JP2009167059A - Reforming unit and fuel cell system - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a fuel cell system equipped with a reforming unit generating hydrogen gas using various raw materials. <P>SOLUTION: A heat exchanger tube 827 is formed in such a way as to pierce a CO conversion vessel 821 in a state in which its inner peripheral face communicates with the outside of the CO conversion vessel 821. Exhaust heat of a burner unit for reforming in a reformer after heating comes in contact with an outer surface of a CO converter 820 to heat the CO converter, and the exhaust heat also circulates in the heat exchanger tube 827 to heat the CO converter also from the inside, whereby a CO conversion reaction region, in which a CO conversion catalyst bed 822 of large volume requiring a high catalyst content is formed, is efficiently heated, and substantially uniform heating of the CO conversion reaction region can be achieved in a short period of time. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a reforming unit that generates a reformed gas from a liquid fuel and a hydrocarbon feed gas, and a fuel cell system including the reforming unit.

Conventionally, as a fuel cell system for generating hydrogen gas and generating electricity with a fuel cell, various configurations such as a configuration using a fuel gas such as city gas as a raw material and a configuration using a liquid fuel such as kerosene as a raw material have been known. (For example, refer to Patent Document 1 or Patent Document 2).
The one described in Patent Document 1 is a fuel reforming section heated by a combustion section. After desulfurization by a desulfurizer, the pressure is increased by a booster and is supplied from a hydrocarbon supply gas and water supply means. Hydrogen gas is generated by the purified water. The hydrogen gas is supplied to the anode electrode, and air is supplied from the oxygen-containing gas supply means to the cathode electrode to generate power.
In the device described in Patent Document 2, the liquid fuel desulfurized by the desulfurizer is supplied to the auxiliary tank so as not to be emptied, and the raw material is supplied from the auxiliary tank to the reformer. A configuration is adopted in which hydrogen gas is generated by reforming while being heated by a reformer, and is supplied to the fuel cell together with air to generate power.

By the way, the amount of heat when the raw material and water vapor are mixed and heated to reform the reformed gas containing hydrogen gas as a main component is the largest. In addition, for example, in the production of reformed gas supplied to a fuel cell that generates power using a polymer membrane, CO gas remaining in the reformed gas may damage the fuel cell. It is necessary to remove CO gas. In this CO removal, since the catalyst is used to react at a certain temperature, the reformer that generates the reformed gas and the CO remover that removes the remaining CO are integrated to improve the energy efficiency. The structure using the residual heat of the heating at the time of quality is also taken. In the fuel cell system, since energy efficiency is important, the generated high-temperature reformed gas is cooled to the temperature of the CO removal reaction by using the residual heat of heating at the time of reforming, or CO 2 In order to effectively use the heat generated by the removal reaction, a configuration is adopted in which water vapor is used for generating reformed gas by exchanging heat with water (for example, Patent Document 3 and Patent). Reference 4).
On the other hand, for example, in the home, the power consumption situation peaks from the evening to the middle of the night, and almost no power is used from late at night to the early morning. For this reason, the fuel cell system is configured not to operate during the day and to stop operation during a time period in which the power consumption is relatively low.
Therefore, when water used for heat exchange is circulated at the time of restarting, dew condensation may occur in a CO remover that is not sufficiently warmed, and the catalyst may be deactivated and sufficient CO removal may not be obtained. On the other hand, when water used for heat exchange is circulated as cooling water after the CO remover has been sufficiently warmed, other parts may be overheated and damaged.

JP 2006-12479 A JP 2003-151608 A JP 2002-356305 A JP 2002-216827 A

  As described above, in the conventional unit configuration, there is a risk that condensed water is generated in the CO remover during the supply of water vapor at the time of activation, and the catalytic activity is reduced.

  In view of these points, an object of the present invention is to provide a reforming unit and a fuel cell system that can generate hydrogen gas satisfactorily using various raw materials.

The reforming unit according to the present invention is a reforming unit that contains hydrogen gas (H ₂ ) by heating at least one of liquid fuel and hydrocarbon raw material gas with steam in a reforming catalyst in a heating device. A reformer that generates gas and a CO remover that removes residual carbon monoxide (CO) by bringing the reformed gas generated in the reformer into contact with a catalyst are accommodated in one housing. The CO remover has an accommodation space filled with the catalyst therein, and is in contact with the catalyst and the inlet through which the reformed gas flows and communicates with the accommodation space. A case body having an outlet through which the reformed gas flows out, and a heat exchange pipe provided through the case body in a state where an inner peripheral surface communicates with the outside of the case body. It is characterized by.
In the present invention, as a CO remover that removes CO remaining in the reformed gas in a housing that accommodates the reformer, the catalyst is filled in the accommodation space, and the reformed gas generated in the reformer is introduced. A heat exchange tube is formed through the case body having an inflow port and an outflow port for flowing out the reformed gas in contact with the catalyst so that the inner peripheral surface communicates with the outside of the case body.
As a result, the exhaust heat of the heating by the heating device when the reformed gas is generated in the reformer can be easily reduced to a processing temperature at which CO is removed from the outer surface of the case body of the CO remover and the inner surface of the heat exchange tube. Heating can be efficiently performed with the configuration.

And in this invention, it is preferable that the said heat exchange pipe | tube is set as the structure provided in the state in which the axial direction substantially followed the vertical direction.
In this invention, the axial direction of the heat exchange tube is provided in a state substantially along the vertical direction.
As a result, a state in which the exhaust heat outside the case body is efficiently circulated through the heat exchange pipe by convection is obtained, and the catalyst can be heated more efficiently.
Here, the state in which the axial direction is substantially along the vertical direction includes a configuration in which the heat is circulated so as to obtain a circulation of exhaust heat by convection, a spiral shape, or an axial direction inclined obliquely.

Moreover, in this invention, it is preferable that the said CO remover is set as the structure filled with the CO conversion catalyst which converts the said residual CO as said catalyst.
That is, in the configuration in which residual CO is removed by the CO conversion catalyst, the catalyst capacity is relatively large, and it takes time to heat the inside of the layer filled with the CO conversion catalyst. Thus, the configuration in which the CO shift catalyst is filled is preferable because it is necessary to improve the heat transfer efficiency to the inside of the layer by the heat exchange pipe and to heat it efficiently.

Furthermore, in the present invention, it is preferable that the CO remover is configured such that the catalyst is filled between the inflow port and the outflow port at a position away from the opening edge of the inflow port and the outflow port.
In the present invention, the catalyst is filled at a position that is located between the inlet and the outlet in the case body and is separated from the opening edge of the inlet and the outlet.
As a result, the reformed gas flowing in from the inflow port flows through the layer filled with the catalyst substantially uniformly and flows out from the outflow port, so that the contact efficiency between the reformed gas and the catalyst is improved, and reforming is performed. Residual CO in the gas is efficiently removed.

In the present invention, in the housing space of the case body, the reformed gas is provided between the diffusion region communicating with the inflow port, the convergence region communicating with the outflow port, and the diffusion region and the convergence region. And a reaction region filled with the catalyst so as to communicate with each other is preferably formed.
According to the present invention, the reaction region filled with the catalyst is defined in the housing space of the case body between the diffusion region communicating with the inflow port and the convergence region communicating with the outflow port.
As a result, the reformed gas flowing in from the inflow port is diffused in the diffusion region, flows substantially uniformly in the reaction region, flows into the converging region, converges to the outflow port, and flows out. Contact efficiency with the catalyst is improved, and residual CO in the reformed gas is efficiently removed.
Here, the diffusion region and the convergence region may be not only a simple space but also a region filled with alumina particles, for example.

A fuel cell system according to the present invention includes a reforming unit according to any one of claims 1 to 5, an oxygen-containing gas supply means for supplying an oxygen-containing gas, and a reformer generated by the reforming unit. And a fuel cell that generates electricity using the oxygen-containing gas supplied by the oxygen-containing gas and the oxygen-containing gas supply means.
In the present invention, the reformed gas produced by the reforming unit according to any one of claims 1 to 5 capable of producing a reformed gas containing hydrogen gas using various raw materials, and the oxygen-containing gas supply means Electricity is generated by the fuel cell using the supplied oxygen-containing gas.
As a result, the fuel cell can efficiently and stably generate power without being limited to the raw material, and is suitable for home use and can stably supply power.

[Configuration of fuel cell system]
Hereinafter, an embodiment according to the fuel cell system of the present invention will be described.
In the present embodiment, the configuration of the fuel cell system including the reforming unit of the present invention is illustrated. However, the configuration is not limited to the configuration used for the fuel cell system, and for example, as a hydrogen gas production apparatus, the reforming unit alone is used. It may be configured. In addition, a configuration using liquid fuel is illustrated as a raw material to be mixed with water vapor, but not limited to liquid fuel, for example, raw material gas is prepared by mixing water vapor using hydrocarbon raw material gas such as liquefied petroleum gas or city gas The present invention can also be applied to a configuration using various hydrocarbon raw materials, such as a configuration to perform. Moreover, although the system configuration for homes is illustrated, it can be applied to a relatively large system configuration used for, for example, an apartment house or various stores.
FIG. 1 is a block diagram showing a schematic configuration of a fuel cell system in the present embodiment.

(overall structure)
In FIG. 1, reference numeral 100 denotes a fuel cell system. The fuel cell system 100 is a system in which, for example, liquid fuel is used as a raw material to be reformed into a fuel gas containing hydrogen as a main component, and the fuel cell 200 generates power.
The fuel cell system 100 includes a liquid fuel storage tank 110 that stores liquid fuel 111, for example, kerosene. Here, the liquid fuel 111 is not limited to kerosene, and various liquid fuels such as light oil and naphtha can be targeted. A desulfurizer 130 is connected to the liquid fuel storage tank 110 via a fuel conveyance path 120 that includes a liquid fuel pump 121 and conveys the liquid fuel 111.
The desulfurizer 130 desulfurizes the liquid fuel 111 that is supplied from the liquid fuel storage tank 110 via the fuel transfer path 120 at, for example, about 300 [ml / hour]. Specifically, the sulfur compound contained in the liquid fuel 111 is adsorbed and removed by heating with an electric heater or the like by a liquid phase adsorption method. The desulfurizer 130 is connected to a reforming unit 300 that also functions as a reformer.

As will be described in detail later, the reforming unit 300 includes a vaporizer as a steam mixing means, a heat exchange device as a steam generating means, a reformer as a reformer, a CO converter and a CO that also function as a CO remover. A CO selective oxidizer as a remover is provided.
The vaporizer is connected to the desulfurizer 130, and the liquid fuel 111 that has been subjected to the desulfurization process is introduced into the vaporizer. Moreover, the heat exchanger is connected to the vaporizer. The vaporizer mixes and vaporizes the water vapor supplied from the heat exchange device with the liquid fuel 111 flowing out from the desulfurizer 130, and converts the vaporized liquid fuel as a raw material gas, which is a mixed gas of the liquid fuel 111 and the water vapor Generate.
A pure water tank 180 that stores pure water 181 is connected to the heat exchange device via a water supply path 183 having a transport pump 182, and pure water 181 is supplied from the pure water tank 180. Then, the heat exchange device cools the exhaust gas after heating the reformer with the supplied pure water 181, generates water vapor, and supplies the generated water vapor to the vaporizer. The pure water tank 180 may store pure water 181 that does not contain impurities such as distilled water, and may have a configuration in which, for example, tap water is purified and supplied as appropriate.
As will be described in detail later, the vaporizer and the heat exchange device exemplify a configuration that is integrated with the reformer, that is, a configuration that is integrated into the reformer unit 300 as an integral unit, but may be configured separately.

The reformer reforms the vaporized liquid fuel that has been desulfurized and mixed with water vapor into a hydrogen-rich fuel gas. The reformer includes a reformer catalyst such as a ruthenium (Ru) catalyst or a nickel (Ni) catalyst (not shown) and a burner unit 151 which is a burner as a heating device. The heating device is not limited to the burner unit 151, and various heating devices such as an electric heater can also be used.
The burner unit 151 is supplied with the liquid fuel 111 from the liquid fuel storage tank 110 via the branched fuel conveyance path 120 and also with the fuel gas discharged from the fuel cell 200 described later. The burner unit 151 burns the liquid fuel 111 and the fuel gas with the air supplied from the air supply blower 170, and the vaporized liquid fuel is steamed into the fuel gas that is a hydrogen-rich reformed gas by the heat generated by the combustion. Reform.
High-temperature exhaust gas generated by the combustion of the burner unit 151 is supplied to a heat exchange device, cooled by heat exchange with water, and exhausted into the outside air.

In addition, a CO converter and a CO selective oxidizer are connected in series to the reformer of the reforming unit 300.
The CO converter is filled with a CO conversion catalyst as a catalyst, and removes carbon monoxide by converting carbon monoxide (CO) contained in the hydrogen-rich fuel gas flowing out from the reformer.
The CO selective oxidizer is filled with a CO selective oxidation catalyst, oxidizes the remaining CO without being converted by the CO converter to carbon dioxide (CO ₂ ), and removes CO in the fuel gas.
Although the CO converter and the CO selective oxidizer will be described in detail later, the reformer and the reformer unit 300 are exemplified as an integral configuration, that is, an integral unit configuration as the reformer and reforming unit 300, For example, a configuration in which only the CO transformer is integrally assembled may be employed. In addition to these CO converter and CO selective oxidizer, a device for removing CO by adsorption is provided separately, or a device for adsorbing and removing CO in place of the CO converter and CO selective oxidizer is provided as a CO remover. You may do it.

