), the reforming side passage (71, 7)
2) and the combustion side passages (63, 66) are wrapped by a heat insulating material (80). That is, the first reforming side passage (71) and the second
A heat insulating material (80) is also provided in a gap between the combustion side passages (66).

-Operation- The air taken into the combustion air passage (26) is introduced into the cylindrical portion (64) of the first combustion side passage (63). The air introduced into the first combustion side passage (63) is supplied to the second heat recovery unit (43).
Into the first flow path (44). The heated air flows into the first combustion gas passage (60) of the combustor (36) through the bottom portion (65) of the first combustion side passage (63).

The natural gas is fed into the fuel nozzle (62) of the combustor (36) through the heating fuel passage (27).
This natural gas is blown out from the fuel nozzle (62) into the first combustion gas passage (60). The natural gas blown into the first combustion gas passage (60) is mixed with the preheated air sent through the first combustion side passage (63) and burns.
The combustion of the natural gas generates a high-temperature combustion gas.

The high-temperature combustion gas passes through the first combustion gas passage (6
0) and flows into the second combustion gas passage (61). Thereafter, the combustion gas flows downward through the second combustion gas passage (61), and releases heat to the second reactor (33) of the reformer (31) during that time. The heat-released combustion gas is sent out from the lower end of the second combustion gas passage (61) to the bottom portion (68) of the second combustion-side passage (66) as combustion exhaust gas.

The combustion exhaust gas flows through the second combustion side passage (66) and is introduced into the second flow path (45) of the second heat recovery device (43). The combustion exhaust gas radiates heat to the air in the first flow path (41) while flowing through the second flow path (45). The exhaust gas after the heat release is exhausted to the outside through the exhaust gas passage (28).

The source gas humidified by the humidifier (39) and flowing through the source gas passage (23) is introduced into the first reforming side passage (71). The raw material gas introduced into the first reforming side passage (71) flows into the first flow path (41) of the first heat recovery unit (40) and is heated. The heated raw material gas is sent to the first reactor (32) of the reformer (31). In the first reactor (32), the fed raw material gas comes into contact with the catalyst, and hydrogen is generated by a partial oxidation reaction.

The reacted gas discharged from the first reactor (32) enters the second reforming side passage (72) and enters the reformer (31).
To the second reactor (33). In the second reactor (33), the fed gas comes into contact with the catalyst, and hydrogen is generated by a steam reforming reaction. At this time, the combustion heat of the natural gas is supplied from the combustor (36) to the second reactor (33), and the reaction heat of the partial oxidation reaction is supplied from the first reactor (32). You. Then, in the second reactor (33), a steam reforming reaction is performed using the supplied heat as reaction heat.

The reacted gas sent out from the second reactor (33) is introduced into the second flow path (42) of the first heat recovery unit (40). The gas after the reaction introduced from the second reactor (33) radiates heat to the raw material gas in the first flow path (41) while flowing through the second flow path (42). The gas after the heat release is sent to the transformer (34) through the internal gas passage (24).

-Effects of Second Embodiment- In the second embodiment, the reformer (31) is disposed so as to surround the combustor (36). Thus, the combustion heat radiated from the combustor (36) can be efficiently supplied to the reformer (31) around the combustor (36). That is, the proportion of the heat of combustion of the natural gas combusted by the combustor (36) that is effectively used as the reaction heat of the steam reforming reaction can be increased, and the supply of natural gas to the combustor (36) can be increased. The amount can be reduced. Therefore, according to the second embodiment, the energy required for operating the reformer (30) can be further reduced.

In the second embodiment, the combustor (36) is disposed inside the second reactor (33) in which the steam reforming reaction is performed, and the partial oxidation is carried out outside the second reactor (33). A first reactor (32) in which the reaction is performed is arranged. Therefore, the combustion heat of the natural gas can be efficiently supplied from the combustor (36) to the second reactor (33), and the heat of the partial oxidation reaction can also be supplied from the first reactor (32). It can be supplied efficiently. Therefore, according to the second embodiment, the supply amount of the natural gas to the combustor (36) can be further reduced by utilizing the reaction heat of the partial oxidation reaction as the reaction heat of the steam reforming reaction,
Energy required for operation of the reformer (30) can be further reduced.

[0110]

Third Embodiment A third embodiment of the present invention is obtained by adding a heat recovery passage (52) to the reformer (30) of the first embodiment. Further, the reforming apparatus (3
In 0), the reformer (31), the shift converter (34), the selective oxidation reactor (35), the combustor (36), the first heat recovery unit (40), the second heat recovery unit (43), and The heat recovery passage (52) is integrated. Here, the third embodiment will be described with reference to the first embodiment.
The differences from the description will be described.

As shown in FIG. 4, the heat recovery passage (52)
The raw material gas passage (23) is provided between the humidifier (39) and the first heat recovery unit (40). This heat recovery passage (52)
Is configured to recover the heat radiated from the transformer (34) to the source gas as a heat medium. That is, in the heat recovery passage (52), the raw material gas flowing from the humidifier (39) toward the first heat recovery device (40) is heated by the heat radiated from the transformer (34).

