JP2010198896A - Cell stack device, fuel cell module, and fuel cell device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a cell stack device, a fuel cell module, and a fuel cell device in which deterioration of a fuel battery cell can be suppressed, a long lifetime can be realized, and maintenance characteristics are improved. <P>SOLUTION: The device is equipped with the cell stack 3, in which a plurality of the hollow flat plate-like fuel battery cells 2 are aligned and electrically connected in an erected state; a manifold 4 for supplying a fuel gas to the fuel battery cells 2; and a reformer 6 which is arranged upward the cell stack 3 and has a vaporization part and a reforming part equipped with a reforming catalyst on its both sides. Since respective reforming parts and the manifold 4 are connected by fuel gas supply tubes 8, 9 and the fuel gas supply tubes 8, 9 are equipped with fuel gas flow rate adjusting means (flow rate adjusting valves) 10, 11 for adjusting the flow rate of the fuel gas, deterioration in the fuel battery cells 2 can be suppressed, the lifetime of the reformer 6 can be prolonged; and the maintenance characteristics can be improved. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a cell stack device including a reformer for generating fuel gas to be supplied to a fuel cell, a fuel cell module, and a fuel cell device.

  In recent years, various fuel cell modules have been proposed in which fuel cells capable of obtaining power using fuel gas (hydrogen-containing gas) and air (oxygen-containing gas) are housed in a storage container as next-generation energy. (For example, refer to Patent Document 1).

  By the way, in generating a hydrogen-containing gas to be supplied to a fuel cell, for example, a steam reforming method is known in which hydrocarbons such as natural gas are reacted with steam to generate hydrogen, and such reforming is known. Various reformers for carrying out the above have been proposed.

  FIG. 8 is an external perspective view showing a conventional fuel cell module 80, in which a cell stack 84 formed by arranging a plurality of fuel cell cells 82 is accommodated in a storage container 81 to constitute the fuel cell module 80.

  Here, a U-shaped reformer 85 is disposed above the cell stack 84, and the raw fuel supplied from the raw fuel supply pipe 87 is subjected to steam reforming or the like in the reformer 85. A reforming reaction is performed to reform the fuel gas (hydrogen-containing gas). The fuel gas generated in the reformer 85 is supplied to the manifold 83 via the fuel gas supply pipe 86, and the hydrogen-containing gas is supplied from the manifold 83 to each fuel cell 82. With this configuration, the cell stack device 88 is configured.

  By the way, in the fuel cell module 80 described above, the fuel gas generated by the reformer 85 is supplied into the manifold 83 from the fuel gas supply pipe 86 connected to one end side of the manifold 83. Sufficient fuel gas could not be supplied to the fuel cells 82 arranged at a position farther from the supply pipe 86, and the fuel cells 82 might be deteriorated and the power generation efficiency of the cell stack 84 might be lowered.

  Therefore, the present applicant has a vaporization portion provided with a raw fuel supply port through which a raw fuel is supplied at the central portion of the cylindrical container, and the raw fuel that has flowed in from the vaporization portion on both sides of the container. A reformer having a reforming catalyst provided with a reforming catalyst provided with a reforming catalyst for reforming the fuel gas into the fuel gas and provided with a fuel gas delivery port for delivering the fuel gas has been filed earlier.

JP 2007-59377 A

  However, in a reformer having a vaporization part in the center of a cylindrical container and having reforming parts on both sides of the container, purification is performed when the reforming catalyst provided in one reforming part deteriorates. Low-grade fuel gas is supplied to the fuel cell, which may cause deterioration of the fuel cell.

  In this case, it is necessary to replace the reformer even if the other reforming section can normally perform the reforming reaction. As a result, the reformer is replaced when the reformer can still be used, so that the life of the reformer cannot be extended, and there is a problem that the maintainability is poor. .

  Therefore, in the present invention, in a cell stack device including a reformer having a vaporizer at the center of a cylindrical container and having reformers on both sides of the container, the deterioration of the fuel cell is prevented. An object of the present invention is to provide a cell stack device, a fuel cell module, and a fuel cell device that can be suppressed, improve the life of the reformer, and have improved maintainability.

  A cell stack device according to the present invention comprises a cell stack formed by arranging and electrically connecting a plurality of hollow flat fuel cells having gas flow paths therein, and the fuel cells A cell stack apparatus comprising a manifold for fixing a lower end and supplying fuel gas to the fuel cell, and a reformer disposed above the cell stack, wherein the reformer is a cylinder A vaporization part provided with a raw fuel supply port through which the raw fuel is supplied at the center of the container, and reforming the raw fuel flowing from the vaporization part into a fuel gas on both sides of the container Each of the reforming sections and the manifold is connected by a fuel gas supply pipe, and the flow rate of the fuel gas is adjusted to the fuel gas supply pipe. Fuel gas flow for Characterized in that it comprises an integer unit.