The fuel cell 200 is connected to the CO selective oxidizer by piping or the like.
The fuel cell 200 reacts hydrogen and oxygen in the fuel gas to generate DC power. The fuel cell 200 is, for example, a solid polymer fuel cell, and includes a positive electrode 201, a negative electrode 202, and a polymer electrolyte membrane (not shown) disposed between the positive electrode 201 and the negative electrode 202. For example, air appropriately humidified by a humidifier (not shown) is supplied to the positive electrode 201 side, and hydrogen-rich fuel gas generated by the reforming unit 300 is supplied to the negative electrode 202 side. Then, hydrogen (fuel gas) and oxygen in the air react to generate water (pure water 181), and DC power is generated between the positive electrode 201 and the negative electrode 202.
The fuel gas supplied from the reforming unit 300 may be appropriately humidified and supplied via a humidifier as necessary. Further, the humidifier can be used in various forms such as being installed independently as a system configuration or a unit configuration built in the fuel cell 200.
The negative electrode 202 side is connected to the burner unit 151 of the reformer as described above, and surplus hydrogen is supplied as fuel for the burner unit 151. A separator 185 is connected to the positive electrode 201 side. The separator 185 is supplied with air used for the reaction from the positive electrode 201 side, and is separated into air for the gas phase and water (pure water 181) for the liquid phase. The separated air is exhausted to the outside air. The separator 185 is connected to a pure water tank 180 and supplies the separated water (pure water 181) to the pure water tank 180.

The fuel cell 200 is provided with a cooling device 187. The cooling device 187 is provided with a heat recovery unit 187A attached to the fuel cell 200. A pure water tank 180 is connected to the heat recovery unit 187A via a circulation path 187D including a pump 187B and a heat exchanger 187C.
The circulation path 187D circulates the pure water 181 between the heat recovery unit 187A and the pure water tank 180 by driving the pump 187B, cools the fuel cell 200 that generates heat accompanying power generation, and recovers heat.
The heat exchanger 187C exchanges heat with the pure water 181 that has been circulated and recovered heat by the heat recovery unit 187A, for example, tap water. The tap water warmed by this heat exchange is directly supplied to other facilities such as a bath for effective use. In addition to heat exchange with tap water, power generation from heat obtained by heat exchange may be used effectively for other facilities.
The heat exchanger 187C is not limited to a configuration in which tap water is directly introduced to exchange heat, but, for example, tap water in which heat is exchanged with air flowing from the positive electrode 201 of the fuel cell 200 to the separator 185 with a heat exchange device (not shown). A configuration may be employed in which water exchanges heat with pure water 181.

The fuel cell system 100 includes a control device (not shown) that controls the operation of the entire system.
This control device controls the flow rate of the liquid fuel 111, controls the power supplied to the electric heater, which is the heating condition of the heating means of the desulfurizer 130, controls the combustion of the burner unit 151 of the reformer, and generates steam with the heat exchange device. For this purpose, supply amount control, temperature management, power generation amount management, and the like of pure water 181 are performed.

(Reforming unit)
Next, the configuration of the reforming unit 300 in the fuel cell system 100 described above will be described in detail.
FIG. 2 is a side sectional view showing a schematic configuration of the reforming unit. FIG. 3 is a side cross-sectional view showing a schematic configuration in the reforming exterior case of the reforming unit of the reforming unit. FIG. 4 is a bottom view showing the reforming section. FIG. 5 is a side sectional view showing a schematic configuration of a combustion chamber portion of the reforming portion. FIG. 6 is a side cross-sectional view showing the rectifying pipe. FIG. 7 is a plan view showing the retaining ring portion attached to the outer cylindrical body. FIG. 8 is a side view showing the heat exchange device. FIG. 9 is a side cross-sectional view showing the piping outer case. FIG. 10 is a plan cross-sectional view showing a pipe exterior case. FIG. 11 is a plan view with a part cut away showing a piping state in a piping portion of the unit main body. FIG. 12 is a side sectional view showing the CO removal exterior case. FIG. 13 is a side view showing the CO transformer. FIG. 14 is a front view with a part cut away showing the CO transformer. FIG. 15 is a plan view showing a CO transformer. FIG. 16 is a side view showing a CO selective oxidizer. FIG. 17 is a front view of the CO selective oxidizer with a part cut away. FIG. 18 is a plan view showing a CO selective oxidizer. FIG. 19 is a plan view showing a partition plate of a CO selective oxidizer. Note that FIGS. 2 to 4 and FIG. 11 are shown with some piping omitted for convenience of explanation. Moreover, FIG. 11 shows the downward side in the vertical direction from the support pedestal part of the reformed exterior case for convenience of explanation.

As described above, the reforming unit 300 has an integrated configuration including a vaporizer, a reformer, a CO converter, a CO selective oxidizer, and a heat exchange device.
As shown in FIG. 2, the reforming unit 300 includes a unit main body portion 400 and a heat insulating portion 500 that covers the unit main body portion 400. The unit main body 400 includes a reforming unit 600, a piping unit 700, and a CO removing unit 800. And the unit main-body part 400 is the reforming part 600 via the piping part 700 in the upper direction with respect to the CO removal part 800 mounted and fixed to the bottom part of the case body which is not shown in figure which accommodates the fuel cell system 100. Are integrally connected.

The reforming unit 600 includes a reformed exterior case 610. The modified exterior case 610 includes a lower case 611 having an upper surface opened, an upper case 612 that covers the upper surface of the lower case 611 and is integrally attached, and a support base that is integrally attached to substantially cover the lower surface of the lower case 611. Part 613.
The lower case 611 is formed, for example, in a substantially cylindrical shape using a steel plate or the like, and more specifically, is formed using a sheet-wound tube made of a steel plate that is a tube material. And the upper connection flange 611A which protrudes in series in a bowl shape toward the inner side is provided at the upper end which is one end in the axial direction of the lower case 611. The upper connecting flange 611A is formed in a shape in which an outer peripheral edge is bent into a substantially cylindrical shape and joined by welding, for example. That is, it is a so-called flange-up shape. In addition, a lower screw hole 611B into which a screw as a connection attachment member (not shown) is penetrated and the support pedestal portion 613 is attached integrally is provided at the lower end which is the other end in the axial direction of the lower case 611.
The upper case 612 is formed of, for example, a steel plate or the like in a substantially cylindrical shape having a diameter smaller than that of the lower case 611, and more specifically, is formed by using a sheet-wound tube of a steel plate that is a tube material. A top plate flange 612A is provided at the upper end, which is one end in the axial direction of the upper case 612, and projects in a bowl shape toward the inside. A cylindrical burner connecting portion 612B is integrally provided on the inner peripheral edge of the top plate flange 612A by welding or the like. Furthermore, a burner connection flange 612C is provided at the upper end, which is one end in the axial direction of the burner connection portion 612B, and protrudes in series in a bowl shape toward the outside. A bolt insertion hole 612E through which, for example, a mounting bolt 612D as a burner mounting member is inserted is formed in the burner connecting flange 612C. And the lower end outer peripheral surface which becomes the other end in the axial direction of the upper case 612 is integrally connected to the inner peripheral edge of the upper connecting flange 611A of the lower case 611 bent in a substantially cylindrical shape by welding or the like. Yes. That is, the joint portion between the upper connecting flange 611A and the upper case 612 of the lower case 611 and the joint portion of the top plate flange 612A of the upper case 612 have a so-called flange-up shape.
As shown in FIGS. 2 and 3, the support pedestal 613 is formed in a substantially bottomed cylindrical shape with, for example, a steel plate so as to substantially close the lower end in the axial direction of the lower case 611. The support pedestal portion 613 has a bottom joint portion 613A that is formed in a cylindrical shape whose outer dimension is substantially the same as the inner diameter dimension of the lower case 611. A partition bottom portion 613B that protrudes inward toward the inside is provided in series at a lower end that is one end in the axial direction of the bottom joint portion 613A. The bottom joint portion 613A is provided with an attachment female screw portion 613C that is screwed in correspondence with the lower screw hole 611B of the lower case 611. It is preferable that the joint portion between the bottom joint portion 613A and the lower case 611 be sealed with, for example, a heat-resistant caulking material. The support pedestal 613 is integrally connected to the other end in the axial direction of the lower case 611 so that a part of the axial direction protrudes from the other end of the lower case 611. A substantially circular heat exchange hole 613D is formed in the partition bottom 613B of the support pedestal 613. Further, as shown in FIG. 4, the support base 613 is provided with a plurality of, for example, three column mounting screw holes 613 </ b> E in the partition bottom 613 </ b> B.

In the reforming exterior case 610, as shown in FIGS. 2 and 3, a reformer 620 and a heat exchanging device 640 as a steam generating means are disposed.
The reformer 620 includes a combustion chamber 621, a burner unit 151, and a reforming vessel 622.

As shown in FIGS. 2 and 5, the combustion chamber portion 621 includes a combustion cylinder portion 621 </ b> A that is formed of a steel plate or the like and has a cylindrical shape slightly smaller in diameter than the burner coupling portion 612 </ b> B of the upper case 612. . The combustion cylinder portion 621A is provided with a positioning dowel 621B that bulges inward at a predetermined position on the upper end side that is one end in the axial direction. Also, a support flange 621C that protrudes outward in a bowl shape is provided at the upper end, which is one end in the axial direction, of the combustion cylinder portion 621A, like the burner connection flange 612C. The support flange 621C is formed with a bolt insertion hole 612E through which the mounting bolt 612D is inserted, similarly to the burner connection flange 612C.
In addition, a flame rectification unit 621F is integrally disposed in the combustion chamber unit 621. The flame rectifying portion 621F has an attachment cylindrical portion 621F1 that has an outer diameter that is substantially the same as the inner diameter of the combustion cylinder portion 621A and is positioned on the upper end side of the combustion cylinder portion 621A and attached integrally by welding or the like. . Further, a funnel-shaped rectifying cylinder portion 621F2 having a diameter gradually decreasing in accordance with the distal end side is provided in series at the lower end, which is one end in the axial direction of the mounting cylindrical portion 621F1. The flame rectifying unit 621F is positioned by a positioning dowel 621B of the combustion cylinder 621A, and the mounting cylinder 621F1 is integrally attached to a predetermined position on the inner peripheral side of the combustion cylinder 621A by welding or the like.

For example, as shown in FIG. 2, the burner unit 151 burns a burner main body portion 651 that is cast, a liquid fuel 111 that is a fuel, and an off gas that is a fuel gas discharged from the negative electrode 202 of the fuel cell 200. And a burner section 652 having a plurality of combustion ports (not shown) for generating a flame.
The burner body 651 has a first air introduction part 651A in which air supplied from the air supply blower 170 is introduced as primary air, and a second air introduction part (not shown) in which supplied air is introduced as secondary air. And an off-gas introduction part 651B for introducing and burning off-gas. Further, a liquid fuel supply pipe 651C to which the liquid fuel 111 is supplied is connected to the first air introduction part 651A, and the supplied liquid fuel 111 is mixed with the primary air and supplied to the burner main body part 651 to be sufficiently vaporized. And burned. As a connection structure of the liquid fuel supply pipe 651C, it is preferable that the liquid fuel supply pipe 651C is connected to a bent portion of the first air introduction portion 651A formed to be bent in a substantially L shape. Further, the burner body 651 is provided with a preheating electric heater 651D for evaporating the liquid fuel 111 and an ignition electrode (not shown). Note that the preheating electric heater 651D is used only at the time of start-up, and once combustion is started, heat for evaporating the liquid fuel 111 is obtained from the surroundings, so that the energization to the preheating electric heater 651D is turned off. The
The burner unit 151 is supported such that the mounting flange 651E provided in a bowl shape on the burner main body 651 further overlaps the burner connecting flange 612C of the overlapping upper case 612 and the support flange 621C of the combustion chamber 621, A mounting bolt 612D is screwed. In this state, the upper end portion of the upper case 612 of the reformed exterior case 610 is closed, and the burner unit 151 is integrally provided.
The attached state of the burner unit 151 corresponds substantially to the upper end of the reforming vessel 622 while the lower end of the burner unit 652 is substantially located within the rectifying cylinder 621F2 of the flame rectifying unit 621F of the combustion chamber 621. Is in position.

As shown in FIGS. 2 and 3, the reforming container 622 has an inner cylindrical body 622A and an outer cylindrical body 622B having different diameters and substantially matching the central axis, and these inner cylindrical body 622A and outer cylindrical body 622A. It is formed in a substantially annular cylindrical shape that partitions and forms a reforming chamber 622 </ b> C having a substantially annular space between the shaped bodies 622 </ b> B, and is disposed in a state of being located in the upper case 612.
Further, the reforming vessel 622 is formed on a reforming vessel that is formed in a substantially ring shape and partitions the reforming chamber 622C on the upper end side that is one end side in the axial direction of the inner cylindrical body 622A and the outer cylindrical body 622B. A closing plate 622D is provided. Further, the reforming vessel 622 has a substantially disc-shaped modification whose peripheral edge fits and closes the lower end portion of the outer cylindrical body 622B on the lower end side which is the other end side in the axial direction of the outer cylindrical body 622B. A quality container lower closing plate 622E is provided.
The reforming container lower closing plate 622E is fitted with the lower end portion of the inner cylindrical body 622A at the periphery, and the reforming container lower closing plate 622E closes the lower end portion of the inner cylindrical body 622A. Partition plates 622F are provided integrally and concentrically.
The reforming chamber 622C defined by the reforming vessel 622 is filled with a reforming catalyst to form a reforming catalyst layer 622G. In addition, as the reforming catalyst layer 622G, a packed bed may be provided on the lower end side in the axial direction so that alumina particles are filled and the steam mixed gas flows through the reforming catalyst layer 622G substantially uniformly.