As shown in FIG. 5, the combustor (36) is formed in a hollow cylindrical shape. A first combustion gas passage (60) and a second combustion gas passage (61) are defined inside the combustor (36). The first combustion gas passage (60) extends up and down along the central axis of the combustor (36). On the other hand, the second
The combustion gas passage (61) is formed in a cylindrical shape along the outside of the first combustion gas passage (60). The second combustion gas passage (61) communicates with the upper end of the first combustion gas passage (60) at the upper end. Further, a fuel nozzle (62) protrudes from the lower end of the first combustion gas passage (60). The fuel nozzle (62) is connected to the heating fuel passage (27), and blows out natural gas supplied as heating fuel into the first combustion gas passage (60).

The end of the combustion air passage (26) is connected to the lower end of the first combustion gas passage (60) in the combustor (36). A first flow path (44) of the second heat recovery device (43) is provided near the end of the combustion air passage (26). On the other hand, a starting end of a combustion exhaust gas passage (28) is connected to a lower end of the second combustion gas passage (61) in the combustor (36). A second flow path (45) of the second heat recovery device (43) is provided near the start end of the flue gas passage (28).

A first reforming side passageway (71) having a columnar shape is defined so that the center axis of the combustor (36) coincides with that of the combustor (36). The first reforming side passage (71) is formed to have a larger diameter than the combustor (36). The combustor (36) is arranged in a posture inserted into a lower part of the first reforming side passage (71). A honeycomb member is provided in the first reforming side passage (71) so as to surround a side portion and an upper portion of the combustor (36). In other words, about two-thirds of the lower portion of the first reforming side passage (71) constitutes the first reactor (32) of the reformer (31) in which the partial oxidation reaction is performed.

Outside the first reforming side passageway (71), the second reforming side passageway (71) is positioned in such a manner that the central axis coincides with the second reforming side passageway (71).
A reforming side passage (72) is defined. The second reforming passage (72) is formed in a cylindrical shape having substantially the same height as the first reforming passage (71), and is provided in close contact with the first reforming passage (71). . The lower end of the second reforming passage (72) communicates with the lower end of the first reforming passage (71). About two-thirds from the bottom of the second reforming side passage (72) is filled with a catalyst filler to constitute a second reactor (33) of the reformer (31).

The first heat recovery unit (40) includes a reformer (31)
Above the first reforming side passageway (71) and the second reforming side passageway (7).
It is arranged across 2). Specifically, the first flow path (41) of the first heat recovery unit (40) is provided above the first reactor (32) in the first reforming side passage (71). The second flow path (42) of the first heat recovery unit (40) is connected to the second reforming side passage (7).
It is provided above the second reactor (33) in 2).

Around the first reforming side passage (71) and the second reforming side passage (72), the heat recovery passage is positioned such that the central axes of the two reforming side passages (71, 72) coincide with each other. (52) and the third reforming-side passage (73) are defined.

The third reforming side passage (73) is formed in a shape such that a bottomed cylinder is turned down, and the first and second reforming side passages (73) are formed.
It is provided so as to surround the reforming side passages (71, 72). More specifically, the third reforming side passage (73) is
4) and a disk portion (75). Third
The cylindrical portion (74) of the reforming side passage (73) is formed in a vertically extending cylindrical shape, and is arranged so as to surround the side of the second reforming side passage (72). The cylindrical portion (74) of the third reforming side passage (73) has a larger diameter than the second reforming side passage (72), and this cylindrical portion (74) and the second reforming side passage (72) Is formed with a gap having a predetermined width. The disk portion (75) of the third reforming side passage (73) is formed in a flat plate shape and a donut shape, and communicates with the upper end portion of the cylindrical portion (74) at the outer periphery.

The disk portion (7) of the third reforming side passage (73)
5) communicates with the upper end of the second reforming-side passage (72) at the inner periphery thereof. In the cylindrical portion (74) of the third reforming side passage (73), a catalyst exhibiting activity for the shift reaction is provided. In other words, the transformer (3
4) is provided.

A selective oxidation reactor (35) is provided below the second reforming side passage (72) and the third reforming side passage (73). The selective oxidation reactor (35) communicates with the lower end of the cylindrical portion (74) in the third reforming side passage (73) via the internal gas passage (24).

The heat recovery passage (52) is formed in a shape such that a bottomed cylinder is turned downward, and is provided so as to surround the third reforming side passage (73). Specifically,
Heat recovery passage (52) consists of cylindrical part (53) and disk part (54)
And is constituted by. The cylindrical portion (53) of the heat recovery passage (52) is formed in a vertically extending cylindrical shape, and is provided in close contact with the outside of the cylindrical portion (74) of the third reforming side passage (73). The disk portion (54) of the heat recovery passage (52) is formed in a flat plate shape and a donut shape, and communicates with an upper end portion of the cylindrical portion (53) at an outer peripheral portion thereof. The disk portion (54) of the heat recovery passage (52) is provided in close contact with the upper side of the disk portion (75) of the third reforming side passage (73).

The disk portion (54) of the heat recovery passage (52)
Communicates with the upper end of the first reforming side passageway (71) at an inner peripheral portion thereof. On the other hand, a raw material gas passage (23) extending from the humidifier (39) is connected to the lower end of the cylindrical portion (53) of the heat recovery passage (52) (see FIG. 4). The cylindrical portion (53) of the heat recovery passage (52) is configured to recover heat radiated from the transformer (34) of the third reforming side passage (73) to the raw material gas as a heat medium. .

