JP2003300703A - Fuel reformer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a fuel reformer which has a relatively simple structure and whose manufacturing cost is low. <P>SOLUTION: This fuel reformer is provided with a combustion chamber 5A where the fuel is combusted, a high temperature unit 2 provided on the outer circumferential surface side of the combustion chamber 5A and having a reforming part 7 where a reforming catalyst is filled annularly, transforming parts (21, 26) which are provided in a side opposed to the side jointed to the high temperature unit 2 and in which a transforming catalyst is filled cylindrically, a middle and low temperature unit 3 provided in a side opposed to the side jointed to the high temperature unit 2 and having a selective oxidation part 36 in which a selective oxidation catalyst is filled cylindrically, a joint flow pipe 19 for supplying a reformed gas passed through the reforming part of the high temperature unit 2 to the transforming part side of the middle and low temperature unit 3, and a vessel integrally housing the high temperature unit 2 and the middle and low temperature unit 3 jointed to each other by the joint flow unit 19. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fuel reformer for reforming a hydrocarbon-based fuel to produce a hydrogen-rich reformed gas, and in particular to an integrated type fuel cell having a relatively simple structure and a low manufacturing cost. The present invention relates to a fuel reformer. Further, the present invention is a solid polymer type which can deal with various hydrocarbon fuels such as city gas, gas fuel such as LPG and anaerobic digestion gas, liquid fuel such as kerosene and gasoline as hydrocarbon fuel. The present invention relates to an integrated fuel reformer that produces a reformed gas suitable for a fuel cell.

[0002]

2. Description of the Related Art In recent years, fuel cell cogeneration systems capable of supplying heat and electricity in combination with the protection of the global environment have been developed. In this system, a hydrocarbon-based fuel such as natural gas is steam-reformed by a reformer to produce a hydrogen-rich reformed gas, and the produced reformed gas is supplied to a fuel cell to generate electricity. . Therefore, the reformer is an important development factor for the economic efficiency and energy efficiency of the entire system.

Generally, when the fuel cell is a phosphoric acid type fuel cell, the reforming device is a reformer for reforming hydrogen into CO by reforming reaction of hydrocarbons with steam in a combustion section for supplying reforming heat. A quality part and a shift part for transforming CO in the reformed gas into hydrogen and CO2 by a shift reaction with steam. When the fuel cell is a polymer electrolyte fuel cell, the reformer selects a combustion section that supplies reforming heat, a reforming section, a shift conversion section, and CO as residual oxygen in the CO shift gas with oxygen. And a selective oxidation part that is removed by a selective oxidation reaction.
In order to make the reformer compact and improve the thermal efficiency, an integrated reformer in which each component of the reformer is integrated has been proposed. For example, a multi-cylinder reformer or a laminated flat plate reformer is proposed. Etc. are disclosed.

[0004]

However, in the conventional multi-cylindrical reformer, a high-temperature burner combustion section, a reforming section for performing a high-temperature endothermic reaction requiring heating, and a medium-low temperature heat radiating reaction requiring cooling. Since the transformation reaction section and the selective oxidation section for carrying out are arranged in a coaxial multi-cylinder body, there is a problem that the structure is considerably complicated and the manufacturing cost becomes high. Further, in the conventional multi-cylindrical reformer, since the length and area of the cylindrical partition wall partitioning each part is large, and the temperature difference between each part is large, the thermal stress generated in the connecting part of each part is large, and It has the property that the heat flow through the partition is large. Therefore, there are problems that temperature distribution of each part influences each other, temperature control is difficult, and startup time is long. Further, the conventional laminated flat plate reformer has basically the same problems as those of the multi-cylinder reformer.

In the conventional reformer, either a gaseous fuel such as city gas or natural gas or a liquid fuel such as gasoline, kerosene or methanol is dealt with. That is, for the gaseous fuel, preheating of the gaseous fuel and a mixing mechanism with water vapor are required. On the other hand, liquid fuel requires a liquid fuel vaporization mechanism. Therefore, in the conventional reforming apparatus, the gas fuel and the liquid fuel are separately prepared to meet the customer's demand.

However, the gas fuel and the liquid fuel are provided by different suppliers, and different treatments are applied to taxation such as gasoline tax. Therefore, there is an advantage for the user of the fuel cell that if the reforming device can handle both the gaseous fuel and the liquid fuel, the optimum fuel can be used according to the temporal fluctuation of the economic environment. Further, compared with the case where the reformer for gas fuel and the reformer for liquid fuel are manufactured separately, when the reformer that can be applied to both gas fuel and liquid fuel is manufactured, the reformer due to mass production effect There is also a possibility that the manufacturing cost of the

The present invention solves the above-mentioned problems.
A first object is to provide a fuel reformer having a relatively simple structure and a low manufacturing cost. The second purpose is
It is an object of the present invention to provide a fuel reformer that is less likely to generate thermal stress and has excellent durability. A third object is to provide a fuel reformer in which the optimum temperature distribution of each part of the fuel reformer can be easily controlled, the thermal efficiency is high, and the startup time is short. A fourth object is to provide a fuel reformer capable of reforming both gas fuel and liquid fuel.

[0008]

As shown in FIG. 1, a fuel reformer of the present invention that achieves the first object is provided with a combustion chamber 5A in which fuel is burned and an outer peripheral surface side of the combustion chamber 5A. A high temperature unit 2 that is provided and has a reforming section 7 that is annularly filled with a reforming catalyst, and a shift section (21) that is provided on the side connected to the high temperature unit 2 and that is tubular or annularly filled with the shift catalyst. , 26) and a medium-low temperature unit 3 provided on the side opposite to the side connected to the high-temperature unit 2 and having a selective oxidation portion 36 filled with a selective oxidation catalyst in a tubular or annular shape, and a modification of the high-temperature unit 2. The reformed gas that has passed through the quality part,
Connection flow pipe 19 for supplying to the shift section side of the low-temperature unit 3
And the high temperature unit 2 connected by the connection flow pipe 19
And a container 13 that houses the medium and low temperature unit 3 integrally.

The combustion chamber 5A typically has a burner 4 inside and burns fuel in the burner 4. Further typically, the burner 4 is provided on the central axis of the combustion chamber 5A. In the high-temperature unit 2 in the fuel reformer configured as described above, the temperature of the reforming unit 7 rises from, for example, a room temperature at startup to an operating temperature during steady operation. In the middle-and-low temperature unit 3, the temperature of the shift section (21, 26) rises from the room temperature at the time of startup to the shift section temperature at the time of steady operation, and the temperature of the selective oxidation section 36 becomes about room temperature at the startup. The temperature is raised from the state to the temperature of the selective oxidation part during steady operation. As described above, the high-temperature unit 2 and the low-temperature unit 3 are divided according to the operating temperature in the steady state, and the reformed gas is circulated along the process flow of reforming → metamorphosis → selective oxidation by the connecting flow pipe 19. In addition, since the container 13 is integrally housed, the structure is simple and the manufacturing cost is low. Preferably, if the axes of the high temperature unit 2 and the intermediate temperature unit 3 are common and the cross-sectional shape is circular or rectangular (including square), a fuel reformer having a shape suitable for the customer's installation location is provided. In particular, the circular shape makes the gas flow uniform and requires less material for manufacturing. A rectangle, especially a square, facilitates installation.

Preferably, in the fuel reformer of the present invention, the reforming additive water passage 40 formed in the gap between the outer wall of the high temperature unit 2 and the medium and low temperature unit 3 and the inner wall of the container 13, and the reformer. It is preferable that the modified water injection port 41 is provided on the opposite side of the medium-low temperature unit 3 of the added water flow path 40 to the side connected to the high temperature unit 2. With this configuration, during steady operation, the reforming-added water flow path 4 passes through the outer walls of the high-temperature unit 2 and the intermediate-low temperature unit 3.
The heat exchange between the reforming additive water flowing through 0 and the reformed gas is performed,
Increases thermal efficiency.

Preferably, in order to further achieve the fourth object, in the fuel reformer of the present invention, a reforming raw material supply passage 50 for supplying a reforming raw material to the high temperature unit 2 and a reforming addition water passage. 40 and the mixing chamber 44 that communicates the reforming raw material supply passage 50 with each other, the reforming additive water in the superheated steam state in the reforming additive water flow passage 40 is used to modify the interior of the mixing chamber 44. The quality raw material is subjected to a treatment for smoothly performing the reforming reaction in the reforming section 7. That is, when the reforming raw material is a liquid fuel, the fuel is vaporized, and when it is a gaseous fuel, the fuel is preheated.