Further, the reforming vessel 622 is attached by closing the inner peripheral side of the lower end portion of the inner cylindrical body 622A, and defines a heating chamber 622H containing the combustion chamber portion 621 on the inner peripheral side of the reforming vessel 622. A heating chamber partition plate 622I is provided. In the heating chamber partition plate 622I, a connecting screw portion 622J having a male screw 622J1 provided on the outer peripheral surface of the tip portion is integrally protruded at a substantially center on the upper surface side which is one surface side.
Further, as shown in FIG. 2, a refractory heat insulating material 622K formed in a flat ring shape is provided on the upper surface side of the heating chamber partition plate 622I so as to fit the connecting screw portion. The refractory heat insulating material 622K is arranged in a state in which the male screw 622J1 of the connecting screw portion 622J protrudes, that is, the temperature on the lower surface side of the heating chamber partition plate 622I is set to a temperature that does not exceed a predetermined temperature, for example, about 500 ° C. Even in the state where the refractory heat insulating material 622K is disposed, the connecting screw portion 622J is formed in a state where the male screw 622J1 of the connecting screw portion 622J protrudes.
Further, a rectifying pipe 622L is connected to the connecting screw portion 622J. As shown in FIGS. 2 and 6, the rectifying pipe 622L is formed in a substantially bottomed cylindrical shape in which one end in the axial direction is substantially closed by a closing plate 622L1. The rectifying pipe 622L has a length dimension in which the axial direction substantially corresponds to the reforming catalyst layer 622G, the outer diameter is smaller than the inner diameter of the combustion cylinder part 621A of the combustion chamber part 621, and the outer peripheral surface of the combustion cylinder part 621A. It is formed so as to face the inner peripheral surface with a predetermined gap. A male screw insertion hole 622L2 into which a male screw 622J1 of the connecting screw portion 622J is fitted and a nut (not shown) is screwed is provided at the approximate center of the closing plate 622L1 of the rectifying tube 622L. Further, the rectifying pipe 622L is integrally provided with a turbulent flow portion 622L3 arranged on the outer peripheral surface in a spiral shape with respect to the central axis by a long steel material. The turbulent flow part 622L3 does not contact the inner peripheral surface of the combustion cylinder part 621A, and the combustion gas of the burner unit 151 that circulates between the outer peripheral surface of the rectifying pipe 622L and the inner peripheral surface of the combustion cylinder part 621A. Is formed so as to circulate spirally with respect to the central axis. 6 shows the turbulent flow portion 622L3 formed of one elongated steel material for convenience of explanation. However, the outer peripheral surface of the rectifying tube 622L may be formed into a plurality of turbulent portions 622L3, for example, so that the cross section has a wave shape. It can be formed in various shapes, such as projecting from or extending in a rib shape, or a combination of these with a long steel material.
The closing plate 622L1 of the rectifying pipe 622L is described as an example of a plate shape in which the combustion gas of the burner unit 151 cannot flow. For example, a plate having a hole through which a part of the combustion gas can flow, mesh Various forms such as a shape can be used. That is, the closing plate 622L1 adds a flow resistance to the combustion gas that tends to flow from the burner unit 151 side to the other end side in the rectifying pipe 622L, and at least a part of the combustion gas from the burner unit 151 is rectified pipe. It functions to flow between the outer peripheral side of 622L and the inner peripheral side of the combustion cylinder portion 621A. Therefore, it is preferable that the gas is completely closed. However, the combustion gas may flow depending on the flow resistance between the rectifying pipe 622L and the combustion cylinder 621A, the degree of heating of the rectifying pipe 622L and the combustion cylinder 621A, and the like. You may make it provide the hole etc. which one part can pass through the obstruction | occlusion board 622L1.
The combustion cylinder portion 621A and the rectifying pipe 622L allow the combustion gas of the burner unit 151 to flow between the outer peripheral surface of the rectifying pipe 622L and the inner peripheral surface of the combustion cylinder portion 621A from within the rectifying pipe 622L. Further, the combustion gas flows between the outer peripheral surface of the outer cylindrical body 622B of the reforming vessel 622B and the upper case 612 from between the outer peripheral surface of the combustion cylindrical portion 621A and the inner peripheral surface of the inner cylindrical body 622A of the reforming vessel 622. Between the inner surface of the lower case 611 and the upper surface of the support pedestal 613.

Further, as shown in FIGS. 2 and 3, a ring-shaped holding ring portion 622 </ b> M is fitted and fixed to the reforming container 622 at the upper end side in the axial direction of the outer cylindrical body 622 </ b> B. As shown in FIG. 7, the holding ring portion 622 </ b> M has a plurality of holding piece portions 622 </ b> M <b> 2 projecting in a tongue-like shape toward the inner peripheral side and having fitting insertion holding holes 622 </ b> M <b> 1. Has been.
Further, as shown in FIGS. 2, 3 and 7, the reforming vessel 622 has a substantially equal interval in the circumferential direction, for example, three locations and a predetermined interval in the axial direction on the outer peripheral surface of the outer cylindrical body 622 </ b> B. For example, positioning protrusions 622N are provided at two locations. These positioning projections 622N are provided in a shape that positions the tip of the positioning container 622 and the upper case 612 so as to be positioned substantially coaxially with their tips substantially in contact with the inner surface of the upper case 612, respectively. The positioning protrusion 622N is formed, for example, such that a steel plate is bent to form a substantially triangular shape in plan view in the vertical direction, that is, the combustion gas of the burner unit 151 in the vertical direction can flow. Furthermore, the reforming vessel 622 is provided with three sensor protection pipes 622O provided with temperature sensors (not shown) for detecting the temperature of the reforming catalyst layer 622G in the axial direction.

The reforming vessel 622 is provided with a circulation part 622P. The circulation unit 622P is configured to flow the raw material gas into the reforming vessel 622 and to flow out, that is, recover the generated reformed gas. As shown in FIGS. 2 and 3, the circulation part 622P has a supply pipe 622Q1 and a return pipe 622Q2 that is fitted into the supply pipe 622Q1 substantially coaxially, and is in the axial direction of the reforming vessel 622. A plurality of double pipe portions 622Q having a double pipe structure that is connected to the lower end of the lower case 611 and located in the lower case 611.
The supply pipe 622Q1 has an upper end that is one end in the axial direction, in the vicinity of the outer peripheral edge of the reforming vessel lower closing plate 622E of the reforming vessel 622, that is, at a position corresponding to the reforming catalyst layer 622G at an approximately equal interval in the circumferential direction. A plurality of circumferential sides are arranged in a state communicating with the reforming catalyst layer 622G.
The return pipe 622Q2 opens at the upper end side, which is one end in the axial direction, through the reforming catalyst layer 622G so that the reformed gas can flow into the upper end side, which is one end side in the axial direction in the reforming chamber 622C. The retaining ring portion 622M of the quality container 622 is inserted into and fixed to the fitting insertion holding hole 622M1, and the other end in the axial direction is disposed so as to protrude from the supply pipe 622Q1 by a predetermined amount.
Thus, the double pipe portion 622Q has one end in the axial direction in the vicinity of the outer peripheral edge of the reforming vessel lower closing plate 622E of the reforming vessel 622, that is, at a substantially equal interval in the circumferential direction at a position corresponding to the reforming catalyst layer 622G. Multiple connections to 7 shows a configuration in which 16 return pipes 622Q2 of the double pipe portion 622Q are connected and held for convenience of explanation, the present invention is not limited to 16. Further, it is preferable that the double pipe portion 622Q is provided with 3 or more and 32 or less.
When the number of the double pipe portions 622Q is two or less, the heat exchange rate is greatly reduced, and the inflowing raw material gas is drifted, so that a good contact efficiency with the reforming catalyst cannot be obtained. There is a risk that it cannot be generated. On the other hand, when the number of the double pipe portions 622Q is 33 or more, the structure becomes complicated as the small reforming unit 300 used particularly for home use, and the productivity may be lowered. Accordingly, the number of the double pipe portions 622Q is preferably 3 or more and 32 or less.

Further, as shown in FIGS. 2 and 3, a substantially disc-shaped flow disc portion 622R1 is provided at the lower end of the double pipe portion 622Q which is the other end in the axial direction of the supply pipe 622Q1. That is, a plurality of supply pipes 622Q1 are connected to the vicinity of the outer peripheral edge of the circulation disk portion 622R1 so as to be substantially equally spaced in the circumferential direction.
Furthermore, a substantially disc-shaped flow partitioning part 622R2 is provided at the lower end, which is the other end in the axial direction, of the return pipe 622Q2 of the double pipe part 622Q. The circulation partition 622R2 is formed in a substantially cylindrical shape having a peripheral edge that fits the outer periphery of the flow disk part 622R1 in a substantially airtight manner, and a substantially center is formed in a substantially cylindrical shape on the side opposite to the peripheral edge. In addition, a partition blocking plate 622R3 that closes substantially the center is integrally provided in the distribution partition portion 622R2.
Then, by these flow disk part 622R1, flow partition part 622R2 and partition closing plate 622R3, a substantially columnar shape communicating with the reforming catalyst layer 622G via the outer peripheral surface of the return pipe 622Q2 and the inner peripheral surface of the supply pipe 622Q1. A source gas supply unit 622R that partitions the space is provided.

Furthermore, a raw material gas supply pipe 622S that is connected to the internal space of the raw material gas supply unit 622R and supplies the steam mixed gas to the raw material gas supply unit 622R is connected to the partition closing plate 622R3. Yes.
The source gas supply pipe 622S has a vaporizer 630 as a water vapor mixing means, as shown in FIGS. The vaporizer 630 includes a liquid fuel connection portion 631 to which a desulfurized fuel supply pipe 740 (see FIG. 11) to which the liquid fuel 111 desulfurized by the desulfurizer 130 is supplied, a CO converter 820 to be described in detail, and Generated by the first water vapor connection portion 632A to which a first water vapor supply pipe (not shown) to which water vapor generated by cooling of the CO selective oxidizer 830 (see FIGS. 2 and 11) is supplied and the heat exchange device 640 are supplied. A steam connection section 632 having a second steam connection section 632B to which a not-shown second steam supply pipe (not shown) is supplied is formed in a substantially T-tube shape. That is, the vaporizer 630 causes the supplied liquid fuel 111 and water vapor to merge and mix to generate vaporized liquid fuel.
Furthermore, the raw material return pipe 622S is connected between the vaporizer 630 and one end serving as a connection position with the raw material gas supply section 622R, and the raw material return pipe 730 (see FIG. 11) is connected. 622S2 is provided. This raw material return section 622S2 is returned by the operation of a safety valve (not shown) provided outside the reforming unit 300 in the raw material return pipe 730, or returned vaporized liquid fuel or reformed gas, or generated vaporized liquid. The fuel flows out of the reforming unit 300 through the raw material return pipe 730. That is, the safety valve is normally closed and there is no flow of the raw material return pipe 730. For example, when the internal pressure in the raw material gas supply unit 622R reaches a predetermined value or more due to the blocking of the reforming catalyst layer 622G, the raw material gas supply unit An operation is performed to cause gas phase components such as vaporized liquid fuel gas and reformed gas in 622R to flow out of the reforming unit 300 from the source gas supply pipe 622S through the source return pipe 730.
The raw material return pipe 730 is not only a gas phase component to be discharged, but also a liquid phase such as condensed water of a liquid phase that is pure water 181 that has not been sufficiently heated at the beginning of startup or the like to become water vapor. It is a structure that can also flow out. In addition, the component condensed from the gas phase component by the outflow of the gas phase component to the outside of the reforming unit 300 such as the vaporized liquid fuel to be discharged may be recovered in a receiving portion provided separately. The receiving part is provided with a window in which the liquid fuel 111, which is a desulfurized fuel that has been collected and condensed, water, etc. can be visually observed, or the fact that it has been recovered by a sensor or the like, and the safety valve functions. It is good to be able to detect what happened. Note that the receiving portion may be configured to store not only the liquid phase component that is a condensed component of the gas phase component but also the gas phase component itself.

  Here, the relationship between the inner diameter A of the liquid fuel connection portion 631 of the vaporizer 630 of the raw material gas supply pipe 622S and the inner diameter B of the flow path from the raw material gas supply pipe 622S to the raw material return pipe 730 returned by the safety valve is B It is preferable to set / A = 1-15. Here, if the relationship of B / A <1 is satisfied, the pressure in the source gas supply unit 622R may not be satisfactorily reduced. On the other hand, even if the relationship of B / A> 15 is satisfied, it is not possible to reduce the outflow resistance of the vaporized liquid fuel and the like, and there is a possibility that the apparatus becomes large. For this reason, it is preferable to set B / A = 1-15. The relationship between the cross-sectional area C of the liquid fuel connection portion 631 and the cross-sectional area D of the flow path from the raw material gas supply pipe 622S to the raw material return pipe 730 is preferably set to D / C = 1 to 220. Similarly, the relationship between the cross-sectional areas is preferably set to D / C = 1 to 220 from the viewpoint of outflow resistance of vaporized liquid fuel and the like, and from the viewpoint of increasing the size of the apparatus. In the household fuel cell system 100 in this embodiment, B / A = 2.0 and D / C = 4.0 are set.

Further, as shown in FIGS. 2 and 3, the circulation partition 622R2 constituting the source gas supply unit 622R is formed in a substantially cylindrical shape that fits the outer periphery of the circulation partition 622R2, and is distributed substantially in the center. A partition cylindrical portion 622T1 formed in a substantially cylindrical shape that fits an inner peripheral edge formed in a substantially cylindrical shape of the partition portion 622R2 is provided. The partition cylindrical portion 622T1 is laminated on the partition bottom portion 613B of the support base portion 613 of the reformed exterior case 610 and attached to the support base portion 613 by welding or the like so as to close the inner peripheral edge of the partition bottom portion 613B. It is done.
The partition tubular portion 622T1 and the flow partition 622R2 define a substantially annular space communicating with the return pipe 622Q2, and reformed by the reforming catalyst layer 622G and generated through the return pipe 622Q2. A reformed gas outflow portion 622T into which gas is introduced is provided.
Further, the partition tubular portion 622T1 is positioned closer to the center side than the inner peripheral edge of the partition bottom portion 613B of the support pedestal 613, and the reformed gas discharge that communicates the reformed gas outflow portion 622T to the outside of the partition tubular portion 622T1. A tube portion 622T2 is provided.