As described above, in the third embodiment, the reformer (31), the shift converter (34), the selective oxidation reactor (35), the combustor (36), the first heat recovery unit (40), The second heat recovery unit (43) and the heat recovery passage (52) are integrally formed, and are wrapped by the heat insulating material (80). That is, the gap between the second reforming side passage (72) and the third reforming side passage (73) also
Insulation (80) is provided.

-Operation- After the air taken into the combustion air passage (26) is heated in the first flow path (44) of the second heat recovery unit (43), the air is taken into the first passage (44) of the combustor (36). 1 The fuel gas is sent to the combustion gas passage (60). On the other hand, natural gas is fed into the fuel nozzle (62) of the combustor (36) through the heating fuel passage (27). This natural gas is supplied from the fuel nozzle (62) to the first combustion gas passage (60).
It is blown out inside. The natural gas blown into the first combustion gas passage (60) is mixed with the preheated air sent from the combustion air passage (26) and burns. The combustion of the natural gas generates a high-temperature combustion gas.

The high-temperature combustion gas passes through the first combustion gas passage (6
0) and flows into the second combustion gas passage (61). Thereafter, the combustion gas flows downward through the second combustion gas passage (61), and radiates heat to the reformer (31) during that time. The combustion gas after the heat release is sent out from the lower end of the second combustion gas passage (61) as combustion exhaust gas. Thereafter, the combustion exhaust gas is introduced into the second flow path (45) of the second heat recovery device (43). The combustion exhaust gas radiates heat to the air in the first flow path (44) while flowing through the second flow path (45). The exhaust gas after the heat release is exhausted through the exhaust gas passage (28).

The raw material gas humidified by the humidifier (39) flows into the cylindrical portion (53) of the heat recovery passage (52) through the raw gas passage (23). The raw material gas absorbs heat from the transformer (34) while flowing through the cylindrical portion (53), and then passes through the disk portion (54) of the heat recovery passage (52) to pass through the first reforming passage (7).
Flow into 1). The raw material gas flowing into the first reforming side passage (71) is further heated in the first flow path (41) of the first heat recovery unit (40), and then is heated in the first reactor of the reformer (31). (32) is introduced.

In the first reactor (32), the fed raw material gas comes into contact with the catalyst, and hydrogen is generated by a partial oxidation reaction. The reacted gas sent out from the first reactor (32) enters the second reforming side passage (72) and enters the second reformer (31).
It is introduced into the reactor (33). In the second reactor (33), the fed gas comes into contact with the catalyst, and hydrogen is generated by a steam reforming reaction. At this time, the combustion heat of the natural gas is supplied from the combustor (36) to the second reactor (33), and the reaction heat of the partial oxidation reaction is supplied from the first reactor (32). You. Then, in the second reactor (33), a steam reforming reaction is performed using the supplied heat as reaction heat.

The reacted gas sent from the second reactor (33) is introduced into the second flow path (42) of the first heat recovery unit (40). The gas after the reaction introduced from the second reactor (33) radiates heat to the raw material gas in the first flow path (41) while flowing through the second flow path (42). The gas after heat release enters the third reforming side passageway (73) and is introduced into the transformer (34). In the transformer (34), a shift reaction is performed. The reacted gas discharged from the transformer (34) is mixed with air from the second branch passage (22) while flowing through the internal gas passage (24),
Thereafter, it is introduced into the selective oxidation reactor (35). In the selective oxidation reactor (35), carbon monoxide in the gas is selectively oxidized, and the gas after the reaction is converted as a reformed gas into a reformed gas passage (2).
Sent to 5).

-Effects of Third Embodiment- In the third embodiment, the reformer (31) is arranged so as to surround the combustor (36). Thus, the combustion heat radiated from the combustor (36) can be efficiently supplied to the reformer (31) around the combustor (36). That is, the proportion of the heat of combustion of the natural gas combusted by the combustor (36) that is effectively used as the reaction heat of the steam reforming reaction can be increased, and the supply of natural gas to the combustor (36) can be increased. The amount can be reduced. Therefore, according to the third embodiment, the energy required for operating the reformer (30) can be further reduced.

In the third embodiment, the reformer (31) is surrounded by the shifter (34) whose temperature is lower than that of the reformer (31). For this reason, the periphery of the reformer (31) can be insulated by the shift converter (34), and heat loss from the reformer (31) can be reduced. Therefore, according to the third embodiment, the reformer (31) can be insulated by using the transformer (34) for generating hydrogen, and the heat loss from the reformer (30) can be reduced. The heat efficiency of the reformer (30) can be improved by reducing the amount.

Further, in the third embodiment, the heat recovery passage (52) is formed so as to surround the periphery of the transformer (34). For this reason, the heat radiated from the transformer (34) can be recovered to the raw material gas, and the heat radiation loss from the reformer (30) can be further reduced.