Preferably, in order to achieve the third and fourth objects, in the fuel reformer of the present invention, a reforming raw material supply passage 50 for supplying the reforming raw material to the high temperature unit 2 is further provided. The second reforming additive water flow path 45 for directly supplying the reforming additive water to the high temperature unit 2 without passing through the low temperature unit 3.
And a mixing chamber 44 that connects the reforming-added water passage 40, the reforming raw material supply passage 50, and the second reforming-added water passage 45 to each other.

When the fuel reformer constructed as described above is started, reforming additive water as a preheating heat medium is supplied from the second reforming additive water passage 45, and heat is exchanged with combustion gas to mix chamber. At 44, steam for reforming addition water is generated. By causing the generated steam to flow back into the reforming-added water flow path 40, the middle- and low-temperature unit 3 is preheated, and the middle- and low-temperature unit 3 is preheated without using a heat medium such as nitrogen gas, thereby starting. Save time. In addition, by preheating the medium-low temperature unit 3 before introducing the reformed gas, it is possible to prevent dew condensation of water in the shift conversion catalyst layer and the selective oxidation catalyst layer of the medium-low temperature unit 3 at the time of introducing the reformed gas, thereby improving the catalyst life. Can be made. Further, at the time of steady operation of the fuel reformer, it is possible to adjust the ratio of the respective water amounts of the reforming-added water passage 40 and the second reformed-addition water passage 45 without changing the total flow rate of the reformed addition water. The temperature of each part can be controlled stably.

The fuel reformer of the present invention which achieves the third object is further provided with a baffle plate 18 provided in a gap between the connecting portion between the high temperature unit 2 and the low temperature unit 3, the high temperature unit 2 and the low temperature unit. A heat exchange part 24 provided on the surface facing the heat exchanger 3, the heat exchange part 24 performing heat exchange between the reformed gas sent from the high temperature unit 2 to the intermediate / low temperature unit 3 and the reforming added water. Then, in the heat exchange unit 24, through the outer walls of the high temperature unit 2 and the low temperature unit 3,
The reforming additive water flowing through the reforming additive water flow path 40 and the reforming gas are heat-exchanged with each other to evaporate the reforming additive water and superheat it, and the temperature distribution inside the fuel reformer becomes appropriate. .

In the fuel reformer of the present invention which achieves the second and third objects, when the connecting flow pipe 19 has a structure which has an expanding and contracting member which expands and contracts in the axial direction of the connecting flow pipe 19, In such a cold state and a state in which the temperature is raised as in the steady operation, the high temperature unit 2, the medium and low temperature unit 3 and the container 1
The strain due to the thermal expansion generated between 3 and 3 can be absorbed by the expansion and contraction of the connecting flow pipe 19, and the influence of the thermal stress can be small even if the startup / operation is repeated. The elastic member includes a member having a corrugated cross section like a bellows and a member such as a diaphragm which is easily bent and deformed. Further, since the surface area of the elastic member is larger than that of the straight pipe, the heat exchange between the reformed gas flowing inside the pipe and the reforming additive water flowing outside the pipe can be efficiently performed.

In the fuel reformer of the present invention, when the high temperature unit 2 is arranged on the upper side and the medium / low temperature unit 3 is arranged on the lower side of the high temperature unit 2, the reforming water addition flow path is provided. In the natural state, the phase change from water to water vapor, the difference in specific gravity between water and water vapor, and the direction of gravity coincide with each other. Also,
In the fuel reformer of the present invention, when the high temperature unit 2 is arranged on the lower side and the medium / low temperature unit 3 is arranged on the upper side of the high temperature unit 2, for example, the supply of water or the supply of the reforming raw material to the fuel reformer is performed. If existing piping is used, it may be convenient to install the fuel reformer by installing it upside down.

Preferably, in the fuel reformer of the present invention, the shift conversion section is provided on the high temperature unit 2 side, and
A first shift section 2 in which a first shift catalyst is filled in a tubular or annular shape.
1 and the second shift conversion section 26 provided on the side of the selective oxidation section 36 and having a second shift catalyst filled in a tubular or annular shape, the temperature distribution in the shift conversion section is optimized and It becomes easy to remove the heat generated by the transformation reaction.
Further, during steady-state operation, the first shift conversion section 21 is at a higher temperature than the second shift shift section 26, so that the shift conversion reaction proceeds efficiently at this steady-state temperature. And the composition of the second shift conversion catalyst can be appropriately selected.

Preferably, in the fuel reformer of the present invention, as shown in FIG. 7, for example, the second shift section 26 is further provided.
Is an inner cylindrical body 29 provided coaxially with the outer wall of the medium-low temperature unit 3, and an intermediate cylindrical body 30 provided coaxially with the outer wall of the medium-low temperature unit 3 and provided on the outer peripheral side of the inner cylindrical body 29. The inner circumferential surface of the inner cylindrical body 29 forms a gas introduction passage 31 for the reformed gas that has passed through the first shift section 21, and the outer circumferential surface of the inner cylindrical body 29 and the inner circumferential surface of the middle cylindrical body 30 form a first The catalyst-filled layer 25 of the second conversion section 26 is formed, and the gas outlet passage 3 is formed by the outer peripheral surface of the middle cylindrical body 30 and the inner peripheral surface of the low-temperature unit 3.
2 is preferably formed. That is, the first shift unit 21
The reformed gas that has passed through passes through the gas introduction flow path 31, the catalyst packed bed 25, the gas discharge flow path 32, and is guided to the selective oxidation section 36.

Preferably, in the fuel reformer of the present invention, as shown in FIG. 7, for example, the second shift section 26 is further provided.
Is the catalyst introduction layer 2 of the gas introduction flow path 31 and the second shift conversion section 26.
5 and the selective oxidation part 36 of the inner cylindrical body 29.
The first opening 33 provided on the side, the catalyst filling layer 25 of the second shift conversion section 26, and the gas derivation flow channel 32 communicate with each other, and the first opening 33 is provided on the side of the first shift conversion section 21 of the middle cylindrical body 30. Second
It is preferable to have a configuration including the opening 28. That is, the reformed gas that has passed through the first shift conversion section 21 flows downward in the gas introduction flow path 3
No. 1 and is turned back at the first opening 33, and passes through the catalyst packed bed 25 in an upward flow. The reformed gas that has flowed out of the catalyst-filled layer 25 is turned back at the second opening 28, passes through the gas outlet passage 32 in a downward flow, and is guided to the selective oxidation unit 36.

Preferably, in the fuel reformer of the present invention, as shown in, for example, FIGS.
26) and a selective oxidation part 36 are provided with a baffle plate 38, and an inlet 58 for the selective oxidation air is arranged inside the central opening of the baffle plate 38. And the selective oxidation air are appropriately mixed, and the selective oxidation reaction in the selective oxidation section 36 effectively progresses.

Preferably, in the fuel reformer of the present invention, as shown in, for example, FIG. 7, the selective oxidation section 36 prevents the reformed gas sent from the shift conversion sections (21, 26) from passing near the center. With the configuration in which the cylindrical hollow portion 36B configured as described above is provided, the flow in the vicinity of the central portion where the amount of reformed gas tends to increase is suppressed, so the selective oxidation portion 3
The reformed gas uniformly flows to the peripheral portion of 6, and the selective oxidation reaction proceeds uniformly. Therefore, the amount of the selective oxidation catalyst filled in the selective oxidation section 36 is optimized and the temperature distribution is also optimized.

Preferably, in the fuel reformer of the present invention, as shown in, for example, FIG. 8, the medium / low temperature unit 3 is provided on the high temperature unit 2 side, and is filled with the first shift catalyst in a tubular or annular shape. The second shift conversion section 26A is provided with the shift shift section (21, 26A) including the first shift shift section 21 and the second shift shift section 26A that is filled with the second shift catalyst in a tubular or annular shape.
Is located coaxially with the selective oxidation section 36A, the second shift conversion section 26A and the selective oxidation section 36A are concentrically arranged, and the entire reformer becomes compact.

Preferably, in the fuel reformer of the present invention, as shown in FIG. 8, for example, the second shift conversion section 26A has an inner cylindrical body 29 provided coaxially with the outer wall of the middle and low temperature unit 3.
A and a middle cylindrical body 30A coaxial with the outer wall of the middle and low temperature unit 3 and provided on the outer peripheral side of the inner cylindrical body 29A. Then, the catalyst packed bed 25A of the second shift conversion section 26A
Is provided in a space formed by the outer peripheral surface of the inner cylindrical body 29A and the inner peripheral surface of the middle cylindrical body 30A. The selective oxidation catalyst packed layer 35A of the selective oxidation section 36A is a medium cylindrical body 30A.
It is provided in the space formed by the outer peripheral surface of and the inner peripheral surface of the low-temperature unit 3. The gas introduction channel 31A has a first
The reformed gas is formed at the facing portion between the shift conversion section 21 and the second shift conversion section 26A, and the reformed gas that has passed through the first shift conversion section 21 flows into the second shift conversion section 26A. 32 A of gas derivation flow paths are formed by 70 A of conduits which connect the bottom face side of the 2nd shift conversion part 26A, and the 1st shift conversion part 21 facing part of 36 A of selective oxidation parts.
The reformed gas that has passed through the shift conversion section 26A is sent to the selective oxidation section 36A.