The heat exchange device 640 has a double tube structure. As shown in FIGS. 2, 3, and 8, the heat exchange device 640 includes a reformed water inner pipe 641 through which pure water 181 is circulated, and an outside of the exhaust air passage into which the reformed water inner pipe 641 is inserted. A tube 642.
The exhaust air duct outer pipe 642 has one end in the axial direction opened, the other end in the axial direction is fitted and fixed to the heat exchange hole 613D of the support base 613 by welding or the like, and has a predetermined diameter smaller than the inner diameter of the lower case 611. It is formed in a spiral shape with a curvature radius of. That is, the exhaust air duct outer pipe 642 is disposed in a state where the upper surface side and the lower surface side of the support pedestal portion 613 communicate with each other, and the combustion gas burned in the burner unit 151 that circulates through the heating chamber 622H of the reformer 620. However, it is the state which distribute | circulates from the upper surface side of the support base part 613 to the lower surface side of the support base part 613 via the inside of the exhaust air path outer tube | pipe 642. As shown in FIGS. 2 and 3, the exhaust air duct outer tube 642 is provided with a spacer 642 </ b> A formed in a substantially drum shape, for example, with a steel plate, and maintains a spiral shape at a predetermined interval.
The reformed water inner pipe 641 has one end side in the axial direction extending from one end where the exhaust air path outer pipe 642 opens, and the other end side in the axial direction is connected to the support base 613 in addition to the exhaust air path outer pipe 642. It extends from the end and is fitted and disposed in the exhaust air duct outer tube 642. Although details will be described later, in terms of heat exchange efficiency between pure water 181 and the combustion gas, the reformed water inner pipe 641 is substantially coaxially fitted into the exhaust air duct outer pipe 642 and disposed. However, a configuration in which a separate member such as a pipe or a spacer for positioning on the same axis is provided may be used. Although the details of the reformed water pipe 641 will be described later, one end side in the axial direction, which is an end corresponding to the outflow side of water vapor generated by heat exchange, passes through the support pedestal 613, and the support pedestal 613. It is arrange | positioned in the state extended to the lower surface side. Note that the penetration portion of the support pedestal 613 of the reformed water inner pipe 641, that is, the penetration portion of the support pedestal 613 of a steam connection pipe (not shown) connected to the reformed water inner pipe 641, is welded or brazed substantially airtightly. It is sealed by etc. Also, the reformed water supply pipe 720 to which pure water 181 as reformed water is supplied to the other end side in the axial direction extending to the lower surface side of the support pedestal 613 in the reformed water inner pipe 641 (FIG. 11). The pure water 181 is circulated in the reformed water inner pipe 641. The other end, which is the tip of the reformed water inner pipe 641 extending to the lower surface side of the support pedestal 613, is the second water vapor in the vaporizer 630 of the source gas supply pipe 622S provided in the reformer 620. A second water vapor supply pipe (not shown) connected to the connection portion 632B is connected. That is, the reformed water inner pipe 641 generates steam by exchanging heat of the pure water 181 by the flow of the combustion gas by the burner unit 151 flowing through the exhaust air duct outer pipe 642, and the generated steam is vaporized. It supplies to 630 via a 2nd water vapor | steam supply pipe | tube.

The piping unit 700 of the reforming unit 300 includes a piping outer case 710 as shown in FIGS. The pipe outer case 710 includes a pipe covering part 711 and a connecting cylinder part 712.
As shown in FIGS. 2 to 4, 9, and 10, the pipe covering portion 711 is formed in a cylindrical shape having substantially the same diameter as the lower case 611 of the reformed exterior case 610, more specifically, a steel plate that is a pipe material It is formed using the plate winding tube. The upper end side, which is one end in the axial direction, of the pipe covering portion 711 is integrally connected by fitting the bottom joint portion 613A of the support pedestal portion 613 of the reforming portion 600 by welding or brazing. The pipe cover 711 includes a reformed water supply pipe 720, a raw material return pipe 730, a desulfurized fuel supply pipe 740, an air supply pipe 750, a fuel gas outflow pipe 760, and a cooling water pipe 770, as shown in FIG. Pipe holes 711A, 711B, 711C, 711D, 711E, and 711F to be inserted are drilled. In addition, a plurality of, for example, four, positioning dowels 711G that bulge into the inner package are provided in the pipe covering portion 711 in the circumferential direction.
The connecting cylinder portion 712 is formed in a substantially cylindrical shape having a diameter dimension that can be fitted to the lower end side, which is the other end in the axial direction of the pipe covering portion 711, and more specifically, a pipe material. It is formed using a sheet-wound tube of a certain steel plate. Further, the other end side in the axial direction of the connecting tube portion 712 is formed in a state of being slightly reduced in diameter. The connecting cylinder portion 712 includes a plurality of engaging recesses 712 </ b> A formed in a recessed shape that are positioned by engaging the positioning dowels 711 </ b> G of the pipe covering portion 711 with the upper end edge in the axial direction corresponding to the positioning dowels 711 </ b> G. For example, four places are provided. Then, the connecting cylinder portion 712 is fitted to the pipe covering portion 711 at the upper end side in the axial direction, the engaging recess 712A is engaged with the positioning dowel 711G and positioned, and the other portion in the axial direction is connected from the pipe covering portion 711 by welding or the like. It is connected so that the end side is exposed. Further, the connecting tube portion 712 has a plurality of connecting female screw holes 712B into which, for example, a screw member (not shown) as a connecting mounting member is screwed at the lower end on the other end side in the axial direction exposed from the pipe covering portion 711. Is provided.

As shown in FIG. 2, the CO removal unit 800 includes a CO removal outer case 810, and a CO converter 820 and a CO selective oxidizer 830 disposed in the CO removal outer case 810. The reformed outer case 610, the pipe outer case 710, and the CO removal outer case 810 constitute the casing of the present invention.
As shown in FIGS. 2 and 12, the CO removal outer case 810 includes a substantially cylindrical lower body portion 811 having substantially the same diameter as the lower case 611 of the reforming outer case 610 and the pipe covering portion 711 of the pipe outer case 710. Have. The lower body portion 811 is formed, for example, in a substantially cylindrical shape using a steel plate or the like, and more specifically, is formed using a sheet-wound tube of a steel plate that is a tube material. The CO removal exterior case 810, the above-described modified exterior case 610, and the piping exterior case 710 constitute an exterior case of the unit main body 400.

A connecting screw hole 811 </ b> A that is screwed corresponding to the connecting female screw hole 712 </ b> B of the connecting tube portion 712 of the pipe exterior case 710 is provided on the upper end side that is one end side in the axial direction of the lower body portion 811. The joint portion between the lower body portion 811 and the connecting tube portion 712 is preferably sealed with, for example, a heat-resistant caulking material. Further, a plurality of screw through holes 811B are provided on the lower end side which is the other end side in the axial direction of the lower body portion 811. In addition, an exhaust gas port 811 </ b> C that communicates the inside with the outside is formed in the lower end side in the axial direction of the lower body portion 811.
In addition, on the lower end side of the lower body portion 811, a heat insulating material support portion 812 that protrudes outward in a bowl shape on the outer peripheral surface and places and supports the heat insulating portion 500 is provided. The heat insulating material support portion 812 has an attachment cylindrical portion 812A whose inner diameter is substantially the same as the outer diameter of the lower body portion 811, and an outward flange at an upper end that is one end in the axial direction of the attachment cylindrical portion 812A. And a cylindrical holding portion 812C formed on the outer peripheral edge of the flange portion 812B in a cylindrical shape on the opposite side to the mounting cylindrical portion 812A and substantially coaxial with the mounting cylindrical portion 812A. Have. As shown in FIG. 2, the heat insulating material support portion 812 is not shown as a mounting member in a screw fitting insertion hole 812A1 provided in the mounting cylindrical portion 812A corresponding to the screw through hole 811B of the lower body portion 811. A screw is inserted and attached to the lower body portion 811 integrally. In this attached state, the flange portion 812B of the heat insulating material support portion 812 is in a state that substantially coincides with the opening edge of the exhaust gas port 811C of the lower body portion 811. In addition, as shown in FIG. 12, one end in the axial direction is attached to the exhaust port 811C of the lower body part 811 in the cylindrical holding part 812C of the heat insulating material support part 812, for example, by welding or brazing. The exhaust gas pipe 840 that exhausts the exhaust gas from the exhaust gas port 811C to the outside of the reforming unit 300 is provided with a notch 812C1 that is formed to be engageable.
Further, as shown in FIG. 2, a bottom plate portion 813 formed in a substantially disc shape with a steel plate or the like is provided on the lower end side which is the other end side in the axial direction of the lower body portion 811. The bottom plate portion 813 includes a substantially disc-shaped bottom plate 813A and a bottom plate connecting portion 813B formed in a series of cylinders whose outer diameter is substantially the same as the inner diameter of the lower body portion 811 from the periphery of the bottom plate 813A. is doing. The bottom plate connecting portion 813B of the bottom plate portion 813 is provided with a mounting female screw hole 813B1 corresponding to the screw through hole 811B of the lower body portion 811 and screwed into the screw through hole 811B. Is attached in a state of closing the lower end side of the lower body portion 811. Further, the bottom plate 813A of the bottom plate portion 813 includes a CO conversion sensor protection tube 825 (see FIG. 14) and a CO selective oxidation sensor protection tube 835 (see FIG. 17) in which a temperature sensor, which will be described in detail later, is provided. Two sensor through-holes (not shown) to be penetrated are provided.
Further, as shown in FIG. 2, a positioning and holding base portion 814 for positioning and holding the CO transformer 820 and the CO selective oxidizer 830 is provided on the upper surface of the bottom plate 813 </ b> A of the bottom plate portion 813. The positioning holding base portion 814 is provided with two pairs of notch recesses 814A to which the CO transformer 820 and the CO selective oxidizer 830 are respectively engaged at the upper end edge.
Further, the bottom plate 813A of the bottom plate portion 813 is provided with a column screw hole (not shown) corresponding to the column mounting screw hole of the support base portion 613 of the modified exterior case 610. Between the bottom plate portion 813 and the support base portion 613 of the modified exterior case 610, as shown in FIGS. 2 and 11, both end portions in the longitudinal direction are column screw holes and column attachments of the support base portion 613, respectively. A plurality of, for example, three support columns 815, which are screwed into the screw holes 613E and connect the bottom plate portion 813 and the support base portion 613, are attached.

As shown in FIGS. 2 and 13 to 15, the CO converter 820 includes a CO conversion container 821 as a case body formed in a hollow, substantially rectangular shape.
As shown in FIGS. 13 to 15, the CO conversion container 821 has a substantially box-shaped CO conversion container main body part 821A that is open on one surface, and one surface of the CO conversion container main body part 821A is closed, for example, by welding or brazing. And a CO conversion container lid 821B attached by, for example. The CO conversion container lid part 821B is connected to the reformed gas discharge pipe part 622T2 of the flow part 622P of the reforming container 622, and the reformed gas supplied from the reformed gas discharge pipe part 622T2 enters the CO conversion container 821. A reformed gas inflow pipe 821A1 connected to an inflow port (not shown) to be supplied is provided at substantially the center in the vicinity of the upper edge serving as one edge. Further, the CO conversion container lid 821B has a reformed gas that flows into the CO conversion container main body 821A at a substantially central position near the lower edge opposite to the side where the reformed gas inflow pipe 821A1 is provided. A reformed gas outlet 821B1 is formed as an outlet for discharging the gas. Further, a reinforcing sheet metal 821B2 is provided at substantially the center of the CO conversion container lid 821B. Note that the configuration is not limited to the configuration in which the reinforcing sheet metal 821B2 is provided, and various types of reinforcement configurations can be applied, for example, a portion other than the peripheral edge to be joined to the CO conversion container main body 821A is formed in an uneven shape such as a wave shape.
In the CO conversion vessel 821, a gas diffusion region 823A serving as a diffusion region communicating with the reformed gas inflow pipe 821A1, a gas converging region 823B serving as a converging region communicating with the reformed gas outlet 821B1, and gas diffusion A CO shift reaction region 823C as a reaction region in which the fuel gas is partitioned between the region 823A and the gas converging region 823B so that the fuel gas can communicate and is filled with the CO shift catalyst layer 822 to form the CO shift catalyst layer 822. Compartments are formed to allow distribution. The gas diffusion region 823A, the gas converging region 823B, and the CO shift reaction region 823C are partitioned by a pair of CO shift partition plates 823D formed in a mesh shape, for example. In addition to the structure formed with a mesh-like member, the CO-transformation partition plate 823D can be applied with any structure that allows fuel gas to flow, such as a steel plate having a plurality of holes. Furthermore, alumina particles or the like may be filled in portions corresponding to the gas diffusion region 823A and the gas convergence region 823B without using the CO-transforming partition plate 823D.

Further, in the CO conversion container 821, a CO conversion cooling pipe 824 that also functions as a water vapor generating means formed in a spiral shape is held and disposed by a cooling pipe mounting plate 821C. One end of the CO shift cooling pipe 824 in the axial direction is connected to the first steam connection of the raw material gas supply pipe 622S of the reforming vessel 622 from one side surface where the reformed gas inflow tube 821A1 of the CO shift vessel main body 821A is provided. It extends in an airtight manner so as to be connectable to a first water vapor supply pipe (not shown) connected to the portion 632A. The other end of the CO shift cooling pipe 824 in the axial direction is near the lower edge on the opposite side to the side where the reformed gas inflow pipe 821A1 of the CO shift vessel main body portion 821A is provided in the CO shift vessel lid portion 821B. It extends through airtightly.
The CO conversion container 821 has a sensor (not shown) of the bottom plate portion 813 of the CO removal exterior case 810 on the other side opposite to the one side where the reformed gas inflow pipe 821A1 of the CO conversion container main body 821A is provided. A CO conversion sensor protective tube 825 is provided that is airtightly inserted into a sensor insertion hole (not shown) provided corresponding to the through-hole for use, and is provided with a temperature sensor (not shown).
Further, the CO conversion container 821 is connected to the reformed gas outlet 821B1 of the CO conversion container lid part 821B, and an air introduction part 826 for mixing air into the reformed gas in the CO conversion container 821. The air inlet 826 is connected to an air supply pipe 750 and is formed in a substantially T-tube shape that mixes air from the air supply pipe 750 with the reformed gas flowing out from the reformed gas outlet 821B1.
In addition, the CO conversion container 821 is formed with a heat exchange pipe 827 penetrating the axial direction substantially along the vertical direction so that both ends in the axial direction are open to the upper and lower surfaces of the CO conversion container 821, respectively. The heat exchange pipe 827 is formed of, for example, a substantially cylindrical steel pipe. The heat exchange tube 827 is not limited to a substantially cylindrical shape, and may be a polygonal cylindrical shape, an elliptical cylindrical shape, a star cylindrical shape, or the like. Furthermore, a plurality of fin-like protrusions for improving the heat exchange efficiency with the CO conversion catalyst may be provided on the outer peripheral surface. Moreover, it is good also as a shape bent not only to a straight tube but to some spirals. In other words, any configuration may be used as long as the axial direction is substantially along the vertical direction and the convection state in which the hot air in the CO removal exterior case 810 flows through the heat exchange pipe 827 is obtained.