[0132]

Fourth Embodiment A fourth embodiment of the present invention is different from the first embodiment in that the first heat recovery passage (5
5), the second heat recovery passage (56), the third heat recovery passage (57),
A third heat recovery unit (46) and a fourth heat recovery unit (49) are added. Further, the reforming apparatus (3
0), the reformer (31), the shift converter (34), the selective oxidation reactor (35), the combustor (36), the first to fourth heat recovery units (40, 43,
46, 49) and the first to third heat recovery passages (55, 56, 57). Here, parts of the fourth embodiment that are different from the first embodiment will be described.

As shown in FIG. 6, the third heat recovery unit (4
6) includes a first flow path (47) and a second flow path (48). The first flow path (47) of the third heat recovery device (46) is provided upstream of the second heat recovery device (43) in the combustion air passage (26). On the other hand, the second flow path (4) of the third heat recovery unit (46)
8) is provided in the internal gas passage (24) between the shift converter (34) and the selective oxidation reactor (35). The third heat recovery device (46) is connected to air flowing through the first flow path (47) and the second flow path (4).
8) It is configured to exchange heat with the gas flowing therethrough.

The fourth heat recovery unit (49) is connected to the first flow path (5
0) and a second flow path (51). 4th heat recovery unit (4
The first flow path (50) of 9) is provided upstream of the third heat recovery device (46) in the combustion air passage (26). on the other hand,
The second flow path (51) of the fourth heat recovery device (49) has an inlet connected to the selective oxidation reactor (35) via an internal gas passage (24), and an outlet connected to a reformed gas passage (25). It is connected to the. The fourth heat recovery device (49) is configured to exchange heat between air flowing through the first flow path (50) and gas flowing through the second flow path (51).

The first heat recovery passage (55) is provided between the humidifier (39) and the first heat recovery device (40) in the raw material gas passage (23). The first heat recovery passage (55) is configured to recover heat radiated from the reformer (31) and the combustor (36) into a raw material gas as a heat medium. That is, in the first heat recovery passage (55), the raw material flowing from the humidifier (39) to the first heat recovery device (40) by the heat radiated from the reformer (31) and the combustor (36). The gas is heated.

The second heat recovery passage (56) is provided between the third heat recovery unit (46) and the fourth heat recovery unit (49) in the combustion air passage (26). This second heat recovery passage (5
6) is configured to recover heat radiated from the selective oxidation reactor (35) to air as a heat medium. That is, in the second heat recovery passage (56), the selective oxidation reactor (35)
The air radiated from the fourth heat recovery device (49) heats the air as a combustion oxidant flowing from the fourth heat recovery device (49) to the third heat recovery device (46).

The third heat recovery passage (57) is provided between the second heat recovery unit (43) and the third heat recovery unit (46) in the combustion air passage (26). This third heat recovery passage (5
7) is configured to recover heat radiated from the transformer (34) to air as a heat medium. That is, the third
In the heat recovery passage (57), the heat radiated from the transformer (34) causes the heat from the third heat recovery device (46) to the second heat recovery device (43).
The air as combustion oxidant flowing to the air is heated.

As shown in FIG. 7, the combustor (36) is formed in a hollow cylindrical shape. A first combustion gas passage (60) and a second combustion gas passage (61) are defined inside the combustor (36). The first combustion gas passage (60) extends up and down along the central axis of the combustor (36). The second combustion gas passage (61) is formed in a cylindrical shape along the outside of the first combustion gas passage (60). This second combustion gas passage (6
1) communicates with the upper end of the first combustion gas passage (60) at its upper end.

At the lower end of the first combustion gas passage (60), a fuel nozzle (62) is provided to protrude. The fuel nozzle (62) is connected to the heating fuel passage (27), and blows out natural gas supplied as heating fuel into the first combustion gas passage (60).

The end of the combustion air passage (26) is connected to the lower end of the first combustion gas passage (60) in the combustor (36). A first flow path (44) of the second heat recovery device (43) is provided near the end of the combustion air passage (26). On the other hand, a starting end of a combustion exhaust gas passage (28) is connected to a lower end of the second combustion gas passage (61) in the combustor (36). A second flow path (45) of the second heat recovery device (43) is provided near the start end of the flue gas passage (28).

A column-shaped second reforming side passage (72) is defined and formed so that the central axis of the combustor (36) coincides with that of the combustor (36). The second reforming side passage (72) is formed to have a larger diameter than the combustor (36). Further, the combustor (36) is arranged in a posture inserted into the lower end of the second reforming side passage (72). The second reforming side passage (72) is filled with a catalyst filler near an upper portion of the combustor (36). The portion of the second reforming side passageway (72) filled with the catalyst filler is the second reactor (33) of the reformer (31) in which the steam reforming reaction is performed.
Is composed.

The first reforming side passage (72) is positioned outside the second reforming side passage (72) in such a manner that the center axis of the second reforming side passage (72) coincides with the first reforming side passage (72).
A reforming-side passage (71) is defined. The first reforming side passage (71) is formed in a cylindrical shape approximately half the height of the second reforming side passage (72), and is provided in close contact with a lower portion of the second reforming side passage (72). ing. The lower end of the first reforming passage (71) communicates with the lower end of the second reforming passage (72). A honeycomb member is provided in the first reforming side passage (71). The lower two thirds of the first reforming passage (71) constitute a first reactor (32) of a reformer (31) in which a partial oxidation reaction is performed.