In the apparatus constructed as described above, the reformed gas that has passed through the first shift conversion section 21 is supplied with the gas introduction passage 31A.
Through the second shift conversion section 26A, and further through the gas outlet flow path 32A to be guided to the selective oxidation section 36A. Further, since the selective oxidation part 36A is annularly positioned with the second shift conversion part 26A as the center part, the flow near the center part of the reformer where the amount of reformed gas tends to increase is suppressed,
The reformed gas uniformly flows to the peripheral portion of the selective oxidation portion 36A, and the selective oxidation reaction proceeds uniformly. As a result, the selective oxidation unit 3
The amount of the selective oxidation catalyst filled in 6A is optimized, and the temperature distribution is also optimized.

Preferably, in the fuel reformer of the present invention, as shown in FIG.
And a second baffle plate 27A provided at a portion facing the second shift portion 26A.
A, the inner peripheral surface of the middle cylindrical body 30A, and the outer peripheral surface of the inner cylindrical body 29A are preferably formed. Preferably, the baffle plate 27A has an annular shape, and when the gas dispersion plate 34A is provided at the center of the annular ring, the reformed gas uniformly flows to the second shift conversion section 26A, and the shift reaction proceeds uniformly.

Preferably, in the fuel reformer of the present invention, the gas outlet passage 32A is, for example, as shown in FIG.
When it is formed by the bottom surface 39 of the middle cylindrical body 30A, the inner peripheral surface of the inner cylindrical body 29, and the conduit 70A that connects the inner peripheral surface of the inner cylindrical body 29A and the selective oxidation portion 36A, a compact shape is reformed. 32A of gas derivation flow paths are effectively arrange | positioned with respect to the container. Preferably, the selective oxidation air inlet port 58 is provided.
Is disposed inside the first opening 33A located on the bottom surface 39 side of the inner cylindrical body 30A of the inner cylindrical body 29A, the reformed gas transformed in the transformation unit (21, 26A) and the selective oxidation The air is appropriately mixed, and the selective oxidation reaction in the selective oxidation unit 36A effectively progresses.

Preferably, in the fuel reformer of the present invention, when the vacuum heat insulating layer 60 is provided on the outer periphery of the container 13, the entire reformer becomes compact, and the high temperature unit 2, the medium and low temperature unit 3 and the reforming addition are performed. Since the heat loss from the reforming added water flowing through the water flow path 40 is small, the thermal efficiency of the reformer is improved. Preferably, when the wall surface forming the vacuum heat insulating layer 60 is formed of a material having high reflectance, for example, silver plating or aluminum plating, heat radiation can be reduced in addition to heat conduction.

The fuel reformer of the present invention which achieves the third and fourth objects is provided, for example, as shown in FIG. 1, in a combustion chamber 5A in which fuel burns, and on the outer peripheral surface side of the combustion chamber 5A. At the same time, a high temperature unit 2 having a reforming section 7 filled with a reforming catalyst, a shift section (21, 26) for shifting the reformed gas that has passed through the reforming section 7 of the high temperature unit 2, and a shift section The medium / low temperature unit 3 having a selective oxidation unit 36 for selectively oxidizing the reformed gas, and the reforming additive water are arranged in the medium / low temperature unit 3 so that heat exchange is possible, and the high temperature unit 2 is subjected to the reforming. A modified additive water channel 40 for supplying additive water;
A second reforming additive water channel 45 for directly supplying the reforming additive water to the high temperature unit 2 without passing through the middle-low temperature unit 3, and a reforming raw material supply channel 50 for supplying the reforming raw material to the high temperature unit 2.
The mixing chamber 44 is provided with the reforming-added water passage 40, the second reforming-added water passage 45, and the reforming raw material supply passage 50 communicating with each other.

When the fuel reformer thus constructed is started, reforming additive water as a preheating heat medium is supplied from the second reforming additive water flow passage 45, and heat is exchanged with the combustion gas to mix chamber. At 44, steam for reforming addition water is generated. By causing the generated steam to flow back into the reforming-added water flow path 40, the middle- and low-temperature unit 3 is preheated, and the middle- and low-temperature unit 3 is preheated without using a heat medium such as nitrogen gas, thereby starting. Save time. In addition, by preheating the medium-low temperature unit 3 before introducing the reformed gas, it is possible to prevent dew condensation of water in the shift conversion catalyst layer and the selective oxidation catalyst layer of the medium-low temperature unit 3 at the time of introducing the reformed gas, thereby improving the catalyst life. Can be made. Further, at the time of steady operation of the fuel reformer, it is possible to adjust the ratio of the respective water amounts of the reforming-added water passage 40 and the second reformed-addition water passage 45 without changing the total flow rate of the reformed addition water. The temperature of each part can be controlled stably.

[0030]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described below with reference to cross-sectional views showing a schematic configuration of a reformer according to the present invention. FIG. 1 is a vertical sectional view showing a first embodiment of a fuel reformer according to the present invention. In the figure, a reformer 1 is provided with a reformer upper portion 2 as a high temperature unit and a reformer lower portion 3 as an intermediate temperature unit. The reformer upper part 2 has a burner 4 for burning fuel, a combustion cylinder 5 arranged coaxially with the burner 4, and an annular reforming section 7 containing a reforming catalyst packed layer 6. ing. The burner 4 is provided substantially on the central axis of the combustion cylinder 5. Reforming catalyst packed bed 6
Any reforming catalyst may be used as long as it promotes the reforming reaction. For example, a Ni-based reforming catalyst or a Ru-based reforming catalyst is used as the type of catalyst. The shape of the reforming catalyst may be granular, columnar, honeycomb-shaped or monolith-shaped. Illustration of details of the burner 4 is omitted.

A peripheral wall of the combustion chamber 5A is formed by the combustion cylinder 5. A combustion gas passage 10, a baffle plate 11, and an outlet 12 are provided in the gap between the combustion cylinder 5 and the reforming section 7. The partition wall 15 separates the combustion gas flow passage 10 and the reformed gas flow passage 16 from each other, and is made of a metal material or the like having high heat resistance. The heat insulating material 14 is provided between the combustion chamber 5A and the partition wall 15 and suppresses heat transfer between the reformed gas that has exited the reforming section 7 and the combustion gas. Baffle board 11
Is to make the flow distribution of the combustion gas in the combustion gas passage 10 uniform, and its structure is annular and has a large number of holes.

The lower part 3 of the reformer comprises a first shift conversion catalyst packed bed 20.
A cylindrical first shift conversion section 21 containing the above, a second cylindrical shift conversion section 26 containing a second shift conversion catalyst packed layer 25, and a cylindrical selective oxidation section 36 containing a selective oxidation catalyst packed layer 35. Is equipped with. As the first shift catalyst used in the first shift catalyst packed bed 20, for example, a Fe—Cr-based high temperature shift catalyst or P
Examples include t-based medium-high temperature shift catalysts. Examples of the second shift catalyst used in the second shift catalyst packed layer 25 include a Cu—Zn low temperature shift catalyst and a Pt low temperature shift catalyst. Examples of the shape of the catalyst used in the first shift conversion catalyst-packed layer 20 and the second shift conversion catalyst-packed layer 25 include a granular shape, a cylindrical shape, a honeycomb shape, and a monolith shape.

The selective oxidation catalyst used in the selective oxidation catalyst packed layer 35 may be any one as long as it has a high selective oxidation property with respect to CO. For example, a Pt-based selective oxidation catalyst, a Ru-based selective oxidation catalyst or a Pt-Ru-based selective oxidation catalyst. and so on. The shape of the catalyst used in the selective oxidation catalyst packed layer 35 may be granular, cylindrical, honeycomb-shaped, monolith-shaped, or the like.

The connecting flow pipe 19 is formed on the bottom surface 1 of the reformer upper portion 2.
7 and the upper surface 23 of the lower reformer 3 are connected, and for example, a corrugated expansion / contraction tube that expands / contracts in the axial direction of the connection flow tube 19 is used. Here, the upper part of the reformer 2 is surrounded by a cylindrical body at its peripheral edge, and the bottom face 17 is provided in a bucket-like bottom plate shape with respect to the upper part 2 of the reformer, and is connected and distributed in the central part. It has an opening leading to the tube 19. The lower part of the reformer 3 is surrounded by a cylindrical body at its periphery, and the upper surface 23 is provided in a lid-like shape with respect to the lower part 3 of the reformer, and the central part thereof has an opening communicating with the connecting flow pipe 19. have. Bottom 43
Is provided in a bucket-like bottom plate shape with respect to the lower portion 3 of the reformer, and has an opening communicating with the reformed gas outlet pipe 55 in the center.