As shown in FIG. 2 and FIGS. 16 to 18, the CO selective oxidizer 830 has a CO selective oxidation vessel 831 as a case body formed in a hollow, substantially rectangular shape.
As shown in FIGS. 16 to 18, the CO selective oxidation container 831 has a substantially box-shaped CO selective oxidation container main body portion 831 </ b> A whose one surface is open, and one surface of the CO selective oxidation container main body portion 831 </ b> A is closed. And a CO selective oxidation container lid portion 831B attached by, for example. The CO selective oxidation vessel lid portion 831B communicates with the reformed gas outlet 821B1 of the CO converter 820 via the air inlet 826, and the reformed gas mixed with the air supplied from the reformed gas outlet 821B1. A reformed gas introduction pipe 831B1 connected to an inlet (not shown) for supplying the gas into the CO selective oxidation vessel 831 is provided at substantially the center in the vicinity of the lower edge serving as one edge. In the CO selective oxidation container main body 831A, a fuel gas, which is a reformed gas that has flowed into the interior and has CO removed therein, is selected at the center of the upper end surface opposite to the reformed gas introduction pipe 831B1. A fuel gas outlet pipe 831A1 connected to an outlet (not shown) that flows out of the oxidation container 831 is provided. The fuel gas outlet pipe 831A1 is connected to the fuel gas outlet pipe 760, and the fuel gas flows out of the reforming unit 300 through the fuel gas outlet pipe 760.
The CO selective oxidation vessel 831 is filled with a diffusion region 831C1 communicating with the reformed gas introduction pipe 831B1, a filler region 831C2 filled with, for example, alumina particles as an inert filler, and a CO selective oxidation catalyst. Thus, the reaction region 831C3 that forms the CO selective oxidation catalyst layer 832 and the convergence region 831C4 that communicates with the fuel gas outlet tube 831A1 are partitioned so that the fuel gas can flow therethrough. The diffusion region 831C1 and the filler region 831C2 are partitioned by a partition plate 831D1, and formed, for example, in a mesh shape between the filler region 831C2 and the reaction region 831C3 and between the reaction region 831C3 and the convergence region 831C4. Each of the partition walls is formed by a CO selective oxidation partition plate 831D2 serving as a partition wall. As shown in FIG. 19, the partition plate 831D1 is formed with a plurality of communication holes 831D3 that allow the diffusion region 831C1 and the filler region 831C2 to communicate with each other. These communication holes 831D3 can mix the air flowing from the reformed gas introduction pipe 831B1 and flow the reformed gas flowing into the diffusion region 831C1 substantially uniformly to the filler region 831C2, for example, 0.3 mm to 6 mm. A plurality of openings are formed.
As in the case of the CO conversion container 821, alumina particles or the like may be filled in portions corresponding to the diffusion region 831C1 and the convergence region 831C4 without using the partition plate 831D1 and the CO selective oxidation partition plate 831D2. In addition, as the partition plate 831D1 and the CO selective oxidation partition plate 831D2, any configuration in which the fuel gas can mutually flow, such as a configuration formed by a mesh-like member or a plate provided with a plurality of holes, can be applied. .
Further, the inert filler filled in the filler region 831C2 is preferably a substantially spherical granular material having the same diameter as that of the CO selective oxidation catalyst. Alumina particles are particularly preferable in terms of handling properties, stability of physical properties, and availability. For example, various inorganic oxides that are ceramics that are stable against heat, moisture, and fuel gas, such as silica and mullite, are used. it can. Further, the inert filler is not limited to a configuration using granular materials, and may be configured to fill, for example, a fiber shape. In the configuration of the present embodiment in which the filler region 831C2 is partitioned and formed vertically below the CO selective oxidation catalyst layer 832, the alumina particles have a higher specific gravity than the CO selective oxidation catalyst. 831D2 may not be provided, but the reaction region 831C3 and the filler region 831C2 are partitioned by the CO selective oxidation partition plate 831D2 and mixed with each other when the external vibration, particularly the CO selective oxidizer 830 is assembled. It is preferable not to do so. On the other hand, in the configuration in which the filler region 831C2 is partitioned upward in the vertical direction with respect to the CO selective oxidation catalyst layer 832, the inert filler has a lower specific gravity than the CO selective oxidation catalyst, for example, it is made porous. The CO selective oxidation partition plate 831D2 may not be provided.

Further, in the CO selective oxidation vessel 831, there is a CO selective oxidation cooling pipe 834 as a flowing water means that also functions as a water vapor generating means that is spirally formed of a pipe material so that pure water 181 can flow inside. The oxidation vessel 831 is held and arranged by a cooling pipe holding plate 831E provided in a rib shape. One end of the CO selective oxidation cooling pipe 834 in the axial direction extends in an airtight manner so as to be connectable to the cooling water pipe 770 from the lower side surface of the CO selective oxidation container 831 corresponding to the lower part of the filler region 831C2. The other end of the CO selective oxidation cooling pipe 834 in the axial direction extends from the upper end surface of the CO selective oxidation container main body 831A where the fuel gas outlet pipe 831A1 is provided, and the CO conversion cooling pipe 824 of the CO converter 820. It is connected to. Then, pure water 181 which is cooling water supplied from the cooling water pipe 770 flows through the CO selective oxidation cooling pipe 834 and flows into the CO shift cooling pipe 824 while appropriately cooling the CO selective oxidation catalyst layer 832, and further CO 2 While the modified catalyst layer 822 is appropriately cooled, it is converted into water vapor by heat exchange and supplied to the vaporizer 630 of the source gas supply pipe 622S.
The CO selective oxidation cooling pipe 834 is formed so that the spiral pitch is finer than the spiral pitch in the other regions in the region of the filler region 831C2 on the upstream side where the pure water 181 flows. 2, 16, and 17 show the helical pitch at equal intervals for convenience.
Further, in the CO selective oxidation container 831, a sensor fitting (not shown) provided on the lower end surface of the CO selective oxidation container main body 831 A corresponding to a sensor through hole (not shown) of the bottom plate portion 813 of the CO removal exterior case 810. A CO selective oxidation sensor protective tube 835 that is inserted into the insertion hole in an airtight manner and is inserted into a sensor insertion hole 831D4 formed in the partition plate 831D1 as shown in FIG. Is provided.
Note that pure water 181 as cooling water supplied to the CO selective oxidation cooling pipe 834 and the CO shift cooling pipe 824 is supplied from the water supply path 183 having the transport pump 182 serving as a path for supplying the heat exchange device 640 to the water supply path 183. Although the structure supplied from the cooling water pipe 770 which comprises a part of this is illustrated (refer FIG. 1), it is good also as supplying from the path | route different from the heat exchange apparatus 640, or a part branched supply. Furthermore, it is not configured to be used for water vapor mixed with the liquid fuel 111. For example, a coolant such as tap water may be circulated as a configuration for recovering the heat of CO conversion and CO selective oxidation like the cooling device 187. Good.

As shown in FIG. 2, the heat insulating part 500 includes a lower heat insulating part 510, an intermediate heat insulating part 520, an upper heat insulating part 530, and a shell 540. Note that the heat insulating portion 500 may be configured without the shell 540.
The lower heat insulating portion 510 is configured in a substantially cylindrical shape by joining a pair of lower block bodies 511 formed by, for example, forming a heat insulating material 511B in a semicircular shape in plan view. The lower heat insulating portion 510 is formed so that the inner diameter is substantially the same as the outer diameter of the CO removing outer case 810 of the CO removing portion 800, and the CO removing portion 800 is included on the inner peripheral side so as to be insulated. . The lower heat insulating portion 510 is formed to have a thickness dimension substantially the same as the inner diameter of the cylindrical holding portion 812C of the heat insulating material support portion 812 of the CO removal exterior case 810, and can be placed on the heat insulating material support portion 812. Has been. Furthermore, on the upper end surface which is one end side in the axial direction of the lower heat insulating portion 510, the reformed water supply pipe 720, the raw material return pipe 730, the desulfurized fuel supply pipe 740, the air supply pipe 750, and the cooling pipe. A concave pipe lower recess 512 is provided at a position corresponding to the water pipe 770 and the fuel gas outflow pipe 760. Further, a concave portion for exhaust gas pipe (not shown) is provided at a position corresponding to the exhaust gas pipe 840 on the lower end surface which is the other end side in the axial direction of the lower heat insulating portion 510. In addition, the lower heat insulating portion 510 is configured by the lower block body 511 that forms a pair, and for example, a heat insulating wool material or a heat insulating material such as a granular material is filled between the shell 540 and the CO removal outer case 810 or the like. It can be formed using various heat insulating materials.
The intermediate heat insulating part 520 is joined to the intermediate block body 521 formed in a substantially semicircular arc shape with the heat insulating material 511B, for example, similarly to the lower heat insulating part 510, and is formed into a substantially cylindrical shape having the same diameter as the lower heat insulating part 510. Is formed. The axial length of the intermediate heat insulating portion 520 is such that the upper end surface of the intermediate heat insulating portion 520 is stacked on the lower heat insulating portion 510 placed on the heat insulating material support portion 812, and the upper end surface is the lower case of the reformed outer case 610. The upper edge of 611 does not protrude from the upper end surface of the intermediate heat insulating portion 520. That is, the intermediate heat insulating portion 520 has an axial length dimension in which the upper end surface is positioned above the thermal expansion dimension of the modified exterior case 610 having a predetermined dimension from the upper end edge of the lower case 611. Is formed. In addition, a concave pipe upper concave portion 522 is provided on the end surface of the intermediate heat insulating portion 520 on the lower heat insulating portion 510 side in the axial direction, corresponding to the pipe lower concave portion 512 of the lower heat insulating portion 510. In addition, it is comprised by the piping lower recessed part 512 of the lower heat insulation part 510, and the piping upper recessed part 522 of the intermediate | middle heat insulation part 520, the reforming water supply pipe 720, the raw material return pipe 730, the desulfurization fuel supply pipe 740, the air supply pipe 750, cooling The opening in which the water pipe 770 and the fuel gas outflow pipe 760 are piped is filled with a heat insulating material (not shown) and closed. Note that the intermediate heat insulating portion 520 can also be formed using various heat insulating materials, similarly to the lower heat insulating portion 510.
The upper heat insulating portion 530 is formed in a substantially cylindrical shape with, for example, a heat insulating material 511B. Note that, similarly to the lower heat insulating portion 510, it may be configured in a substantially cylindrical shape by a block body formed in a substantially semicircular arc shape. The upper heat insulating portion 530 can also be formed using various heat insulating materials. The upper heat insulating portion 530 has an outer diameter substantially the same as that of the lower heat insulating portion 510 and the intermediate heat insulating portion 520 and an inner diameter substantially equal to the outer diameter of the upper case 612 of the reformed exterior case 610. Further, the upper heat insulating portion 530 is formed such that the upper end thereof is substantially positioned at the upper end portion of the upper case 612 with the axial length dimension being stacked on the arranged intermediate heat insulating portion 520.
The shell 540 is formed in a substantially cylindrical shape using, for example, a steel plate so as to wrap around the outer peripheral surfaces of the lower heat insulating portion 510, the intermediate heat insulating portion 520, and the upper heat insulating portion 530 stacked in the axial direction. The shell 540 is formed in a cylindrical shape by winding a steel plate so as to surround the outer peripheral surfaces of the stacked lower heat insulating portion 510, intermediate heat insulating portion 520, and upper heat insulating portion 530, and screwing, bonding, tape fixing or the like. . For example, the lower end portion of the shell 540 is interposed between the outer peripheral surface of the lower heat insulating portion 510 and the cylindrical holding portion 812C of the heat insulating material supporting portion 812, and is fixed by screwing or the like from the cylindrical holding portion 812C.

[Operation of fuel cell system]
(Reforming unit assembly operation)
Next, the assembly operation of the reforming unit 300 in the fuel cell system 100 described above will be described.

First, the flow passage 622P is integrally provided in the reforming vessel 622 and filled with the reforming catalyst. Further, the heat exchanging device 640 is integrally attached to the support base 613. And the partition cylindrical part 622T1 of the distribution | circulation part 622P connected with the modification | reformation container 622 is connected with the support base part 613 to which the heat exchange apparatus 640 was attached by welding etc., for example. Furthermore, one end of the reformed water inner pipe 641 of the heat exchange device 640 that is the outflow side of steam passing through the support pedestal 613 is connected to the second steam connection section 632B of the source gas supply pipe 622S and piped.
Thereafter, the outer pipe case 710 is welded or brazed to the support base 613, and the pipe holes 711A, 711B, 711C, 711D, 711E, and 711F of the pipe cover 711 of the pipe outer case 710 are modified. The water supply pipe 720, the raw material return pipe 730, the desulfurized fuel supply pipe 740, the air supply pipe 750, the cooling water pipe 770, and the fuel gas outflow pipe 760 are fitted and welded. The reforming water supply pipe 720 is connected to the reforming water inner pipe 641 of the heat exchange device 640, the raw material return pipe 730 is connected to the raw material return section 622S2 of the raw material gas supply pipe 622S, and the desulfurized fuel supply pipe 740 is used as the raw material. A pipe is connected to the liquid fuel connecting portion 631 of the gas supply pipe 622S.