The first heat recovery unit (40) includes a reformer (31)
Above the first reforming side passageway (71) and the second reforming side passageway (7).
It is arranged across 2). Specifically, the first flow path (41) of the first heat recovery unit (40) is provided above the first reactor (32) in the first reforming side passage (71). The second flow path (42) of the first heat recovery unit (40) is connected to the second reforming side passage (7).
It is provided above the second reactor (33) in 2).

The first reforming-side passage (71) is positioned outside the first reforming-side passage (71) such that the center axis of the first reforming-side passage (71) coincides with the first reforming-side passage (71).
A heat recovery passage (55) is defined. The first heat recovery passage (55) is formed in a cylindrical shape having substantially the same height as the first reforming passage (71), and is arranged so as to surround the side of the first reforming passage (71). ing. Also, the first heat recovery passage (55)
Has a larger diameter than the first reforming side passageway (71), and a gap having a predetermined width is formed between the first heat recovery passageway (55) and the first reforming side passageway (71).

At the lower end of the first heat recovery passage (55),
A source gas passage (23) extending from the humidifier (39) is connected (see FIG. 6). The upper end of the first heat recovery passage (55) is connected to the first reforming passage (71) via the raw material gas passage (23).
It communicates with the upper end. The first heat recovery passage (55) is configured to recover heat radiated from the reformer (31) and the combustor (36) into a raw material gas as a heat medium.

The upper half of the second reforming side passage (72) contains a shift converter (34) and a selective oxidation reactor (35). The selective oxidation reactor (35) is arranged above the shift converter (34). Further, a reformed gas passage (25) is connected to an upper end of the second reforming side passage (72).

A combustion-side passage (69) is defined outside the second reforming-side passage (72) in such a manner that its central axis coincides with that of the second reforming-side passage (72). The combustion side passage (69) is formed in a cylindrical shape approximately half the height of the second reforming side passage (72), and is provided in close contact with a substantially upper half portion of the second reforming side passage (72). Have been. A combustion air passage (26) is connected to the upper end of the combustion side passage (69), and air taken in as a combustion oxidant is introduced. A combustion air passage (26) extending toward the second heat recovery unit (43) is connected to a lower end of the combustion side passage (69).

The third heat recovery unit (46) includes a transformer (34)
Is disposed over the second reforming side passage (72) and the combustion side passage (69). Specifically, the third heat recovery unit (46)
The second flow path (48) is provided between the shift converter (34) and the selective oxidation reactor (35) in the second reforming side passage (72). The first flow path (47) of the third heat recovery device (46) is provided in the combustion side passage (69) so as to surround the periphery of the second flow path (48). The third heat recovery unit (46) is configured to exchange heat between the gas flowing from the shift converter (34) toward the selective oxidation reactor (35) and the air flowing through the combustion side passage (69). .

The fourth heat recovery unit (49) is disposed above the selective oxidation reactor (35) so as to straddle the second reforming side passage (72) and the combustion side passage (69). Specifically, the second flow path (51) of the fourth heat recovery device (49) is provided above the selective oxidation reactor (35) in the second reforming side passage (72).
The first flow path (50) of the fourth heat recovery device (49) is connected to the second flow path (5
It is provided in the combustion side passageway (69) so as to surround the periphery of 1). The fourth heat recovery device (49) is configured to exchange heat between the gas sent from the selective oxidation reactor (35) and the air flowing through the combustion side passage (69).

The portion of the combustion side passage (69) between the third heat recovery unit (46) and the fourth heat recovery unit (49) forms a second heat recovery passage (56). This second heat recovery passage (56)
In the portion that constitutes, the heat radiated from the selective oxidation reactor (35) is recovered into air as a heat medium. Further, a portion of the combustion side passage (69) below the third heat recovery unit (46) forms a third heat recovery passage (57). In the portion constituting the third heat recovery passage (57), the heat radiated from the transformer (34) is recovered to air as a heat medium.

An air supply nozzle (81) is provided in the second reforming side passage (72). This air supply nozzle (81)
The transformer (34) in the second reforming side passage (72) and the third
It protrudes between the heat recovery units (46). The air supply nozzle (81) is connected to the second branch passage (22) of the air supply passage (20).

As described above, in Embodiment 4, the reformer (31), the shift converter (34), the selective oxidation reactor (35), the combustor (36), the first to fourth heat recovery units ( 40, 43, 46, 49) and the first to third heat recovery passages (55, 56, 57) are integrally formed, and these are surrounded by a heat insulating material (80). That is, the heat insulating material (80) is also provided in the gap between the first reforming side passage (71) and the third heat recovery passage (57).

-Operating Operation- The air taken into the combustion air passage (26) as a combustion oxidant is introduced into the combustion side passage (69). The air flowing through the combustion-side passage (69) is supplied to the first flow passage (50) of the fourth heat recovery device (49), the second heat recovery passage (56), and the first flow passage of the third heat recovery device (46). (47), sequentially pass through the third heat recovery passage (57),
During that time it is heated. Specifically, the air flowing through the combustion side passageway (69) absorbs heat from the gas in the second passageway (51) in the first passageway (50) of the fourth heat recovery unit (49), and the second heat recovery passageway. In (56), heat is absorbed from the selective oxidation reactor (35),
In the first flow path (47) of the heat recovery unit (46), the second flow path (4
The heat is absorbed from the gas of 8) and is absorbed from the transformer (34) in the third heat recovery passage (57). The air heated while flowing through the combustion side passageway (69) is introduced into the first flow path (44) of the second heat recovery unit (43), where it is further heated.
It is sent to the first combustion gas passage (60) of 6).