When a corrugated expansion tube is used as the connecting flow tube 19, thermal expansion and contraction of the reformer upper part 2 and the reformer lower part 3 can be absorbed by the axial deformation of the expansion tube, so that the bottom surface 1
A material having high rigidity may be used for 7 and the upper surface 23. Further, the attachment position of the connecting flow pipe 19 to the bottom surface 17 and the upper surface 23 is not limited to the central portion, but may be the peripheral portion, or a plurality of connecting flow pipes 19 may be provided on the bottom surface 17 and the upper surface 23. When a straight pipe is used for the conduit portion of the connecting flow pipe 19, the bottom surface 1
In order to absorb the thermal expansion and contraction of the reformer upper part 2 and the reformer lower part 3 by the bending deformation of 7 and the upper surface 23, the connecting flow pipe 19
The bottom 17 and the upper surface 23 may be attached to the central portion, and the bottom 17 and the upper surface 23 may be made of a steel plate made of the same material as the other parts of the upper reformer 2 and the lower reformer 3. It is preferable that the bottom surface 17 and the top surface 23 be subjected to corrugation molding because bending deformation is further facilitated. By doing so, a normal pipe having no elasticity can be used as the connecting flow pipe 19.

The vessel 13 is a cylindrical body that integrally houses the reformer upper portion 2 and the reformer lower portion 3 connected by a connecting flow pipe 19, and has a first reforming additive water inlet 41 and a reformer on the bottom surface. A gas outlet pipe 55 is provided. The container 13 is provided coaxially with the cylindrical upper reformer 2 and the lower reformer 3.
The heat insulating layer 60 is provided on the outer periphery of the container 13 and the upper surface of the reformer upper portion 2, and as the heat insulating layer to be used, for example, a vacuum heat insulating layer is suitable. The gas dispersion plate 22 is provided in the space formed between the upper reforming lower surface 23 and the first shift conversion catalyst packed layer 20, and the reformed gas flowing from the connecting flow pipe 19 is uniformly distributed over the first shift catalyst. A perforated plate is used so as to flow into the packed bed 20. The gas dispersion plate 37 is a space formed in the gap between the bottom surface of the second shift conversion catalyst packed layer 25 and the selective oxidation catalyst packed layer 35, and is provided below the annular baffle plate 38. A perforated plate is used so that the shift gas flowing from the central opening of 38 uniformly flows into the selective oxidation catalyst packed bed 35.

The first reforming-added water channel 40 is provided in the upper part 2 of the reformer.
Is formed in a gap between the outer wall of the reformer and the outer wall of the lower reformer 3 and the inner wall of the container 13. Here, the upper reformer 2 and the lower reformer 3 are cylinders provided coaxially with the container 13. Because of this, it has an annular space in cross section. In addition, the first reforming-added water flow path 40 is formed by a pipe with a reformer upper portion 2 and a reformer lower portion 3
It may be formed of a tube material that penetrates through and can exchange heat. The first reforming-added water inlet 41 is provided at the lower end of the first reforming-added water channel 40 on the reformer lower portion 3 side. The first reformed added water injection flow path 66 is a conduit for supplying the reformed added water to the first reformed added water flow path 40 via the flow rate adjusting valve 64 and the first reformed added water injection port 41. is there. The drain solenoid valve 63 is opened at the time of startup to open the first reforming addition water flow path 4
0 allows the reformed added water or steam to flow backward,
It is closed during steady operation to prevent the reformed additive water supplied to the first reformed additive water flow path 40 from leaking to the outside.

The mixing chamber 44 is provided at the upper end of the upper part 2 of the reformer, and has a first reforming additive water channel 40, a second reforming additive water channel 45, a reforming raw material channel 50 and a reforming section inlet. The gas flow path 8 communicates with each other, and during normal operation, the reforming additive water and the reforming raw material are supplied, and the mixed gas of the reforming additive water and the reforming raw material is sent to the reforming unit 7. The second reformed added water flow path 45 is provided above the mixing chamber 44 so as to communicate with the mixing chamber 44, and has, for example, an annular shape. A dispersion plate 46 and an injection port 47 are provided in the second reformed added water flow passage 45, and the reformed added water is supplied through a flow rate adjusting valve 65 provided in the second reformed added water injection passage 67. It The reforming raw material flow passage 50 as the reforming raw material supply passage is provided with the second reforming added water passage 4
5 is an annular flow path provided below 5 and communicated with the mixing chamber 44. The reforming raw material flow path 50 is
This is a conduit provided with a dispersion plate 51 and an injection port 52.

The annular baffle plate 18 is provided in the gap between the reformer upper bottom surface 17 and the reformer lower upper surface 23.
The baffle plate 18 interferes with the flow of the first reforming-added water passage 40 and guides the flow of the reforming-added water to the side of the connecting flow pipe 19 to improve the reforming-added water reformer upper bottom surface 17 and The heat exchange with the lower part upper surface 23 is made efficient. Heat exchange section 24
Is an annular space formed by the reformer upper bottom surface 17, the reformer lower upper surface 23, the baffle plate 18, and the connecting flow pipe 19, and heat exchange between the reformed gas and the first reformed additive water is performed. .

The reformed gas outlet pipe 55 and the selective oxidation air inlet pipe 57 are provided in a double pipe shape on the bottom surface 43 of the reformer lower portion 3. The selective oxidation air introduction port 58 is an opening provided on the gap side between the second shift conversion catalyst filling layer 25 and the selective oxidation catalyst filling layer 35 of the selective oxidation air introduction pipe 57, and is the center of the annular baffle plate 38. It is installed inside the opening. The solenoid valve 62 is provided at the reformed gas outlet of the reformed gas outlet pipe 55, and is closed at the time of startup and opened at the time of steady operation.

Next, a method of operating the fuel reformer of the present invention will be described. FIG. 2 is a flow chart for explaining the operating procedure at the time of startup in the device of FIG. FIG. 3 is a preheating state at the time of startup in the apparatus of FIG. 1, FIG. 4 is a reforming raw material supply start state,
FIG. 5 is a vertical cross-sectional view for explaining a supply start state of the first reformed added water. 3 to 5, the valves 62, 6
When 3, 64 and 65 are closed, they are painted black, and when they are open, they are outlined.

First, the operation method at the time of start-up will be described. Combustion air is sent to the burner 4 to pre-purge the burner 4, the combustion cylinder 5 and the combustion gas passage 10, and the ignition device is operated, and at the same time, the supply of burner fuel is started. Then, the burner is ignited (S100). When the burner ignition is confirmed, the injection of the second reforming additive water as the heat medium at startup is started from the second reforming additive water inlet 47 (see FIG. 3). The high-temperature combustion gas after ignition turns back at the bottom of the combustion cylinder 5 and preheats the reforming catalyst filling layer 6 while passing through the combustion gas channel 10, and also causes the second reforming additive water channel 45 and the mixing chamber 44 to flow. The second reforming additive water as the heating medium flowing at the time of start-up is evaporated and superheated. At startup, the solenoid valve 62 at the reformed gas outlet is closed, and the first
Since the drain solenoid valve 63 of the reforming-added water passage is opened, the generated superheated steam flows back through the first reforming-added water passage 40 to preheat the lower reformer 3 (S102). In this way, by preheating the lower part of the reformer 3 above the dew point of the introduced reformed gas before introducing the reformed gas, it is possible to prevent water from condensing in the catalyst layer at the time of introducing the reformed gas and thus improve the catalyst life. You can Then, it is judged whether the inlet temperature of the reforming catalyst packed bed 6 has reached a predetermined temperature (S104), and the preheating of the lower reformer 3 is continued until it reaches the predetermined temperature. The predetermined temperature with respect to the inlet temperature of the reforming catalyst packed bed 6 varies depending on the type of fuel to be reformed, but is preferably in the range of 450 to 550 ° C, for example.

When the inlet temperature of the reforming catalyst packed bed 6 reaches a predetermined temperature, the reformed gas outlet solenoid valve 62 is opened and the drain solenoid valve 63 of the first reforming additive water flow passage is closed (S1).
06). Then, about 30 to 50% of the fuel at the rated load and the fuel as the selective oxidizing air and the selective oxidizing air are supplied from the fuel inlet 52 and the selective oxidizing air inlet 58, respectively, and the reforming of the fuel is started (S108). ; See FIG. 4).