In addition, the CO transformer 820 and the CO selective oxidizer 830 are positioned and held on the positioning holding base portion 814 of the bottom plate portion 813 and are integrally attached. When attaching the bottom plate portion 813 to the CO converter 820 and the CO selective oxidizer 830, the air introduction portion 826 and the reformed gas introduction pipe 831B1 of the CO selective oxidizer 830 that are integrally attached to the CO converter 820 are provided. A CO conversion cooling pipe 824 extending from the CO conversion container lid 821B of the CO converter 820 and a CO selective oxidation cooling pipe 834 extending from the upper part of the CO selective oxidation container 831A of the CO selective oxidizer 830 are connected. Then, the CO transformer 820 and the CO selective oxidizer 830 are assembled together.
And while attaching the end of the support | pillar part 815 to the baseplate part 813, attaching the other end of the support | pillar part 815 to the support base part 613 to which the piping exterior case 710 mentioned above was attached, and connected.
In this state, the CO shift cooling pipe 824 of the CO shift converter 820 is connected to the first steam connection 632A of the raw material gas supply pipe 622S of the reforming vessel 622, and the CO selective oxidation cooling pipe 834 of the CO selective oxidizer 830 is connected. The cooling water pipe 770 is connected and piped. Further, the reformed gas inflow pipe 821A1 of the CO converter 820 is connected to the reformed gas discharge pipe 622T2 constituting the flow part 622P of the reforming vessel 622, and is piped. Further, the fuel gas outlet pipe 831A1 of the CO selective oxidizer 830 is connected to the fuel gas outflow pipe 760 for piping.

Thereafter, the heat insulating material support portion 812 is inserted into the lower body portion 811 positioned on the outer peripheral side from the bottom plate portion 813 side, and the lower body portion 811 and the connecting tube portion 712 of the pipe exterior case 710 are brought into contact with each other. Then, the female screw hole 813B1 of the bottom plate connecting portion 813B of the bottom plate portion 813 and the screw fitting hole 812A of the mounting cylindrical portion 812A of the screw through hole 811B and the heat insulating material support portion 812 corresponding to the screw through hole 811B of the lower body portion 811. 812A1 is communicated, and screws are screwed together to be assembled together. When screwing, the joint is sealed with a heat-resistant caulking material. Further, the exhaust gas pipe 840 is connected to the exhaust gas port 811C of the lower body part 811 by welding or the like. Note that the exhaust pipe 840 may be connected in advance to the lower body portion 811 to be assembled with the bottom plate portion 813.
Further, the refractory heat insulating material 622K is placed on the heating chamber partition plate 622I in the heating chamber 622H of the reforming vessel 622, and the closing plate 622L1 of the rectifying tube 622L is screwed to the connecting screw portion 622J to thereby connect the rectifying tube 622L. Assemble.
Thereafter, the exposed reforming container 622 is attached so as to cover the reforming outer case 610, and the lower case 611 of the reforming outer case 610 is brought into contact with the pipe outer case 710. In this state, the screw into which the lower screw hole 611B of the lower case 611 is fitted is screwed into the mounting female screw portion 613C of the support base 613, and is assembled integrally. Furthermore, the combustion chamber portion 621 is fitted into the heating chamber 622H, and the support flange 621C of the combustion chamber portion 621 is suspended and supported by being superimposed on the burner connection flange 612C of the upper case 612 of the reformed exterior case 610.
Thereafter, the lower heat insulating portion 510 is placed and fixed on the heat insulating material support portion 812, the intermediate heat insulating portion 520 is stacked on the lower heat insulating portion 510 on the same axis, and the upper heat insulating portion 530 is further stacked. Then, the shell 540 is wound around the outer peripheral surfaces of the stacked lower heat insulating portion 510, intermediate heat insulating portion 520, and upper heat insulating portion 530, and the heat insulating portion 500 is configured. Further, the burner unit 151 is placed on the upper case 612, and the upper case 612, the combustion chamber portion 621, and the burner unit 151 are integrally assembled with the mounting bolt 612D, and the reforming unit 300 is assembled.

(Power generation operation of fuel cell system)
Next, the power generation operation in the fuel cell system 100 described above will be described. In the present embodiment, a configuration in which the fuel cell 200 generates power using the liquid fuel 111 as a main raw material is illustrated.

First, when the control device acquires a signal related to a power generation request, liquid fuel 111 or raw material gas and air are supplied to the burner unit 151 to heat the reformer 620 to, for example, 500 ° C. or higher.
Combustion gas from the burner unit 151 flows into the inner peripheral side of the opposing rectifying pipe 622L to heat the rectifying pipe 622L, and from the upper end of the expansion, the outer peripheral surface of the rectifying pipe 622L and the combustion cylinder of the combustion chamber 621 It flows between the inner peripheral surface of the part 621A downward in the vertical direction. At the time of this flow, the turbulent flow part 622L3 flows spirally with respect to the central axis of the reformer 620. By this flow, the rectifying pipe 622L and the combustion cylinder portion 621A are heated. Further, the combustion gas flows upward from the lower end of the combustion cylinder portion 621A between the outer peripheral surface of the combustion cylinder portion 621A and the inner peripheral surface of the reforming vessel 622, and passes through the combustion cylinder portion 621A and the reforming vessel 622. Heat. The combustion gas that has flowed to the upper part of the reforming vessel 622 flows downward between the outer peripheral surface of the reforming vessel 622 and the upper case 612 and flows into the lower case 611. Further, the combustion gas flows from the lower case 611 between the inner peripheral side of the exhaust air passage outer pipe 642 and the outer peripheral side of the reformed water inner pipe 641 of the heat exchange device 640 and flows into the piping unit 700. Further, the combustion gas that has flowed into the CO removal unit 800 from the piping unit 700 is appropriately heated by the CO converter 820 and the CO selective oxidizer 830 and is exhausted from the exhaust gas pipe 840 to the outside. When the CO converter 820 is heated by the combustion gas, the combustion gas also flows through the heat exchange pipe 827 of the CO converter 820, and the CO conversion catalyst layer 822 of the CO converter 820 is heated not only from the outside but also from the inside. And is efficiently heated to a higher CO conversion reaction temperature than CO selective oxidation.
In this way, the reformer 620 is heated, and the heat exchanger 640, each pipe, the CO converter 820, and the CO selective oxidizer 830 are heated.

Then, in a state where the CO converter 820 and the CO selective oxidizer 830 are heated to some extent, the control device drives the transport pump 182 to store the pure water 181 stored in the pure water tank 180 from the water supply path 183. Through a cooling water pipe 770 constituting a part of H.183, the gas is supplied to a CO selective oxidation cooling pipe 834 of the CO selective oxidizer 830 and a CO conversion cooling pipe 824 of the CO converter 820 in order.
If the CO selective oxidizer 830 is not sufficiently heated during the distribution of the pure water 181, there is a risk of condensation on the outer surface of the CO selective oxidation cooling pipe 834, but even if condensation occurs, the pure water 181 Therefore, there is no inconvenience such as deactivation of the CO selective oxidation catalyst due to dew condensation. That is, dew condensation fills at least the reformer 620 with a reformed gas or an inert gas when the operation is stopped, and when only the water vapor flows when pushing out the internal reformed gas or the inert gas at the time of startup. Since the CO selective oxidizer 830 is not sufficiently heated when flowing pure water 181 to generate water vapor, it is filled with an inert filler under such operating conditions and the CO selective oxidation catalyst by dew condensation is generated. It is necessary to prevent deactivation.
Further, the pure water 181 stored in the pure water tank 180 by the drive of the transport pump 182 is supplied to the reformed water inner pipe 641 of the heat exchange device 640 via the reformed water supply pipe 720 constituting a part of the water supply path 183. To be supplied. The supplied pure water becomes steam by heat exchange with the flowing combustion gas, and is supplied to the vaporizer 630 from the second steam connection part 632B of the source gas supply pipe 622S. In addition, although mentioned later for details, the water vapor | steam supplied from the CO removal part 800 is also supplied to the vaporizer | carburetor 630 from the 1st water vapor | steam connection part 632A of source gas supply pipe | tube 622S.

Further, the control device heats the electric heater of the desulfurizer 130 and drives the liquid fuel pump 121 to supply the liquid fuel 111 from the liquid fuel storage tank 110 to the desulfurizer 130 at, for example, about 300 [ml / hour]. To do.
The liquid fuel 111 supplied to the desulfurizer 130 flows into the desulfurization agent container, and the flow velocity distribution in a cross section of a desulfurization catalyst layer (not shown) formed by filling the desulfurization agent container with the desulfurization catalyst is substantially uniform. It is desulfurized while being heated. The desulfurized liquid fuel 111 is mixed with water vapor supplied by the vaporizer 630 and vaporized, and is supplied from the raw material gas supply unit 622R to the reforming vessel 622 as vaporized liquid fuel. The vaporized liquid fuel is reformed by the reformer 620 into a hydrogen-rich fuel gas.
Here, in the flow of the combustion gas of the burner unit 151 in the reformer 620, the heated rectifying pipe 622L heats the reforming vessel 622 to, for example, about 700 ° C. through the combustion cylinder portion 621A by radiant heat. Note that the rectifying pipe 622L is not positioned at the lower end portion of the reforming catalyst layer 622G of the reforming vessel 622, that is, the closing plate 622L1 of the rectifying tube 622L is positioned above the lower end portion of the reforming catalyst layer 622G of the reforming vessel 622. Since it is arranged in a state, the proportion of the upstream side of the reforming catalyst layer 622G due to the radiant heat of the rectifying pipe 622L is reduced. For this reason, the temperature at the lower end of the reforming catalyst layer 622G where the raw material gas flows is somewhat lower than that at the upper end, so that overheating is suppressed and coking of the reforming catalyst portion 622G can be prevented. Therefore, the vaporized liquid fuel that has flowed into the lower end of the reforming catalyst layer 622G is reformed over substantially the entire area in the axial direction of the reforming catalyst layer 622G, and is efficiently and stably processed.

Then, the fuel gas reformed by the reformer 620 is supplied to the CO gas converter 820 and the CO selective oxidizer 830 sequentially from the reformed gas outlet 622T, and the CO gas converter 820 and the CO selector are selected. The CO in the fuel gas is transformed and selectively oxidized and removed by the oxidizer 830 and supplied to the fuel cell 200 from the fuel gas outlet pipe 760 of the reforming unit 300.
Further, the fuel gas supplied to the fuel cell 200 is supplied to the negative electrode 202 side of the fuel cell 200. In addition, when this fuel gas flows into the fuel cell 200, it may be appropriately humidified with a humidifier, for example, as necessary. The hydrogen of the fuel gas supplied to the negative electrode 202 side is appropriately humidified as necessary and reacts with oxygen in the air supplied to the positive electrode 201 side of the fuel cell 200 to generate water. DC power is generated between the negative electrodes 202.
The fuel gas containing surplus hydrogen on the negative electrode 202 side is supplied to the burner unit 151 of the reformer 620 and burned, for example.

  On the other hand, for example, when the reforming catalyst layer 622G of the reforming vessel 622 is closed during a power generation operation, the internal pressure in the source gas supply unit 622R reaches a predetermined value or more and is connected to the source gas supply pipe 622S. The safety valve of the raw material return pipe 730 thus operated operates. The safety valve then causes gas phase components such as vaporized liquid fuel gas and reformed gas in the source gas supply unit 622R to flow out of the reforming unit 300 from the source gas supply pipe 622S through the source return pipe 730. Further, the vaporized liquid fuel generated in the vaporizer 630 is not supplied to the raw material gas supply unit 622R, but flows out of the reforming unit 300 through the raw material return pipe 730. In addition, you may collect | recover the vaporized liquid fuel etc. which flow out to the receiving part etc. which were provided separately.

[Effects of fuel cell system]
As described above, in the above-described embodiment, the heat exchange pipe 827 is formed through the CO conversion container 821 so that the inner peripheral surface communicates with the outside of the CO conversion container 821.
As a result, the combustion gas, which becomes exhaust heat after heating of the burner unit 151 for the reforming process in the reformer 620, comes into contact with the outer surface of the CO converter 820 and heats it. The CO shift reaction region 823C, which is in circulation and is heated from the inside, is filled with the CO shift catalyst and forms the CO shift catalyst layer 822, is efficiently heated, and the CO shift reaction region 823C is heated substantially uniformly for a short time. It is obtained with.
In particular, the CO converter 820 has a larger catalyst capacity and a larger volume as compared with the CO selective oxidizer 830 that aims to remove CO in the same manner, so that the CO converter 820 is heated to the inside of the CO conversion reaction region 823C. However, the overall heat can be efficiently obtained by the heat exchange tube 827.

Further, the axial direction of the heat exchange pipe 827 is in a state substantially along the vertical direction of the installed CO transformer 820. As a result, the temperature in the heat exchange tube 827 that penetrates through the CO shift reaction region 823C that is difficult to be heated is lower than the temperature on the outer surface side of the CO shift vessel 821, and the combustion gas is convected in the heat exchange tube 827. It becomes easy to distribute. For this reason, the CO shift reaction region 823C can be heated more efficiently.
Then, the CO conversion reaction region 823C can be heated more efficiently by providing a configuration in which the heat exchange tube 827 is formed in a slightly spiral shape or provided with a fin or the like to increase the contact area with the CO conversion catalyst. .
Furthermore, when the reformer 620 is started from a cold state, it is easy to raise the temperature (preheating) to a temperature necessary for the reaction.