On the other hand, natural gas is fed into the fuel nozzle (62) of the combustor (36) through the heating fuel passage (27). This natural gas is blown out from the fuel nozzle (62) into the first combustion gas passage (60). The natural gas blown into the first combustion gas passage (60) is mixed with the preheated air sent from the combustion air passage (26) and burns. The combustion of the natural gas generates a high-temperature combustion gas.

The high-temperature combustion gas passes through the first combustion gas passage (6
0), flows upward and into the second combustion gas passage (61),
Subsequently, it flows downward through the second combustion gas passage (61). Meanwhile, the combustion gas is supplied to the second reactor (33) of the reformer (31),
Heat is released from the gas flowing from the first reactor (32) to the second reactor (33). The combustion gas after the heat release is sent out from the lower end of the second combustion gas passage (61) as combustion exhaust gas. Thereafter, the combustion exhaust gas is introduced into the second flow path (45) of the second heat recovery device (43). The combustion exhaust gas radiates heat to the air in the first flow path (44) while flowing through the second flow path (45). The exhaust gas after the heat release is exhausted through the exhaust gas passage (28).

The source gas humidified by the humidifier (39) flows into the first heat recovery passage (55) through the source gas passage (23). The raw material gas absorbs heat from the reformer (31) and the combustor (36) while flowing through the first heat recovery passage (55).
It flows into the reforming side passage (71). Subsequently, the raw material gas flows into the first flow path (41) of the first heat recovery device (40) and absorbs heat from the gas in the second flow path (42).

Thereafter, the raw material gas is supplied to the first reformer (31).
It is introduced into the reactor (32). In the first reactor (32), the fed raw material gas comes into contact with the catalyst, and hydrogen is generated by a partial oxidation reaction. The reacted gas sent out from the first reactor (32) flows into the second reforming side passage (72), and is heated by the combustion heat from the combustor (36), and then heated in the reformer (31). To the second reactor (33). In the second reactor (33), the fed gas comes into contact with the catalyst, and hydrogen is generated by a steam reforming reaction. At that time, the combustion heat of the natural gas is supplied from the combustor (36) to the second reactor (33). Then, in the second reactor (33), a steam reforming reaction is performed using the supplied heat as reaction heat.

The reacted gas sent out from the second reactor (33) is introduced into the second flow path (42) of the first heat recovery device (40). The gas after the reaction introduced from the second reactor (33) radiates heat to the raw material gas in the first flow path (41) while flowing through the second flow path (42). The gas after heat release is subsequently introduced into the transformer (34). In the transformer (34), a shift reaction is performed.

The reacted gas sent out from the transformer (34) is mixed with air from the air supply nozzle (81) and then introduced into the second flow path (48) of the third heat recovery unit (46). Is done. The reacted gas introduced from the transformer (34) radiates heat to the air in the first flow path (47) while flowing through the second flow path (48). The gas after the heat release is subsequently introduced into the selective oxidation reactor (35). In the selective oxidation reactor (35), carbon monoxide in the gas is selectively oxidized to carbon dioxide.

The reacted gas sent from the selective oxidation reactor (35) is introduced into the second flow path (51) of the fourth heat recovery unit (49). The reacted gas introduced from the selective oxidation reactor (35) radiates heat to the air in the first flow path (50) while flowing through the second flow path (51). The gas after the heat release is sent out to the reformed gas passage (25) as a reformed gas.

-Effect of Embodiment 4- In Embodiment 4, the reformer (31) is arranged so as to surround the combustor (36). Thus, the combustion heat radiated from the combustor (36) can be efficiently supplied to the reformer (31) around the combustor (36). That is, the proportion of the heat of combustion of the natural gas combusted by the combustor (36) that is effectively used as the reaction heat of the steam reforming reaction can be increased, and the supply of natural gas to the combustor (36) can be increased. The amount can be reduced. Therefore, according to the fourth embodiment, the energy required for operating the reformer (30) can be further reduced.

In the fourth embodiment, the first heat recovery passage (55) is formed so as to surround the reformer (31). For this reason, the heat radiated from the reformer (31) can be recovered into the raw material gas, and the radiation loss from the reformer (30) can be further reduced. Further, by surrounding the periphery of the reformer (31) with the first heat recovery passage (55), it is possible to reliably insulate the reformer (31).

According to the fourth embodiment, the second and third
Since the heat recovery passages (56, 57) and the third and fourth heat recovery units (46, 49) are provided, the transformer (34) and the selective oxidation reactor (35)
From the heat. Therefore, according to the fourth embodiment, the heat loss from the reformer (30) can be further reduced, and the thermal efficiency of the reformer (30) can be improved.

[0164]

Fifth Embodiment In the fifth embodiment of the present invention, in the first embodiment, the heat of the combustion exhaust gas is recovered to the raw material gas, and the heat of the gas sent from the reformer (31) is oxidized for combustion. It is intended to be collected in air as an agent. Here, parts of the fifth embodiment that are different from the first embodiment will be described.