When the reforming of the fuel is started, the shift conversion reaction and the selective oxidation reaction are exothermic reactions as will be described later, so that the first shift conversion catalyst packed bed 20, the second shift conversion catalyst packed bed 25 and the selective oxidation catalyst packed bed 35 are separated from each other. The temperature rises due to the heat generated by the reaction. Then, the temperature of the catalyst layer that becomes the rate-determining value for shifting to the steady operation, for example, in the apparatus of FIG. 1, the inlet temperature of the second shift conversion catalyst packed layer 25 as the catalyst layer that takes the longest time to raise the temperature becomes a predetermined temperature. It is determined whether it has arrived (S110). The reforming of the fuel with the second reforming additive water is continued until the inlet temperature of the second shift conversion catalyst packed bed 25 reaches a predetermined temperature. The predetermined temperature with respect to the inlet temperature of the second shift conversion catalyst packed bed 25 is preferably in the range of 180 to 220 ° C. when a Cu—Zn-based low temperature shift catalyst is used as the second shift catalyst, for example.

When the inlet temperature of the second shift conversion catalyst packed bed 25 reaches a predetermined temperature, the first reforming additive water injection port 41
At the same time when the injection of reforming additive water is started (S112), the introduction amount of fuel and air for selective oxidation is gradually increased to the rated flow rate, and the startup state is terminated and a steady state is entered (FIG. 5).
reference). Further, the reformed gas discharged from the outlet of the reformed gas outlet pipe 55 can be guided to the burner 4 and used as burner fuel. As a start-up operation of the fuel reformer of the present invention, by providing a step of preheating each catalyst packed bed of the fuel reformer, the start-up time can be shortened and the startability can be improved. Further, according to the present invention, the reforming additive water is used as the heat medium for preheating the reformer, and it is not necessary to use the heat medium such as nitrogen as in the conventional product. Therefore, the fuel reformers are dispersed and arranged in various places. In this case, it becomes easy to secure the heat medium.

Next, the operating state of the fuel reformer according to the present embodiment during steady operation will be described. Here, the conditions under which the first reformed additive water, the second reformed additive water and the reforming raw material are treated in the upper part of the reformer 2 and the lower part of the reformer 3 are shown in FIG. Will be described with reference to FIG. First
The first reformed additive water injected from the reformed additive water inlet 41 flows through the first reformed additive water flow passage 40 in a counterflow with the reformed gas flowing inside the lower reformer 3. The first reformed added water flowing through the first reformed added water flow channel 40 is supplied to the selective oxidation unit 36, the second
The shift conversion section 26 and the first shift conversion section 21 are cooled and evaporated at the same time, and are superheated by the high temperature reformed gas discharged from the reforming section 7 in the heat exchanging section 24 and introduced into the mixing chamber 44. Fuel inlet 5
The reforming raw material injected from 2 is vaporized by the superheated steam of the first reforming additive water in the mixing chamber 44 in the case of liquid fuel such as kerosene, and is preheated in the case of gaseous fuel such as city gas. Here, since the temperature of the first reformed addition water superheated steam entering the mixing chamber 44 can be set in the range of 400 to 600 ° C., for example, the superheated steam has a sufficiently high capacity as a heat source for vaporizing or preheating the fuel. Have.

On the other hand, the second reformed added water injected from the second reformed added water inlet 47 is heated by the combustion gas and evaporated while flowing through the second reformed added water flow path 45, and then mixed in the mixing chamber. At 44, the mixed gas of the second reforming added water and the reforming raw material merges, and is introduced into the reforming catalyst packed bed 6 through the reforming section inlet gas flow path 8. In the reforming catalyst packed bed 6, a steam reforming reaction of fuel is mainly performed. For example, when the reforming raw material is methane, a steam reforming reaction according to the following equation is performed. CH ₄ + H ₂ O → CO + 3H ₂ (1)

Since the hydrocarbon steam reforming reaction is an endothermic reaction, the higher the reaction temperature, the higher the hydrocarbon reforming rate and the faster the reaction rate. However, if the temperature is set too high, the heat resistance specification of the reformer material becomes stricter, and the thermal efficiency tends to decrease due to the increase of heat radiated from the reformer. Therefore,
The temperature distribution of the reforming catalyst packed bed 6 is set to, for example, 550 to 800 ° C. in the gas flow direction, and the optimum temperature distribution can be further limited depending on the type of the reforming raw material. Further, the larger the amount of steam involved in the reaction, the higher the reforming rate, but since the heat efficiency decreases due to the increase in the amount of heat for generating steam, the S / C is, for example, in the range of 2.2 to 3.5. Is preferred. The reforming reaction heat is supplied to the reforming catalyst packed bed 6 by using the combustion heat of the burner fuel in the combustion chamber 5A as a heat source to radiate heat from the combustion cylindrical body 5 and the combustion gas passage 10.
And heat transfer from the combustion gas flowing through it.

After the reformed gas exiting the reforming section 7 has been cooled by the heat exchanging section 24, the first shift section 21 and the second shift section 26.
, The transformation reaction of the following formula is carried out. CO + H ₂ O → CO ₂ + H ₂ (2) Since this shift reaction is an exothermic reaction, lowering the reaction temperature is advantageous because the CO concentration of the reformed gas after shift is low. However, there is a point that the reaction speed becomes slow.

Therefore, in this embodiment, the first shift section 21 having a relatively high reaction temperature and the second shift section 26 having a low reaction temperature.
Is provided to increase the reaction speed in the first shift section 21,
By reducing the CO concentration of the reformed gas in the shift conversion unit 26,
It improves the efficiency of the overall conversion reaction. The temperature distribution of the first shift conversion catalyst packed bed 20 is, for example, 50 in the gas flow direction.
0-280 ℃, preferably 450-300 ℃, the second
The temperature distribution of the shift conversion catalyst packed bed 25 is, for example, 280 to 170 ° C., preferably 250 to 190 ° C. in the gas flow direction.
It is better to The CO concentration of the reformed gas in each part is
It is about 10% at the inlet of the first shift conversion catalyst-packed layer 20, about 3 to 5% at the inlet of the second shift conversion catalyst-packed layer 25, and about 0.3 to 1% at the outlet of the second shift conversion catalyst-packed layer. In this way, the temperature distribution of each shift catalyst packed bed is optimized to lower the residual CO concentration in the reformed reformed gas, and at the same time, the total amount of shift catalyst packed is reduced to make the reformer compact and reduce the cost. Can be achieved.

The reformed gas leaving the second shift section 26 is guided to the selective oxidation section 36, and the CO selective oxidation reaction of the following formula is performed between the reformed gas and the selective oxidation air introduced from the selective oxidation air introduction port 58. Done. CO + (1/2) O ₂ → CO ₂ (3) Oxygen in the air for selective oxidation is obtained by oxidizing CO in the reformed gas according to the reaction formula (3) and removing the reformed gas. Since the hydrogen contained therein is also oxidized and consumed, it is important to suppress the oxidation reaction between oxygen and hydrogen in order to improve the hydrogen production efficiency of the reformer, that is, the thermal efficiency.

In the present embodiment, an annular baffle plate 38 is provided in the space between the second shift conversion section 26 and the selective oxidation section 36, and the selective oxidation air introduction port 58 is arranged at the central opening of the baffle plate 38. The reformed gas and the selective oxidation air are uniformly mixed. The temperature distribution of the selective oxidation catalyst packed bed 35 is, for example, 200 to 100 ° C, preferably 150 to 110 ° C in the gas flow direction. The introduction amount of the selective oxidation air may be determined so that the residual CO concentration of the reformed gas after the selective oxidation is, for example, 100 ppm or less, preferably 10 ppm or less. In order to increase the hydrogen production efficiency of the reformer, the molar ratio (O ₂ / CO) of oxygen in the selective oxidation air and CO in the reformed gas introduced into the selective oxidation section 36 is, for example, 1.2. ~ 3.0 is desirable, 1.2 ~
The range of 1.8 is more desirable.

Thus, by optimizing the temperature distribution of the selective oxidation catalyst packed bed 35 and improving the mixing of the reformed gas and the selective oxidation air, the C of the reformed gas after selective oxidation is improved.
It is possible to reduce the residual concentration of O, suppress the consumption of hydrogen, and improve the thermal efficiency of the reformer.

In the first embodiment, the selective oxidization section 36 has one stage as described above, but the selective oxidization section 36 has two stages.
For example, the second selective oxidation section may be provided below the selective oxidation section 36 shown in FIG. 1, and the second selective oxidation section may be provided downstream of the reformer 7.

Further, although the reformed gas after selective oxidation that has exited the selective oxidation section 36 is obtained from the outlet of the reformed gas outlet pipe 55, the obtained reformed gas can be supplied to a fuel cell to generate electricity ( Illustration of details of the fuel cell is omitted). Generally, in the case of fuel cell power generation using a hydrocarbon reformed gas as a fuel, 70 to 80% of hydrogen in the reformed gas is consumed, and the remaining hydrogen is discharged as an anode off gas. According to the first embodiment, the anode off gas of the fuel cell can be used as the burner fuel.