The CO shift reaction region 823C filled with the CO shift catalyst to form the CO shift catalyst layer 822 has an inlet (not shown) serving as an opening edge of the connected reformed gas inlet pipe 821A1, and a reformed gas outlet 821B1. Are defined between the inlet and the opening edge of the reformed gas outlet 821B1. Specifically, the fuel gas flows between the CO shift reaction region 823C between the gas diffusion region 823A communicating with the reformed gas inlet pipe 821A1 and the gas converging region 823B communicating with the reformed gas outlet 821B1. The partition is formed as possible.
For this reason, the fuel gas flowing in from the inlet through the reformed gas inflow pipe 821A1 is diffused in the gas diffusion region 823A, flows substantially uniformly in the CO shift reaction region 823C, and flows into the gas convergence region 823B. Since the gas is converged to flow out to the gas outlet 821B1, the contact efficiency between the fuel gas and the catalyst is improved, and the remaining CO in the fuel gas can be efficiently removed.
Similarly, the CO selective oxidizer 830 is filled with a CO selective oxidation catalyst between the diffusion region 831C1 communicating with the reformed gas introduction pipe 831B1 and the convergence region 831C4 communicating with the fuel gas outlet pipe 831A1. Since the reaction region 831C3 for forming the selective oxidation catalyst layer 832 is partitioned, the flowing fuel gas flows through the reaction region 831C3 substantially uniformly, and CO can be efficiently removed.

The CO selective oxidation catalyst is filled, and the reformed gas introduction pipe 831B1 connected to the inlet into which the fuel gas generated by the reformer 620 is introduced, and the fuel gas in contact with the CO selective oxidation catalyst is discharged. A CO selective oxidation vessel 831 having a fuel gas outlet pipe 831A1 connected to the outflow port passes through a CO selective oxidation cooling pipe 834 through which pure water 181 heated by heat exchange with a CO selective oxidation catalyst can flow. Provided. Then, the CO selective oxidation vessel 831 corresponding to the upstream side of the CO selective oxidation cooling pipe 834 is filled with an inert filler such as alumina particles.
For this reason, since the inert filler is filled in the upstream side of the CO selective oxidation cooling pipe 834 through which the pure water 181 that exchanges heat with the CO selective oxidation catalyst is circulated, for example, even if dew condensation occurs at the time of start-up, the dew condensation occurs Since the generated range is a region filled with an inert filler, it is possible to prevent moisture due to condensation from adhering to the CO selective oxidation catalyst and deactivating. Therefore, even if the repeated operation is carried out for a long period of time, the activity of the catalyst can be maintained, inconvenience such as blockage of the fuel gas circulation space due to the deactivation of the CO selective oxidation catalyst can be prevented, and the total amount of the CO selective oxidation catalyst can be reduced. Efficient CO removal can be obtained by contributing to the reaction, and hydrogen gas can be generated stably and satisfactorily.

In the above-described embodiment, the pure water 181 circulates from the vertical lower portion to the upper portion of the CO selective oxidation vessel 831 in a state where the CO selective oxidizer 830 is assembled and arranged for piping and the like. A CO selective oxidation cooling pipe 834 is provided. In this embodiment, a CO selective oxidation partition plate 831D2 is provided that partitions the filler region 831C2 and the reaction region 831C3 so that the reformed gas can flow.
As a result, the filler region 831C2 is positioned below the reaction region 831C3 in the vertical direction, but the inert filler is generally formed of alumina particles having a higher specific gravity than the CO selective oxidation catalyst. , Mixing with each other can be prevented, and CO removal by an efficient CO selective oxidation catalyst can be obtained.

Further, the CO selective oxidation cooling pipe 834 is spirally formed by a pipe member, and the upstream side where the pure water 181 flows, that is, the part corresponding to the filler region 831C2 is formed in a state where the helical pitch is finer than other regions. is doing.
For this reason, it is possible to reduce the filler region 831C2 in which condensation in the CO selective oxidation vessel 831 may occur, to sufficiently secure the reaction region 831C3 of the CO selective oxidation catalyst layer 832, and to reduce the size of the CO selective oxidizer 830. Can be easily achieved.

Furthermore, as an inert filler for preventing adverse effects due to dew condensation, alumina particles are used that are relatively easy to handle and obtain with stable characteristics that do not change due to dew condensation even if dew condensation occurs.
For this reason, it is possible to easily manufacture the CO selective oxidizer 830 that can efficiently remove CO by the CO selective oxidation catalyst.

Moreover, what was formed in the granule of the substantially the same diameter as a CO selective oxidation catalyst is used as an inert filler.
For this reason, the flow resistance of the fuel gas between the reaction region 831C3 filled with the CO selective oxidation catalyst and the filler region 831C2 filled with the inert filler becomes substantially equal, and the inert filler is used in order to prevent adverse effects due to condensation. The CO selective oxidizer 830 can be easily manufactured even with the filling configuration.

Furthermore, as a unit configuration, both the CO converter 820 and the CO selective oxidizer 830 are incorporated together with the reformer 620.
For this reason, the reformed gas reformed by the reformer 620 is immediately processed by the CO converter 820 and the CO selective oxidizer 830, so that, for example, a configuration for supplying hydrogen gas for the fuel cell 200 can be easily obtained. It can be easily used for home use and the like, and can be downsized easily. Further, the reforming unit 300 has a unit configuration combined with the heat exchange device 640 and the vaporizer 630. For this reason, better thermal efficiency can be easily obtained, and downsizing can be easily achieved.

Further, as a configuration for generating steam, not only the heat exchange device 640 but also the CO conversion cooling pipe 824 and the CO conversion passage through which pure water 181 that is cooling water for preventing overheating of the CO conversion device 820 and the CO selective oxidizer 830 is circulated. A selective oxidation cooling pipe 834 is provided.
For this reason, it is possible to share a configuration in which a high-temperature reformed gas is cooled for CO conversion and CO removal and a configuration in which steam is generated to prepare raw material gas by mixing with liquid fuel that has been separately desulfurized, Further simplification of configuration and further improvement of thermal efficiency are obtained.
Then, the CO conversion container 821 of the CO converter 820 includes a substantially box-shaped CO conversion container main body 821A whose one surface is open, and a CO conversion container attached by, for example, welding by closing one surface of the CO conversion container main body 821A. It is comprised with the cover part 821B. Similarly, the CO selective oxidation container 831 of the CO selective oxidizer 830 is closed by substantially welding a box-shaped CO selective oxidation container main body portion 831A having one surface open and one surface of the CO selective oxidation container main body portion 831A, for example, by welding. It is comprised with the CO selective oxidation container cover part 831B attached. For this reason, the CO conversion container 821 and the CO selective oxidation container 831 can be easily formed, and the productivity can be improved.
Further, pure water 181 serving as cooling water is circulated from the CO selective oxidation cooling pipe 834 to the CO conversion cooling pipe 824. That is, since the temperature required for CO transformation is higher than the temperature required for CO selective oxidation, cooling is performed in order from the lowest temperature, and each part is cooled by pure water 181 flowing at an appropriate temperature, which is good. Processing is obtained.

In the above-described embodiment, the reforming unit 300 is integrated with the reforming outer case 610, the pipe outer case 710, and the CO removal outer case 810 that are integrally connected to each other.
For this reason, the reforming unit 300 has a substantially columnar configuration, the surface area can be reduced, heat loss can be prevented, and energy efficiency can be improved. Furthermore, it becomes easy to heat-treat with the heat insulation part 500 of the simple structure comprised in substantially cylindrical shape, and workability | operativity can be improved.
In the above-described embodiment, the reforming unit 300 is configured such that the position corresponding to the reforming vessel 622 is a substantially circular tower having a stepped shape with a small diameter of the upper case 612.
That is, since the thickness of the heat insulating material 511B at the position of the reforming vessel 622 that is the highest temperature is increased, the maximum outer diameter of the reforming unit 300 can be minimized by forming a correspondingly small diameter. Can be easily reduced in size.
Furthermore, the reforming unit 300 is configured in a cylindrical shape with no step on the outer peripheral surface, and the appearance can be improved.

In the above-described embodiment, the heat insulating portion 500 of the reforming unit 300 has a substantially cylindrical block shape.
Therefore, assembly of the reforming unit 300 and disassembly for maintenance and inspection can be facilitated, and manufacturability can be improved and management such as maintenance and inspection can be facilitated. In particular, the substantially cylindrical heat insulating portion 500 is configured by a semicircular arc block body having a so-called half shape. For this reason, the modification unit 300 can be assembled and disassembled more easily.
Further, when the intermediate heat insulating portion 520 is disposed, the upper end surface of the intermediate heat insulating portion 520 is higher than the thermal expansion dimension of the modified outer case 610 having a predetermined dimension from the upper edge of the lower case 611 where the upper end surface is a step. It is configured to be located in
For this reason, due to the thermal expansion of the unit main body 400 such as the reformed exterior case 610, the upper heat insulating part 530 rides on the lower case 611, and the intermediate heat insulating part 520 and the upper heat insulating part 530 are positioned at the level difference. It is possible to easily prevent the inconvenience that a gap is generated between them and heat loss occurs.

Further, in the above-described embodiment, the heat insulating portion 500 is protruded outwardly in a bowl shape on the outer peripheral surface at the lower portion of the CO removing outer case 810 positioned at the lower portion constituting the outer case of the unit main body 400 of the reforming unit 300. A heat insulating material support portion 812 for mounting and supporting is provided.
For this reason, the heat insulation of the required part of the reforming unit 300 is obtained, the heat insulating part 500 can be minimized, and the displacement of the heat insulating part 500 for heat insulating the required part can be prevented, and reliable heat insulation is simple. Easy to get in configuration.

In the above embodiment, the reformer unit 300 is provided with the burner unit 151 at the upper part in the vertical direction, and the combustion gas of the burner unit 151 is circulated through the reformer unit 300 to the lower part in the vertical direction. The exhaust gas is exhausted from an exhaust gas port 811C provided at the lower part of the unit 300.
For this reason, by heating the CO converter 820 and the CO selective oxidizer 830 when the combustion gas in the burner unit 151 flows, the thermal energy of the combustion gas can be used effectively, and the energy efficiency can be improved.

In the above embodiment, the reformer 620 is disposed at the upper part of the reforming unit 300, and the CO converter 820 and the CO selective oxidizer 830 are disposed at the lower part. The reformer 620 and the CO converter A piping unit 700 is provided between the 820 and the CO selective oxidizer 830 for piping.
For this reason, the liquid fuel 111, which is the raw material for the fuel gas of the fuel cell 200, and the pure water 181 supplied as water vapor are from the middle position of the reforming unit 300, the total length of each pipe is minimized, and the size of the apparatus is reduced. And piping work can be done easily. Furthermore, since the total length of the piping is the shortest, the risk of leakage can be reduced and the manufacturing can be made relatively inexpensively.
Further, the fuel gas outflow pipe 760 is led out from the piping position which is an intermediate position of the reforming unit 300, and the generated fuel gas is caused to flow out to the outside.
For this reason, for example, when the fuel gas is allowed to flow out from the lower portion, the fuel cell 200 is disposed above the flow-out position in the vertical direction, so that the water vapor content in the fuel gas is condensed and in the piping. Therefore, the fuel gas can be supplied stably to the fuel cell 200 with ease.
Further, a heat exchange device 640 serving as a steam generating means is disposed at an intermediate position of the reforming unit 300, that is, between the reforming vessel 622, the CO converter 820 and the CO selective oxidizer 830. .
For this reason, the temperature in the reforming vessel 622 necessary for reforming, the temperature necessary for generating steam, and the temperature necessary for preheating the CO converter 820 and the CO selective oxidizer 830 are sequentially reduced in the vertical direction. The arrangement relationship is such that the temperature decreases in order from the upper side to the lower side. Therefore, since the temperature required for using the combustion gas of the burner unit 151 is arranged in the order of high temperature, each part can be heated by the combustion gas at an appropriate temperature, and good thermal efficiency can be easily obtained. It is done.

Further, in the above-described embodiment, the burner unit 151 is provided on the upper portion, that is, the upper end portion of the reforming unit 300 in the vertical direction.
Therefore, the burner unit 151 can be easily attached and detached, and management such as maintenance and inspection of the burner unit 151 is facilitated. In particular, by providing it at the upper end, it is only necessary to attach and detach with the mounting bolt 612D, and management such as maintenance and inspection becomes easier, and simplification of the configuration can be easily obtained.
Further, the burner unit 151 is disposed in a state in which the combustion gas flows out substantially downward in the vertical direction, and a rectifying pipe 622L is disposed in a state of being positioned below the burner unit 151 and opening upward. ing.
For this reason, it is possible to prevent liquid from dripping from the burner unit 151 such as liquid dripping from the burner unit 151 and condensation of moisture on the surface of the rectifying pipe 622L when operation is stopped. Therefore, the burner unit 151 can be prevented from being clogged or damaged by dripping, and a stable combustion gas can be generated, and a stable operation can be easily obtained.

Further, in the above-described embodiment, as the reforming unit 300, a pipe that is a joint between the liquid fuel 111 that is a raw material of the fuel gas of the fuel cell 200 and the pure water 181 that is supplied as water vapor, or a pipe that flows out the fuel gas to the outside. Etc., that is, a reforming water supply pipe 720, a raw material return pipe 730, a desulfurized fuel supply pipe 740, an air supply pipe 750, a fuel gas outflow pipe 760 and a cooling water pipe 770 in the intermediate pipe section 700. Piping.
For this reason, a pedestal or the like for securing a space for piping at the bottom is not necessary, and the installation space for the reforming unit 300 can be reduced. In particular, piping at the intermediate portion facilitates piping processing, enables raw materials to be brought together in the shortest distance, and facilitates downsizing of the apparatus and improvement of piping work. Further, the reforming unit 300 can be easily arranged in the case when the fuel cell system 100 is unitized.