As shown in FIG. 8, the second flow path (42) of the first heat recovery unit (40) is connected to the flue gas passage (28). In the first heat recovery unit (40), heat exchange is performed between the raw material gas flowing through the first flow path (41) and the combustion exhaust gas flowing through the second flow path (42). By this heat exchange, the heat of the combustion exhaust gas discharged from the combustor (36) is recovered by the raw material gas supplied to the reformer (31).

On the other hand, the second flow path (4) of the second heat recovery device (43)
5) is connected between the reformer (31) and the shift converter (34) in the internal gas passage (24). Second heat recovery unit (43)
Then, the air flowing through the first flow path (44) and the gas flowing through the second flow path (45) exchange heat. By this heat exchange, the heat of the reacted gas sent out from the reformer (31) is recovered by the air supplied to the combustor (36) as a combustion oxidant.

[0167]

Other Embodiments of the Invention The present invention may be configured as follows in each of the above embodiments.

-First Modification- In each of the above embodiments, as shown in FIG.
An internal heat recovery unit (82) may be provided inside 4). still,
FIG. 9 shows a case where the present modified example is applied to the first embodiment. The internal heat recovery device (82) is provided between the humidifier (39) and the first heat recovery device (40) in the source gas passage (23). The raw material gas sent from the humidifier (39) flows through the internal heat recovery unit (82),
4) Absorbs heat from the gas flowing inside. That is, in the internal heat recovery unit (82), the reaction heat of the shift reaction, which is an exothermic reaction, is recovered to the raw material gas.

-Second Modification- In each of the above embodiments, the second heat recovery unit (43) exchanges heat between the combustion exhaust gas and air as the oxidizing agent for combustion. On the other hand, as shown in FIG. 10, both the air as the combustion oxidant and the natural gas as the heating fuel are supplied to the second
The heat recovery unit (43) may exchange heat with the combustion exhaust gas. FIG. 10 shows a case where the present modified example is applied to the first embodiment.

-Third Modification- In each of the above embodiments, air is used as the oxidizing agent for combustion, and natural gas is used as the fuel for heating. On the other hand, the cathode exhaust gas may be used as the combustion oxidant, and the anode exhaust gas may be used as the heating fuel.

As shown in FIG. 11, in the third modification, the first flow path (44) of the second heat recovery device (43) is connected to the mixed gas passage (83). An air electrode exhaust passage (13) and a fuel electrode exhaust passage (14) are connected to the start end of the mixed gas passage (83). Also, the end of the mixed gas passage (83)
Connected to combustor (36). FIG. 11 shows a case where the present modified example is applied to the first embodiment.

The air electrode exhaust gas as the combustion oxidant and the fuel electrode exhaust gas as the heating fuel flow into the mixed gas passage (83) and merge. The mixed gas of the air electrode exhaust gas and the fuel electrode exhaust gas flows through the mixed gas passage (83), and is supplied to the combustor (36) after being heated in the first flow path (44) of the second heat recovery unit (43). You. In the combustor (36), hydrogen in the fuel electrode exhaust gas reacts with oxygen in the air electrode exhaust gas to burn. Then, the heat of combustion of hydrogen is supplied from the combustor (36) to the second reactor (33) of the reformer (31).

In the third modification, the fuel electrode exhaust gas discharged from the fuel cell is used as a heating fuel. Therefore, in order to supply the reaction heat of the steam reforming reaction, it is possible to effectively use the hydrogen remaining in the fuel electrode exhaust gas.

Fourth Modification In each of the above embodiments, as shown in FIG. 12, a heater (84) is provided between the first reactor (32) and the second reactor (33). You may. FIG. 12 shows a case where the present modified example is applied to the first embodiment. This heater (8
4) is provided inside the combustor (36). In the heater (84), the gas sent from the first reactor (32) to the second reactor (33) is heated by the high-temperature combustion gas.
That is, the heat of the steam reforming reaction performed in the second reactor (33) is supplied to the gas in the heater (84).

-Fifth Modification-In each of the above embodiments, the humidifier (39) supplies steam directly to the source gas. May be provided to humidify the source gas.

In this modified example, two spaces separated by a water vapor permeable film are formed in the humidifier (39).
Then, a source gas is introduced into one space, and a gas containing a large amount of water vapor is introduced into the other space. For example, an air electrode exhaust gas containing a large amount of water vapor generated by a battery reaction is introduced into the other space. In this case, water vapor in the air electrode exhaust gas passes through the water vapor permeable membrane and is provided to the source gas. That is, it is possible to humidify the raw material gas using the water vapor in the air exhaust gas.

[Brief description of the drawings]

FIG. 1 is a schematic configuration diagram of a fuel cell system according to a first embodiment.

FIG. 2 is a schematic perspective view illustrating a configuration of a reformer according to the first embodiment.

FIG. 3 is a schematic sectional view showing a main part of a reformer according to a second embodiment.

FIG. 4 is a schematic configuration diagram of a fuel cell system according to Embodiment 3.

FIG. 5 is a schematic cross-sectional view illustrating a main part of a reformer according to a third embodiment.

FIG. 6 is a schematic configuration diagram of a fuel cell system according to Embodiment 4.

FIG. 7 is a schematic sectional view showing a main part of a reformer according to a fourth embodiment.