Further, in the above embodiment, in the burner 4, the burner fuel at the time of steady operation is covered by the anode off-gas only, or the mixed burner system in which the reforming raw material is supplied as the auxiliary fuel together with the anode off-gas. May be used. The combustion gas generated by the combustion by the burner 4 flows downward in the combustion cylinder 5, is folded back below the combustion cylinder 5, flows in the combustion gas flow path 10 in the upward flow, and flows through the baffle plate. It is discharged from the combustion gas discharge port 12 via 11.

FIG. 6 is a configuration block diagram for explaining the second embodiment of the present invention. Here, a first reforming addition water flow rate control unit 70 and a second reforming addition water flow rate control unit 72 are provided so as to be suitable for the steady-state operation of the fuel reformer shown in FIG. The first reforming addition water flow rate control unit 70 includes thermometers T1 to T5 such as thermocouples that measure the temperatures of the reformer upper part 2 and the reformer lower part 3 as input meters, and the first reforming addition water. It has a first flow meter F1 for measuring the flow rate of the first reforming added water flowing through the water flow path 40, and sends a valve opening signal to the flow rate adjusting valve 64. The reformer upper part 2 is provided with a first thermometer T1 for measuring the temperature of the first reforming added water near the mixing chamber 44 and a second thermometer T2 for measuring the temperature of the reforming section 7. . In the reformer lower part 3, the third thermometer T3 for measuring the temperature of the first shift conversion section 21, the fourth thermometer T4 for measuring the temperature of the second shift conversion section 26, and the temperature of the selective oxidation section 36 are measured. A fifth thermometer T5 is provided.

The second reforming added water flow rate control section 72 is a first flow meter F1 for measuring the flow rate of the first reforming addition water flowing through the first reforming addition water passage 40 as an input instrument, and the second reforming addition water. A second flow meter F2 for measuring the flow rate of the second reforming additive water flowing through the water flow channel 45, a third flow meter F3 for measuring the flow rate of the reforming raw material flowing through the reforming raw material flow channel 50, and a flow rate adjusting valve. 6
5, the valve opening signal is sent to 5.

The first reforming additive water flow rate control unit 70 controls the temperatures of the upper part of the reformer 2 and the lower part of the reformer 3 by the first thermometer T1.
When measured by the fifth thermometer T5 and the temperature is lower than the preset temperature set in each part, the valve of the flow rate adjusting valve 64 is closed to reduce the first reformed additive water flow rate. Then, for example, the temperature of each part such as the first shift conversion part 21 is raised, and is maintained at the set temperature by the feedback control by the first reforming added water flow rate control part 70. Second reforming added water flow rate control unit 72
Is the amount of carbon in the reforming raw material to be reformed, for example, from the flow rate signal of the third flow meter F3 and the composition of the reforming raw material, and the reforming having a constant ratio to the calculated carbon amount. The amount of added water is calculated (hereinafter, the molar ratio of the reforming added water and the carbon in the reforming raw material is represented by "S / C" (Steam / Carbon)). Then, the second reformed added water flow rate control unit 72 subtracts the amount of the first reformed added water measured by the first flow meter F1 from the calculated amount of reformed added water to obtain the second reformed added water. The amount of water to be supplied as water is calculated, and a valve opening signal is sent to the flow rate adjusting valve 65 so that the flow rate of the second reforming additive water measured by the second flow meter F2 becomes the calculated amount of supplied water. To control.

According to the present embodiment, since the second reforming addition water flow rate control unit 72 is provided, the total flow rate of reforming addition water, that is, S / C is changed during the steady operation of the reformer. The flow rate ratio of the first reforming additive water and the second reforming additive water can be adjusted without the need. Therefore, the temperature of each part can be stably controlled by the first reformed added water flow rate control part 70. For example, when the temperature distribution of the first shift converter 21 shifts to the high temperature side for some reason, the first reformed added water flow rate control unit 70 and the second reformed added water flow rate control unit 72 are linked,
The flow rate adjusting valve 64 on the first reforming added water injection channel 66 and the second
By operating the flow rate adjusting valve 65 on the reforming added water injection flow channel 67 to appropriately reduce the flow rate of the second reforming added water and at the same time increase the flow rate of the first reforming added water, the first shift conversion unit 21 The temperature distribution of can be returned to an appropriate temperature distribution. Thus, the thermal efficiency of reforming can be improved by always maintaining the optimum S / C in each operating load.

Next, a third embodiment of the fuel reformer according to the present invention will be described. FIG. 7 is a vertical cross-sectional view of the fuel reformer according to the third embodiment. In FIG. 7, members or elements which are the same as or correspond to those in FIG. 1 are designated by the same reference numerals, and duplicate explanations are omitted.

In the figure, the inner cylinder 29 and the middle cylinder 30 are shown.
Is provided coaxially with the outer wall of the reformer lower portion 3 of the second shift conversion unit 26, and the inner cylindrical body 29 is provided on the center side and the intermediate cylindrical body 30 is provided on the peripheral side. The gas introduction flow path 31 is a space formed on the center side of the inner cylindrical body 29, and
An annular baffle plate 27 is provided at the end of the first metamorphicing unit 21 side of 9
The openings are connected. Second shift conversion catalyst packed bed 25
Is a space formed between the peripheral side of the inner cylindrical body 29 and the center side of the middle cylindrical body 30, and is filled with the second shift conversion catalyst.
The gas outlet passage 32 is provided with a circular baffle plate 27 and a second annular baffle plate 27, which are installed in the peripheral side of the middle cylindrical body 30 and the outer wall of the lower reformer 3, and in the gap between the first shift conversion section 21 and the second shift conversion section 26. It is a space formed by the bottom surface 39 of the metamorphic portion. The gas introduction flow path 31 and the second shift conversion catalyst packed layer 25 are communicated with each other by a lower end opening 33 as a first opening of the inner cylindrical body 29. The second shift conversion catalyst packed layer 25 and the gas outlet flow path 32 are formed by the upper end opening 2 serving as the second opening of the middle cylindrical body 30.
It is connected by 8.

In the second shift section 26 thus configured, the reformed gas exiting the first shift section 21 passes through the gas introduction flow path 31 in a downward flow to open the lower end of the inner cylindrical body 29. Part 3
3 and then passes upward through the second shift conversion catalyst-packed layer 25, and the reformed gas that exits the second shift catalyst-packed layer 25 is folded back at the upper end opening 28 of the middle cylinder 30 and moves downward. The gas flows in a counterflow through the gas outlet channel 32 and is guided to the selective oxidation section 36. The selective oxidation section 36 is provided with a cylindrical hollow section 36B at the center of the selective oxidation section 36, through which reformed gas cannot pass. When the cylindrical hollow portion 36B is provided, the catalyst filling amount and the temperature distribution of the selective oxidation portion 36 are optimized. Thus, the temperature distribution in the shift conversion section and the selective oxidation section of the fuel reformer according to the present embodiment can be optimized, and the performance of the reformer can be further improved. The operation method of the fuel reformer according to the present embodiment is the same as that of the first embodiment described above, and thus the description thereof is omitted.

Next, a fourth embodiment of the fuel reformer according to the present invention will be described. FIG. 8 is a vertical cross-sectional view of the fuel reformer according to the fourth embodiment. In FIG. 8, members or elements that are the same as or correspond to those in FIG. 1 are designated by the same reference numerals, and redundant description will be omitted. In the figure, the medium-low temperature unit 3 includes a first shift portion 21 in which a first shift catalyst is cylindrically filled, a second shift portion 26A in which a second shift catalyst is annularly filled, and a second shift portion 26A. A selective oxidation part 36A located in a coaxial cylindrical shape is provided along the outer circumference of the.

In the second shift section 26A, the low temperature unit 3
The inner cylindrical body 29A is provided coaxially with the outer wall of the inner cylindrical body 29A, and the inner cylindrical body 30A is provided coaxially with the outer wall of the middle and low temperature unit 3 and is provided on the outer peripheral side of the inner cylindrical body 29A. The catalyst packed layer 25A of the second shift conversion section 26A is an annular space in which the second shift catalyst is housed, and is formed by the outer peripheral surface of the inner cylindrical body 29A and the inner peripheral surface of the middle cylindrical body 30A. The annular baffle plate 27A includes a first shift portion 21 and a second shift portion 2
It is installed in a gap with 6A, and a gas dispersion plate 34A is provided at the center of the ring.