In the above embodiment, the reforming outer case 610, the pipe outer case 710, and the CO removal outer case 810 constituting the outer case of the unit main body 400 of the reforming unit 300 are formed in a cylindrical shape with a steel plate, particularly a steel plate. It is formed using the plate winding tube.
For this reason, since it can be easily formed to have an arbitrary diameter, there is no inconvenience that, for example, a configuration in which so-called halved members are combined makes it difficult to match due to a difference in inner diameter due to a dimensional tolerance or the like. . Therefore, the exterior case can be easily formed by the plate-wound tube formed in a cylindrical shape with an appropriate plate thickness in advance.

The reforming unit 300 described above is used as the fuel cell system 100.
For this reason, it is possible to provide a small system configuration that can generate power efficiently and stably, and it can be easily used for home use, and the use can be easily expanded.

[Modification of Embodiment]
The aspect described above shows one aspect of the present invention, and the present invention is not limited to each of the above-described embodiments, and within the scope of achieving the objects and effects of the present invention. Needless to say, variations and improvements are included in the content of the present invention. In addition, the specific structure and shape in carrying out the present invention may be used as other structures and shapes within the scope of achieving the object and effect of the present invention.

That is, as described above, the reforming unit 300 of the present invention has been described as being used in the fuel cell system 100, but may be applied as, for example, a hydrogen gas production apparatus used in the fuel cell system 100. .
Further, as described above, the unit configuration is not limited to a configuration in which all of the heat exchange device 640, the vaporizer 630, the CO converter 820, and the CO selective oxidizer 830 are incorporated.
Furthermore, although the CO converter 820 and the CO selective oxidizer 830 are arranged to face each other, for example, the CO converter 820 and the CO selective oxidizer 830 are arranged in a state where they are positioned in the vertical direction, It may be formed in a columnar shape, and the other may be formed in a state of being annularly arranged on one outer peripheral side.

Further, the heat exchanger tube 827 is provided in the CO converter 820, but it may be provided only in the CO selective oxidizer 830 or both.
In addition, as described above, the heat exchange tube 827 is not limited to a cylindrical shape, and may have various cross-sectional shapes such as a polygonal shape, an elliptical cylindrical shape, and a star shape. In addition, the heat exchange pipe 827 is provided in a state in which the axial direction is substantially along the vertical direction, but the present invention is not limited to this. Further, it may be bent, spiraled or branched. In addition, a fin or the like may be provided on the outer peripheral surface of the heat exchange tube 827 that comes into contact with the catalyst to increase the surface area.

In addition, although the configuration in which the CO selective oxidizer 830 is filled with the inert filler is illustrated, the CO converter 820 may be filled with the inert filler. In particular, when the fuel cell 200 that is not damaged even if the fuel gas is supplied to the fuel cell 200 after the CO conversion without using the CO selective oxidizer 830, dew condensation occurs on the upstream side of the CO conversion cooling pipe 824 in the CO converter 820. Since there exists a possibility, it is especially effective for the structure filled with an inert filler in this area | region.
When the CO selective oxidizer 830 having the CO selective oxidation cooling pipe 834 is provided, the pure water 181 has already been heated to a temperature at which no dew condensation occurs and flows into the CO converter 820. Therefore, it is necessary to provide the CO converter 820. Absent.
In addition, with the configuration in which the CO selective oxidizer 830 is not provided, the pure water 181 flows through the CO conversion cooling pipe 824 of the CO converter 820 from the lower part to the upper part in the vertical direction, and upstream of the CO conversion cooling pipe 824. A corresponding position may be filled with an inert filler. That is, the region filled with the inert filler is preferably positioned below the region filled with the CO shift catalyst in the vertical direction. With this configuration, even if dew condensation occurs, it is possible to prevent the inconvenience that moisture drops on the CO conversion catalyst and deactivates it, and more reliably prevents deactivation of the catalyst due to dew condensation. Furthermore, since the specific gravity of alumina particles is generally heavier than the specific gravity of the CO shift catalyst, the CO shift catalyst and the inert filler are mixed by external vibrations without providing the CO shift partition plate 823D. It is possible to prevent inconvenience. Therefore, the member to partition can be abbreviate | omitted, the simplification of a structure can be obtained easily, and the improvement of manufacturability and reduction of cost can be obtained easily.
The same applies to a configuration in which the CO selective oxidizer 830 is provided but the CO selective oxidation cooling pipe 834 is not provided. That is, in the CO transformer 820, condensation may occur at a position corresponding to the upstream side through which the pure water 181 flows, and thus this region is filled with an inert filler.

  Further, the configuration in which the pure water 181 is circulated from the lower part to the upper part in the vertical direction in the CO selective oxidizer cooling pipe 834 of the CO selective oxidizer 830 is illustrated. However, like the CO converter 820, the pure water 181 is circulated from the upper part to the lower part. You may pipe. According to this configuration, the piping of the cooling water pipe 770, the CO selective oxidation cooling water 834, and the CO shift cooling pipe 824 can be easily performed, and assembly manufacturability can be improved.

  The CO selective oxidation cooling pipe 834 is formed with a finer pitch in the region of the filler region 831C2 on the upstream side through which the pure water 181 circulates, but may be formed in the same pitch. .

  Further, in each of the above-described embodiments, as a configuration of supplying the raw material gas to the reforming vessel 622 and outflow of the reforming gas from the reforming vessel 622, for example, the modified portion is not used without using the double-pipe structure circulation portion 622P. Any configuration can be used such as supplying the raw material gas from one end side of the quality container 622 in the axial direction and recovering the reformed gas from the other end side.

Further, although the rectifying pipe 622L is provided, the radiant heat generated by heating the combustion cylinder portion 621A may be used without providing the rectifying pipe 622L.
Furthermore, the turbulent flow part 622L3 may not be provided. Further, the turbulent flow part 622L3 is provided on the outer peripheral surface of the rectifying pipe 622L. For example, the turbulent part 622L3 is provided on the inner peripheral surface of the combustion cylinder part 621A, or between It may be arranged on the surface.

In addition, the burner unit 151 is provided at the upper end of the reforming unit 300. However, the burner unit 151 is not limited to the upper end. For example, the reformer unit 300 may be disposed at the upper portion that is the peripheral surface of the upper case 612. .
Further, although the burner unit 151 is disposed in a state in which the combustion gas is ejected downward, the burner unit 151 is ejected from the outer peripheral side to the inner peripheral side, or from the outer peripheral side to be swirled in the circumferential direction. May be.
Similarly, the exhaust gas port 811C is formed in the lower body portion 811 of the CO removal exterior case 810. For example, the exhaust gas pipe 840 is formed in the bottom plate portion 813 of the CO removal exterior case 810 to form the exhaust gas pipe 840 in the bottom plate portion 813 of the lower body portion 811. You may extend from the lower end side. That is, the bottom plate portion 813 may have a raised bottom shape for the temperature sensor wiring.
Then, the modified outer case 610, the pipe outer case 710, and the CO removal outer case 810 constituting the outer case are formed of the pipe material. However, the present invention is not limited to the structure formed of the pipe material. Various configurations such as processed ones can be used.
Furthermore, as the exterior case, in addition to the modified exterior case 610, the piping exterior case 710, and the CO removal exterior case 810, for example, the modified exterior case 610, the piping exterior case 710, and the CO removal exterior case 810 are a series. Or may be configured by connecting two or four or more members.
Further, as each pipe, a reforming water supply pipe 720, a raw material return pipe 730, a desulfurized fuel supply pipe 740, an air supply pipe 750, a fuel gas outflow pipe 760, and a cooling water pipe 770 are connected to a pipe portion 700 which is an intermediate portion in the vertical direction. Although it was set as the collected structure, what is necessary is just the structure which does not pipe from bottom, such as a lower part and an upper part. Furthermore, it is not limited to the configuration in which the respective pipes are collected in the middle part, and for example, as in the exhaust gas pipe 840, the pipes may be appropriately provided in the upper part or the lower part.

Moreover, although the structure which produces electric power using the liquid fuel 111 as a main raw material was illustrated, for example, raw material gas is used as a main raw material, for example, supply of raw material gas by the state where city gas is not supplied by a disaster etc. May not be obtained, the control device may detect this by using a flow meter, a pressure gauge, or the like, and switch the valves as appropriate to supply the liquid fuel 111 instead of the raw material gas to generate power as described above.
Further, by manual switching of the user, the liquid fuel 111 and the raw material gas are switched and supplied to generate electric power, or the control device automatically operates based on the fuel cost and the power generation amount of the liquid fuel 111 and the raw material gas. You may change the raw material to supply.

  The raw material gas supply pipe 622S is provided with a vaporizer 630 and a raw material return unit 622S2, and the supply path of the liquid fuel 111 and the hydrocarbon raw material gas to the reforming vessel 622 is partially shared. The supply path of the mixed gas to the reforming container 622 and the path having the raw material return pipe 730 for operating the safety valve and allowing the gas phase component in the reforming container 622 to flow out may have different piping configurations. It should be noted that a part of the raw material gas supply pipe 622S can simplify the structure more easily, and can easily obtain a structure in which water vapor is mixed even with different raw materials. Is also preferable because it can be easily obtained.

  Moreover, although the structure which provides the opening for piping in the piping lower recessed part 512 of the lower heat insulation part 510 and the piping upper recessed part 522 of the intermediate heat insulation part 520 was illustrated, for example of the lower heat insulation part 510 or the intermediate heat insulation part 520 It is good also as a structure which provides the recessed part for piping in either. In addition, when providing in either one, it is preferable to set it as the structure provided in the intermediate | middle heat insulation part 520 from the point of assembly property.

  In addition, the specific structure and shape in the implementation of the present invention may be other structures as long as the object of the present invention can be achieved.

  The present invention relates to a reformed gas containing hydrogen gas by heating with a burner in a reforming catalyst using a raw material gas containing a hydrocarbon raw material such as a liquid fuel such as kerosene or a hydrocarbon raw material gas such as liquefied petroleum gas. And the remaining CO can be removed with a catalyst. In particular, it can be effectively used as a reforming unit in a fuel cell system.

1 is a block diagram showing a schematic configuration of a fuel cell system according to the present invention. It is side surface sectional drawing which shows schematic structure of the reforming unit in the said fuel cell system. It is side surface sectional drawing which shows schematic structure in the modification | reformation exterior case of the modification part of the said modification unit. It is a bottom view which shows the modification part of the said modification unit. It is side surface sectional drawing which shows schematic structure of the combustion chamber part of the said modification | reformation part. It is side surface sectional drawing which shows the rectification | straightening pipe | tube of the said modification part. It is a top view which shows the holding | maintenance ring part attached to the outer side cylindrical body of the said modification | reformation container. It is a side view which shows the heat exchange apparatus of the said modification | reformation unit. It is side surface sectional drawing which shows the piping exterior case of the piping part of the said modification | reformation unit. It is a plane sectional view showing the piping exterior case. It is the top view which notched a part which shows the piping state in the piping part of the unit main-body part of the said modification | reformation unit. It is side surface sectional drawing which shows the CO removal exterior case of the CO removal part of the said modification | reformation unit. It is a side view which shows the CO transformer of the said CO removal part. It is the front view which notched a part which shows the said CO transformer. It is a top view which shows the said CO transformer. It is a side view which shows the CO selective oxidizer of the said CO removal part. It is the front view which notched a part which shows the said CO selective oxidizer. It is a top view which shows the said CO selective oxidizer. It is a top view which shows the partition plate of the said CO selective oxidizer.

Explanation of symbols

DESCRIPTION OF SYMBOLS 100 ......... Fuel cell system 111 ......... Liquid fuel 151 ......... Burner unit 200 which is a heating device 200 ......... Fuel cell 210 ......... Blower 300 as an oxygen-containing gas supply means ......... Reforming unit 610 ... ...... Modified exterior case 620 ......... Reformer 710 ......... Pipe exterior case 810 composing casing 810 ... CO removal exterior case 820 composing casing ...... CO remover CO converter 821 as a CO body 821B1 as a casing body 821B1 reformed gas outlet as an outlet 823A gas diffusion area as a diffusion area 823B gas convergence area as a convergence area 823C CO conversion reaction region 827 as a reaction region ......... Heat exchange tube 830 ......... CO selective oxidizer 831 that also functions as a CO remover ......... Case CO selective oxidation vessel 831C1 ... diffusion region 831C2 ... filler region 831C4 ... converging region also can function as a reaction region 831C3 ... converging region as

Claims (6)

A reformer configured to generate a reformed gas containing hydrogen gas (H ₂ ) by heating at least one of a liquid fuel and a hydrocarbon feed gas together with steam in a reforming catalyst in a heating device; A reforming unit in which a CO remover that removes residual carbon monoxide (CO) by bringing the reformed gas generated in a reformer into contact with a catalyst is housed in one housing;
The CO remover is
A case having an accommodating space filled with the catalyst therein, an inlet that communicates with the accommodating space and into which the reformed gas flows, and an outlet that flows out the reformed gas in contact with the catalyst Body,
And a heat exchange pipe provided through the case body in a state in which an inner peripheral surface communicates with the outside of the case body. The reforming unit according to claim 1,
The reforming unit, wherein the heat exchange pipe is provided in a state in which an axial direction is substantially along a vertical direction. The reforming unit according to claim 1 or 2,
The reformer unit, wherein the CO remover is filled with a CO shift catalyst that converts the residual CO as the catalyst. A reforming unit according to any one of claims 1 to 3,
The reformer unit, wherein the CO remover is packed in a position where the catalyst is separated from an opening edge of the inlet and the outlet between the inlet and the outlet. A reforming unit according to any one of claims 1 to 3,
In the housing space of the case body, the reformed gas communicates between the diffusion region communicating with the inflow port, the convergence region communicating with the outflow port, and the diffusion region and the convergence region. A reforming unit characterized in that a reaction zone filled with the catalyst is partitioned. The reforming unit according to any one of claims 1 to 5,
An oxygen-containing gas supply means for supplying an oxygen-containing gas;
A fuel cell that generates power using the reformed gas generated by the reforming unit and the oxygen-containing gas supplied by the oxygen-containing gas supply means;
A fuel cell system comprising:

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