  In such a cell stack device, since the fuel gas supply pipe for connecting the reforming section of the reformer and the manifold is provided with fuel gas flow rate adjusting means for adjusting the flow rate of the fuel gas, the reforming section When it is determined that the reforming catalyst provided in the fuel tank has deteriorated, it is possible to suppress (stop) the supply of fuel gas having a low purity to the manifold by operating the fuel gas flow rate adjusting means.

  Thereby, it can suppress (stop) that fuel gas with a low purity degree is supplied to a fuel cell, and it can control that a fuel cell deteriorates.

  In addition, when it can be determined that the reforming catalyst provided in one reforming unit has deteriorated, and the reforming catalyst provided in the other reforming unit can perform a reforming reaction normally. , The fuel gas delivered from one reforming section can be suppressed (stopped) from being supplied to the manifold, and the fuel gas delivered from the other reforming section can be supplied to the fuel cells. . Thereby, even when the reforming catalyst provided in one reforming part deteriorates, the other reforming part can be used as it is, thereby improving the life of the reformer. Can do. Thereby, maintainability can be improved.

  In the cell stack device of the present invention, it is preferable that the vaporization unit includes a water supply port to which water for vaporization and mixing with the raw fuel is supplied.

  In such a cell stack apparatus, since the vaporization section includes a water supply port to which water for vaporization and mixing with the raw material is supplied, a steam reforming reaction with high reforming efficiency is performed in the reformer. be able to.

  In the cell stack device of the present invention, it is preferable that a reforming unit temperature measuring means for measuring the temperature of the reforming unit is disposed in each reforming unit.

  In such a cell stack device, when steam reforming is performed in the reforming unit, the steam reforming reaction is an endothermic reaction, so when the temperature of the reforming unit becomes a predetermined temperature or higher, It can be determined that the reforming catalyst has deteriorated. Here, since the reforming part temperature measuring means for measuring the temperature of the reforming part is arranged in each reforming part, it is possible to accurately grasp the deterioration of the reforming catalyst.

  Since the fuel cell module of the present invention is formed by storing the cell stack device in a storage container, it is possible to suppress deterioration of the fuel cell and improve the life of the reformer. A fuel cell module having improved maintainability can be obtained.

  The fuel cell device of the present invention is a fuel cell device comprising the fuel cell module described above and a control device for controlling the operation of the fuel gas flow rate adjusting means. The fuel gas supplied to the manifold from the one reforming part is stopped when the temperature of the one reforming part measured by the mass part temperature measuring means becomes equal to or higher than a predetermined temperature. The operation of the gas flow rate adjusting means is controlled.

  In such a fuel cell apparatus, when the temperature of one reforming part measured by the reforming part temperature measuring means becomes equal to or higher than a predetermined temperature, the control device is provided with a modification provided for the one reforming part. It is judged that the quality catalyst has deteriorated. When it is determined that the reforming catalyst provided in one reforming portion has deteriorated, fuel gas having a low degree of purification is supplied from one reforming portion to the manifold so as not to be supplied to the manifold. The operation of the fuel gas flow rate adjusting means is controlled so as to stop the fuel gas.

  As a result, it is possible to stop the supply of fuel gas with low purity to the manifold (fuel cell), so that deterioration of the fuel cell can be suppressed and the life of the reformer is improved. In addition, a fuel cell device with improved maintainability can be obtained.

  In addition, the fuel cell device of the present invention includes an alarm device that indicates the replacement time of the reformer, and the control device stops the fuel gas supplied to the manifold from the one reforming unit. It is preferable to control the alarm device to be activated when the fuel gas flow rate adjusting means is activated.

  As described above, when the reforming catalyst included in one reforming unit deteriorates and the reforming catalyst included in the other reforming unit can perform the reforming reaction normally, the reforming catalyst is modified in the other reforming unit. By performing the quality reaction, the fuel cell device can be continuously operated. However, when only one reforming unit is operated, the reforming efficiency is lowered, so that the power generation of the fuel cell device Efficiency may be reduced.

  Therefore, an alarm device indicating the replacement time of the reformer is provided, and the control device operates when the fuel gas flow rate adjusting means is operated so as to stop the fuel gas supplied from one reforming section to the manifold. By controlling the alarm device to indicate the replacement time of the reformer, it is possible to appropriately grasp the replacement time of the reformer.