The gas introduction flow path 31A has a circular cylindrical baffle plate 27A and a middle cylindrical body 3 located inside the selective oxidation section 36A.
0A inner peripheral surface of the first conversion portion 21 side, and the inner cylindrical body 29
In the space formed by the outer peripheral surface of the first shift portion 21 side, the reformed gas that has passed through the first shift portion 21 is transferred to the second shift portion 2
6A is a flow path to be introduced. The gas outlet flow path 32A is provided with the inner peripheral surface of the middle cylindrical body 30A on the bottom surface 43 side, the second shift portion 26A.
70 for connecting the bottom surface 39 of the inner cylindrical body 29A, the inner peripheral surface of the inner cylindrical body 29A, and the facing portion of the first oxidization portion 21 of the selective oxidation portion 36A.
In the space formed by A, it is a flow path for introducing the reformed gas that has passed through the second shift conversion section 26A into the selective oxidation section 36A. The conduit 70A is connected to one end of the inner cylindrical body 29A,
The tubular body has a circular cross section or a rectangular cross section that passes through the middle cylindrical body 30A, and has a tube diameter that does not hinder the flow of the gas introduction flow path 31A. The conduit 70A has a second opening 28A provided on the gas introduction flow path 71A side. The first opening 33A is provided at one end of the inner cylindrical body 29 located on the bottom surface 39 side of the middle cylindrical body 30A. The selective oxidation air introduction port 58 is arranged in the vicinity of the first opening 33A, and is preferably arranged slightly inserted inside the first opening 33A. Since the inlet port 58 for the selective oxidation air is installed in the vicinity of the first opening 33A, the reformed gas transformed by the second shift conversion unit 26A and the selective oxidation air are appropriately mixed, Selective oxidation unit 36
The selective oxidation reaction at A effectively proceeds.

The selective oxidation section 36A has a selective oxidation catalyst packed layer 35A formed by the inner peripheral surface of the intermediate and low temperature unit 3 and the outer peripheral surface of the intermediate cylindrical body 30A, and further has a gas introduction flow passage 71A and gas derivation. A flow path 72A is provided. The gas introduction flow path 71A is a space formed by the inner peripheral surface of the middle-and-low temperature unit 3, the outer peripheral surface of the middle cylindrical body 30, and the annular baffle plate 27A, and selectively oxidizes the reformed gas that has passed through the second shift section 26A. Lead to the catalyst packed bed 35A. Gas dispersion plate 37A
For homogenizing the flow of gas,
It is provided in A. The gas outlet passage 72A includes the inner peripheral surface of the middle-low temperature unit 3, the outer peripheral surface of the middle cylindrical body 30A, the bottom surface 39 of the second shift section 26A, the bottom surface 43 of the middle-low temperature unit 3, and the reformed gas outlet pipe 55. In the space formed by the peripheral surface, the reformed gas that has passed through the selective oxidation catalyst packed layer 35A is guided to the reformed gas outlet pipe 55.

In the second shift conversion section 26A thus constructed, the reformed gas passing through the first shift conversion section 21 passes downward through the gas introduction passage 31A and the gas dispersion plate 34A,
Next, it passes through the catalyst packed bed 25A. Then, the reformed gas that has passed through the second shift conversion catalyst-packed layer 25A is discharged into the first opening 3
It turns back at 3 A, passes through the gas outlet passage 32 A in an upward flow, passes through the second opening 28 A, and passes through the gas inlet passage 71.
It is led to the selective oxidation part 36A via A. That is, the second
The reformed gas that has passed through the shift conversion section 26A is supplied to the gas introduction passage 71.
A through the gas dispersion plate 37A, then through the selective oxidation catalyst packed bed 35A in a downward flow, and further through the gas outlet passage 72A.
Is led to the outside of the system.

When the second shift conversion section 26A and the selective oxidation section 36A are concentrically arranged in this manner, the second shift conversion section 26A is located in the central portion where the amount of the reformed gas tends to increase. The reforming gas uniformly flows to the selective oxidization portion 36A located at the outer peripheral edge of the two-transition portion 26A, and the selective oxidation reaction proceeds uniformly. Therefore, the amount of the selective oxidation catalyst filled in the selective oxidation section 36A is optimized, and the temperature distribution is also optimized.

In the first to fourth embodiments described above, the reformer upper part 2 as the high temperature unit is arranged on the upper side, and the reformer lower part 3 as the middle and low temperature unit is arranged on the lower side. Although the reformer has been described, the present invention is not limited to this, and the fuel reformer can be used upside down.

In the first to fourth embodiments, an annular baffle plate 18 is provided in the gap between the upper part of the reformer 2 and the lower part of the reformer 3, and the bottom surface of the upper part of the reformer 2 is The case where the heat exchange part 24 between the reformed gas and the reforming added water is formed by the upper surface of the reformer lower part 3 and the connecting flow pipe 19 is shown, but the present invention is not limited to this. In short, it suffices that the first reforming addition water is evaporated and superheated, and at the same time, the optimum temperature distribution of each part can be achieved.

For example, the bottom surface of the first shift portion 21 and the top surface of the second shift portion 26 are connected by a connecting flow pipe, and an annular baffle plate is provided in the gap between the connecting portions, so that the first shift portion 21 You may provide the 2nd heat exchange part which exchanges heat between a reformed gas and a 1st reforming addition water with a bottom face, the upper surface of the 2nd shift conversion part 26, and a connection distribution pipe. Furthermore, the second shift unit 2
The bottom surface of 6 and the top surface of the selective oxidation portion 36 are connected by a connecting flow pipe, and an annular baffle plate is provided in the gap between the connection portions. The bottom surface of the second shift portion 26, the top surface of the selective oxidation portion 36, and It is also possible to provide a third heat exchanging section for exchanging heat between the reformed gas and the first reformed added water by the connecting flow pipe. In addition, when the third heat exchange section is provided, an inlet for the selective oxidation air may be installed inside the connection flow pipe that connects the bottom surface of the second shift conversion section 26 and the upper surface of the selective oxidation section 36. it can.

[0073]

EFFECTS OF THE INVENTION According to the fuel reformer of the present invention, a high temperature having a combustion chamber in which fuel burns and a reforming section provided on the outer peripheral surface side of the combustion chamber and annularly filled with a reforming catalyst. A unit and a shift section provided on the side connected to the high temperature unit, and a shift section filled with a shift catalyst in a tubular or annular shape;
Since it is provided on the side opposite to the side connected to the high temperature unit and has a structure having an intermediate and low temperature unit having a selective oxidation section filled with a selective oxidation catalyst in a tubular or annular shape, it has two units of high temperature and low temperature. The structure is largely divided into two, and the structure of the integrated fuel reformer can be simplified, and the manufacturing cost can be reduced and the thermal efficiency can be improved. Further, according to the fuel reformer of the present invention, the reformed gas that has passed through the reforming section of the high-temperature unit is connected to the connecting flow tube that supplies the shift section side of the low-temperature unit to the connecting flow tube. Since the container that integrally houses the high temperature unit and the medium and low temperature unit is provided, the occurrence of thermal stress can be significantly reduced, and the durability of the fuel reformer can be improved.

Further, according to the fuel reformer of the present invention, the reforming additive water channel formed in the gap between the outer wall of the high temperature unit and the medium and low temperature unit and the inner wall of the container, and the reforming raw material to the high temperature unit. If a configuration is provided in which the reforming raw material supply channel for supplying and the mixing chamber for connecting the reforming additive water channel and the reforming raw material supplying channel are provided, the reforming additive water channel is improved by heat exchange between the high temperature unit and the low temperature unit. Quality additive water is evaporated and overheated by the sensible heat of the reformed gas, and the high temperature superheated steam of the reformed additive water generated is used to preheat the fuel in the case of gaseous fuel and vaporize the fuel in the case of liquid fuel. be able to. Thus, the fuel reformer of the present invention can be applied to gas fuels such as city gas, LPG and anaerobic digestion gas, and to liquid fuels such as kerosene and naphtha.

Further, according to the fuel reformer of the present invention, the reforming raw material supply passage for supplying the reforming raw material to the high temperature unit and the reforming additive water directly to the high temperature unit without passing through the middle and low temperature unit. And a mixing chamber that connects the reforming-added water channel, the reforming raw material supply channel, and the second reforming-added water channel to each other.
The start-up time can be greatly shortened and the temperature control of each reaction part can be facilitated.

Further, according to the fuel reformer of the present invention, the medium-low temperature unit is provided on the high-temperature unit side, and the first shift conversion section is filled with the first shift catalyst in a tubular or annular shape, A second cylinder-shaped or annularly packed second metamorphic catalyst
If a configuration is provided in which a metamorphic portion having a metamorphic portion is provided, and the second metamorphic portion is positioned coaxially with the selective oxidization portion, the second metamorphic portion and the selective oxidization portion are concentrically arranged and reformed. The whole vessel becomes compact.