FIG. 8 is a schematic configuration diagram of a fuel cell system according to Embodiment 5.

FIG. 9 is a schematic configuration diagram of a fuel cell system according to a first modification of the embodiment.

FIG. 10 is a schematic configuration diagram of a fuel cell system according to a second modification of the embodiment.

FIG. 11 is a schematic configuration diagram of a fuel cell system according to a third modification of the embodiment.

FIG. 12 is a schematic configuration diagram of a fuel cell system according to a fourth modification of the embodiment.

[Explanation of symbols]

 (10) Fuel cell body (fuel cell) (30) Reformer (31) Reformer (reformer) (32) First reactor (first reactor) (33) Second reactor (second) (Reaction section) (34) Transformer (transformation section) (36) Combustor (combustion section) (37) Honeycomb member (38) Catalyst packing (40) First heat recovery unit (first heating means) (43) 2 Heat recovery unit (second heating means) (52) Heat recovery passage (55) First heat recovery passage (56) Second heat recovery passage (57) Third heat recovery passage

Continued on the front page (72) Inventor Shuji Ikegami 3-12 Chikushinmachi, Sakai-shi, Osaka Daikin Industries Co., Ltd.Rinkai Plant (72) Inventor Kazuo Yonemoto 1304, Kanaokacho, Sakai-shi, Osaka Daikin Industries Co., Ltd. 4G040 EA03 EA06 EB03 EB12 EB44 EB46 4G140 EA03 EA06 EB03 EB12 EB44 EB46 5H027 AA02 BA01 BA09 BA17

Claims (13)

[Claims] 1. A reforming section (31) which is supplied with a raw material gas containing a hydrocarbon-based raw fuel and generates hydrogen by a partial oxidation reaction and a steam reforming reaction. And a combustion section (36) for burning the heating fuel to supply the reaction heat of the steam reforming reaction to the reforming section (31) with the supply of fuel. A reforming device for producing a reformed gas, comprising: a first heating means (40) for heating the raw material gas by a reacted gas flowing out of the reforming section (31); A) a second heating means (43) for heating the combustion oxidant with the combustion exhaust gas discharged from the above). 2. A reforming section (31) to which a raw material gas containing a hydrocarbon-based raw fuel is supplied to generate hydrogen by a partial oxidation reaction and a steam reforming reaction, a combustion oxidizing agent containing oxygen and a heating oxidizer. And a combustion section (36) for burning the heating fuel to supply the reaction heat of the steam reforming reaction to the reforming section (31) with the supply of fuel. A reforming device for generating a reformed gas, a first heating means (40) for heating the raw material gas by a combustion exhaust gas discharged from the combustion section (36), and the reforming section (31). A second heating means (43) for heating the combustion oxidant with the reacted gas flowing out of the reactor. 3. The reformer according to claim 1, wherein the fuel electrode exhaust gas discharged from the fuel electrode (12) of the fuel cell (10) to which the reformed gas generated by the reformer is supplied. A reformer that supplies fuel for heating to the combustion section (36). 4. The reformer according to claim 1, wherein the reforming section (31) includes a first reaction section (32) in which a partial oxidation reaction is performed and a second reaction section (32) in which a steam reforming reaction is performed. Reaction part (33)
And a reforming apparatus provided with: 5. The reforming apparatus according to claim 4, wherein the reforming section (31) introduces the reacted gas flowing out of the first reaction section (32) into the second reaction section (33). The reformer that is configured. 6. The reformer according to claim 4, wherein the first reaction section (32) includes a catalyst exhibiting an activity for a partial oxidation reaction and is formed into a honeycomb member (37).
A reformer in which the second reaction section (33) is filled with a large number of catalyst fillers (38) having a catalyst exhibiting activity in a steam reforming reaction. 7. The reforming apparatus according to claim 1, wherein the reforming section (31) is provided so as to surround the combustion section (36) and is formed integrally with the combustion section (36). Have reformer. 8. The reforming apparatus according to claim 4, wherein the reforming section (31) surrounds the combustion section (36) with the second section.
A reformer provided with a reaction section (33) and a first reaction section (32) surrounding the second reaction section (33) and integrally formed with the combustion section (36). 9. The reformer according to claim 7, wherein the reformer (34), which is supplied with the reacted gas from the reformer (31) and generates hydrogen by a shift reaction, comprises the reformer (34). 31)
Reformer provided so as to surround the periphery. 10. The reformer according to claim 1, wherein a gas after the reaction is supplied from the reformer (31) to generate hydrogen by a shift reaction, and a combustion unit (36). ), A heat recovery passage (52, 55,...) Through which a heat medium flows to absorb heat radiated from one or more or all of the reforming unit (31) and the shift unit (34). A reformer equipped with: 11. The reformer according to claim 10, wherein the heat medium flowing through the heat recovery passages (52, 55,...) Is a raw material gas supplied to the reformer (31). 12. The reformer according to claim 10, wherein the heat medium flowing through the heat recovery passages (52, 55,...) Is a combustion oxidant supplied to the combustion section (36). . 13. A reformer (30) according to any one of claims 1 to 12, and a fuel cell (10) to which reformed gas generated by the reformer (30) is supplied. Fuel cell system.