  The fuel cell device of the present invention is a fuel cell device comprising the fuel cell module described above and a control device for controlling the operation of the fuel gas flow rate adjusting means. Control is performed so that the operation of the fuel cell device is stopped when the temperature of each of the reforming portions measured by the mass portion temperature measuring means becomes equal to or higher than a predetermined temperature.

  In such a fuel cell device, if the reforming catalyst provided in both reforming units deteriorates, the fuel cell device may fail if the fuel cell device is continuously operated.

  Therefore, the control device can suppress the failure of the fuel cell device by controlling the operation of the fuel cell device to stop when the temperature of each reforming section becomes equal to or higher than a predetermined temperature. it can.

  A cell stack device according to the present invention comprises a cell stack formed by arranging and electrically connecting a plurality of hollow flat fuel cells having gas flow paths therein, and the fuel cells A cell stack apparatus comprising a manifold for fixing a lower end and supplying fuel gas to the fuel cell, and a reformer disposed above the cell stack, wherein the reformer is a cylinder A vaporization part provided with a raw fuel supply port through which the raw fuel is supplied at the center of the container, and reforms the raw fuel flowing from the vaporization part into a fuel gas on both sides of the container Each of the reforming units and the manifold is connected by a fuel gas supply pipe, and the flow rate of the fuel gas is adjusted in the fuel gas supply pipe Fuel gas flow adjustment for Since with a stage, it is possible to suppress degradation of the fuel cell, it is possible to improve the life of the reformer, also it is possible to improve the maintainability. In addition, by providing the cell stack device described above, a fuel cell module capable of suppressing deterioration of the fuel cell, improving the life of the reformer, and improving maintainability A fuel cell device can be obtained.

It is an external appearance perspective view which shows an example of the cell stack apparatus of this invention. It is a disassembled perspective view which extracts and shows a part of cell stack apparatus shown in FIG. FIG. 3 is a plan view of the reformer shown in FIG. 2. It is an external appearance perspective view which shows another example of the cell stack apparatus of this invention. It is an external appearance perspective view which shows an example of the fuel cell module of this invention. It is sectional drawing of the fuel cell module shown in FIG. It is a block diagram which shows an example of the fuel cell apparatus of this invention. It is an external appearance perspective view which shows an example of the conventional cell stack apparatus.

  FIG. 1 is an external perspective view of a cell stack apparatus 1 of the present invention. FIG. 2 is an extract of the reformer 6 and fuel gas supply pipes 8 and 9 shown in FIG. 1, and the upper lid of the reformer 6 is removed. FIG. 3 is a plan view of the reformer 6 shown in FIG. 2. In the following drawings, the same numbers are assigned to the same members.

  The cell stack apparatus 1 shown in FIG. 1 is electrically connected with a current collecting member (not shown) interposed between a plurality of fuel cells 2 each having a gas flow path. The lower end of the fuel cell 2 constituting the cell stack 3 is fixed to the manifold 4 that supplies fuel gas to the fuel cell 2 with an insulating adhesive, and the fuel cell 2 (cell The reformer 6 is disposed above the stack 3), and fuel gas supply pipes 8 and 9 connected to the respective fuel gas delivery ports of the reformer 6 are provided at both ends of the manifold 4. Here, the end portion means a side surface orthogonal to the arrangement direction of the fuel cells 2 among the space from the end portion of the cell stack 3 to the end portion of the manifold 4 and the side surface of the manifold 4. At both ends of the cell stack 3, conductive members 5 having current drawing portions 14 for collecting and drawing the current generated by the power generation of the fuel cell 2 to the outside are disposed.

  Here, the fuel battery cell 2 has a hollow flat plate shape having a gas flow path through which fuel gas (hydrogen-containing gas) circulates in the longitudinal direction. On the surface of the support, a fuel-side electrode layer, a solid electrolyte layer, and The solid oxide fuel cell 2 in which the oxygen side electrode layer is provided in order is illustrated.

  The reformer 6 disposed above the cell stack 3 includes a vaporization section 15 provided with a raw fuel supply port through which a raw fuel is supplied to a central portion in a cylindrical container. A raw fuel supply pipe 7 is connected to the mouth. Moreover, it has the reforming part 17 provided with the reforming catalyst 19 on both sides of the container (that is, on both sides of the vaporizing part 15), and on the end side opposite to the vaporizing part 15 of each reforming part 17, A fuel gas delivery port for delivering fuel gas produced by reforming the raw fuel is provided, and fuel gas supply pipes 8 and 9 are connected to the fuel gas delivery port. The vaporizing section 15 and the reforming section 17 are separated by a wall 16 having air permeability. Further, since the reformer 6 and the manifold 4 are connected by the two fuel gas supply pipes 8 and 9, the reformer 6 and the manifold 4 can be firmly connected.