[Brief description of drawings]

FIG. 1 is a vertical sectional view showing a basic configuration of a first embodiment of the present invention.

FIG. 2 is a flow chart illustrating an operating procedure at the time of startup in the device of FIG.

FIG. 3 is a vertical sectional view for explaining a preheating state at the time of startup in the apparatus of FIG.

FIG. 4 is a vertical cross-sectional view illustrating a supply start state of a reforming raw material in the apparatus of FIG.

5 is a vertical cross-sectional view for explaining a supply start state of the first reforming additive water in the apparatus of FIG.

FIG. 6 is a configuration block diagram illustrating a second embodiment of the present invention.

FIG. 7 is a vertical cross-sectional view showing a third embodiment of the present invention.

FIG. 8 is a vertical cross-sectional view showing a fourth embodiment of the present invention.

[Explanation of symbols]

1 reformer 2 Upper part of reformer (high temperature unit) 3 Lower reformer (mid-low temperature unit) 4 burners 5 Combustion cylinder 6 Reforming catalyst packed bed 7 reforming section 8 reforming section inlet gas flow path 10 Combustion gas flow path 13 containers 14 Insulation 15 partitions 16 Reformed gas flow path 17 Top reformer bottom 18 baffle board 19 Corrugated expansion / contraction pipe (connecting distribution pipe) 20 First shift catalyst packed bed 21 First Metamorphosis Department 24 heat exchange section 25, 25A Second shift catalyst packed bed 26, 26A Second metamorphic part 28, 28A Middle cylinder upper end opening (second opening) 29, 29A inner cylinder 30, 30A Medium cylindrical body 31, 31A gas introduction flow path 32, 32A gas outlet channel 33, 33A Inner cylinder lower end opening (first opening) 35, 35A selective oxidation catalyst packed bed 36, 36A Selective oxidation part 40 First reforming water channel (reforming water channel) 44 mixing chamber 45 Second reforming addition water channel 50 Fuel flow path (reforming material supply path)

Claims (17)

[Claims] 1. A combustion chamber in which fuel burns, and a high temperature unit provided on the outer peripheral surface side of the combustion chamber and having a reforming section annularly filled with a reforming catalyst; a side connected to the high temperature unit. And a selective oxidization unit that is provided on the side opposite to the side connected to the high-temperature unit and that is provided with a selective oxidation catalyst that is tubular or annular and that is provided with a selective oxidation catalyst that is tubular or annular. And a reformed gas that has passed through the reforming section of the high temperature unit,
A fuel reformer, comprising: a connection flow pipe that is supplied to the shift section side of the low-temperature unit, and a container that integrally houses the high-temperature unit and the low-temperature unit that are connected by the connection flow pipe. vessel. 2. The fuel reformer according to claim 1, wherein:
A reforming additive water channel formed in a gap between an outer wall of the high temperature unit and the middle and low temperature unit and an inner wall of the container; and connected to the high temperature unit of the middle and low temperature unit of the reforming water adding channel. A reformer-added water inlet provided on the opposite side of the fuel reformer side; 3. The fuel reformer according to claim 2, wherein:
A fuel reformer further comprising: a reforming raw material supply passage for supplying a reforming raw material to the high temperature unit; and a mixing chamber for communicating the reforming additive water passage and the reforming raw material supply passage with each other. 4. The fuel reformer according to claim 2, wherein:
A reforming raw material supply path for supplying a reforming raw material to the high temperature unit; a second reforming addition water flow path for directly supplying the reforming addition water to the high temperature unit without passing through the middle and low temperature unit; And a mixing chamber that connects the reforming raw material supply passage and the second reforming added water passage to each other. 5. A baffle plate provided in a gap between a connecting portion between the high-temperature unit and the medium-low temperature unit; a heat exchange unit provided on a facing surface between the high-temperature unit and the medium-low temperature unit, 5. The fuel reformer according to any one of claims 2 to 4, further comprising: a heat exchange section that exchanges heat between a reformed gas sent from a unit to the low-temperature unit and the reforming additive water. vessel. 6. The fuel reformer according to claim 1, wherein the connection flow pipe has an elastic member that expands and contracts in the axial direction of the connection flow pipe. 7. The shift conversion section is provided on the high temperature unit side, and is provided on the side of the selective oxidation section and a first shift section filled with a first shift conversion catalyst in a tubular shape or an annular shape, and a tubular shape. Alternatively, the fuel reformer according to any one of claims 1 to 6, further comprising: a second shift conversion section in which a second shift conversion catalyst is annularly filled. 8. The second metamorphic portion further includes: an inner cylindrical body provided coaxially with an outer wall of the middle and low temperature unit; and an outer cylindrical side coaxial with the outer wall of the middle and low temperature unit. A middle cylindrical body provided; and an inner peripheral surface of the inner cylindrical body forms a gas introduction flow path for the reformed gas that has passed through the first shift portion; and an outer peripheral surface of the inner cylindrical body and the middle cylindrical body. The fuel according to claim 7, wherein the inner peripheral surface of the cylindrical body forms a catalyst packed layer of the second shift conversion section; and the outer peripheral surface of the middle cylindrical body and the inner peripheral surface of the low-temperature unit form a gas outlet passage. Reformer. 9. The first shift conversion section further comprises: a first communication section that connects the gas introduction flow path to the catalyst packed bed of the second shift conversion section and is provided on the side of the selective oxidation section of the inner cylindrical body. An opening; and a second opening provided on the side of the first shift section of the middle cylindrical body while connecting the catalyst packed layer of the second shift section and the gas outlet channel. 8. The fuel reformer according to item 8. 10. A baffle plate is provided in a gap between the shift conversion section and the selective oxidation section, and an introduction port for the selective oxidation air is arranged inside a central opening of the baffle plate. The fuel reformer according to claim 9. 11. The selective oxidization section is provided with a cylindrical hollow section arranged in the vicinity of the central section so as not to pass the reformed gas sent from the shift conversion section. The fuel reformer according to claim 10. 12. The medium-low temperature unit is provided on the high-temperature unit side, and comprises a first shift conversion section in which a first shift catalyst is filled in a tubular or annular shape and a second shift shift catalyst in a tubular or annular shape. A metamorphic part having a filled second metamorphic part;
The fuel reformer according to any one of claims 1 to 6, wherein the second shift conversion section is positioned coaxially with the selective oxidation section. 13. The second shift section is provided on an inner cylindrical body provided coaxially with an outer wall of the middle and low temperature unit, and on an outer peripheral side of the inner cylindrical body coaxial with an outer wall of the middle and low temperature unit. An inner cylindrical body provided with the catalyst; a catalyst packed layer of the second shift section provided in a space formed by an outer peripheral surface of the inner cylindrical body and an inner peripheral surface of the inner cylindrical body; A selective oxidation catalyst filling layer of the selective oxidation section, which is provided in a space formed by the outer peripheral surface of the body and the inner peripheral surface of the low-temperature unit; and an opposing section between the first shift conversion section and the second shift conversion section. A gas introduction flow path for allowing the reformed gas that has passed through the first shift conversion section to flow into the second shift conversion section; and a bottom surface side of the second shift conversion section and the first shift conversion of the selective oxidation section. Flow path for communicating with the part facing part, which is a gas discharge flow of the reformed gas that has passed through the second shift conversion part. A fuel reformer according to claim 12, comprising: 14. A baffle plate provided at an opposing portion of the first shift portion and the second shift portion; the gas introduction flow passage has an inner circumference of the baffle plate and the middle cylindrical body. The fuel reformer according to claim 13, which is formed by a surface and an outer peripheral surface of the inner cylindrical body. 15. The gas outlet channel is formed by a bottom surface of the middle cylindrical body, an inner peripheral surface of the inner cylindrical body, and a conduit connecting the inner peripheral surface of the inner cylindrical body and the selective oxidation section. The fuel reformer according to claim 13, wherein 16. The fuel reformer according to claim 1, further comprising a vacuum heat insulating layer provided on an outer circumference of the container. 17. A combustion chamber in which fuel burns, and a high temperature unit provided on the outer peripheral surface side of the combustion chamber and having a reforming section filled with a reforming catalyst; passing through the reforming section of the high temperature unit. A low-temperature unit having a shift section for transforming the reformed gas and a selective oxidation section for selectively oxidizing the reformed gas transformed in the shift section; And a reforming-added water flow path for supplying the reforming-added water to the high-temperature unit; and a second reforming for directly supplying the reforming-added water to the high-temperature unit without passing through the intermediate-low temperature unit. An additive water flow path; a reforming raw material supply path for supplying a reforming raw material to the high temperature unit; a reforming additive water flow path, the second reforming additive water flow path, and a mixing chamber for communicating the reforming raw material supply path with each other And; Pawn.