  In the reformer 6 shown in FIGS. 2 and 3, the partition plate 18 is provided in the vaporization section 15 and the reforming section 17 so that the flow path through which the raw fuel flows in the reformer 6 becomes a meandering flow path. Is arranged.

  Here, with the power generation of the cell stack 3, there may be a temperature distribution in which the temperature on the center side of the cell stack 3 is high and the temperature on the end side is low. Therefore, by arranging the partition plate 18 along the width direction of the fuel cell 2, the raw fuel flows from the higher temperature to the lower temperature, and the temperature change of the raw fuel can be suppressed repeatedly. The reforming efficiency can be improved. In addition, by making the partition plate 18 a member having high heat conductivity, heat transfer to the raw fuel and the reforming catalyst 19 can be promoted, and reforming efficiency can be improved.

  In the reformer 6 shown in FIGS. 2 and 3, an example is shown in which one channel structure is formed from the vaporization section 15 to the fuel gas delivery port of the reforming section 17. In this way, by forming one flow path structure from the vaporization section 15 to the fuel gas delivery port of the reforming section 17, it is possible to suppress (prevent) the occurrence of raw fuel drift. Thereby, the raw fuel can be reformed efficiently.

  Note that, based on the size of the reformer 6 and the performance and quantity of the reforming catalyst 19, only a part of the flow path through which the raw fuel flows can be used as a meandering flow path. It can also be configured.

  Accordingly, the flow path through which the raw fuel flows can be lengthened, and the raw fuel can be efficiently reformed in the reformer 6 having the reforming sections 17 on both sides of the vaporizing section 15.

  In addition, as the reforming catalyst 19 provided in the reforming unit 17, it is preferable to use a reforming catalyst excellent in reforming efficiency and durability. For example, a porous catalyst such as γ-alumina, α-alumina, or cordierite is used. A reforming catalyst or the like in which a noble metal such as Ru or Pt or a base metal such as Ni or Fe is supported on a porous carrier can be used. As the reforming catalyst 19, a generally known reforming catalyst can be used as appropriate in accordance with the reforming reaction performed in the reforming unit 17.

  In the cell stack device 1 described above, raw gas such as natural gas and kerosene supplied via the raw fuel supply pipe 7 is reformed, and fuel gas (hydrogen-containing gas) obtained by the reforming reaction is converted into fuel gas. The fuel gas supplied to the manifold 4 through the supply pipes 8 and 9 is supplied to the fuel cell 2. On the other hand, an oxygen-containing gas is supplied from the outside of the fuel cell 2. Thereby, power generation is performed in the fuel battery cell 2.

  By the way, in the reformer 6 provided with the reforming units 17 on both sides of the vaporizing unit 15 as described above, when the reforming catalyst 19 provided in one reforming unit 17 deteriorates, a fuel gas with a low purification degree is produced. The fuel cell 2 is supplied to the fuel cell 2 through the manifold 4, and the fuel cell 2 may be deteriorated.

  Further, even when the reforming catalyst 19 provided in one reforming portion 17 is deteriorated, when the reforming catalyst 19 provided in the other reforming portion 17 is not deteriorated, the other reforming portion 17 is provided. The reforming reaction can be carried out normally at the same time, but the reforming catalyst 19 provided in one reforming portion 17 deteriorates, so that it is necessary to replace the reformer 6, and the life of the reformer 6 is long. There is also a problem that it cannot be realized and maintenance is poor.

  Therefore, in the cell stack apparatus 1 shown in FIG. 1, the flow rate of the fuel gas supplied from the reforming unit 17 to the manifold 4 is adjusted to the fuel gas supply pipes 8 and 9 that connect the reforming unit 17 and the manifold 4. As fuel gas flow rate adjusting means for this purpose, flow rate adjusting valves 10 and 11 are provided, respectively.

  Therefore, for example, when it is determined that the reforming catalyst 19 provided in the reforming unit 17 located on the left side in FIG. 1 has deteriorated, the fuel gas supplied to the manifold 4 is operated by operating the flow rate adjusting valve 10. Can be stopped (or decreased).

  Thereby, it can suppress that fuel gas with a low purity degree is supplied to the fuel cell 2, and can suppress (prevent) that the fuel cell 2 deteriorates. Further, in this case, when the reforming catalyst 19 provided in the reforming unit 17 located on the right side in FIG. 1 can normally perform the reforming reaction, the flow rate adjusting valve 11 is not operated and is continued as it is. By performing the reforming reaction, the fuel gas generated in the reforming unit 17 located on the right side flows through the fuel gas supply pipe 9 and is supplied to the manifold 4 and then supplied to the fuel cell 2. .

  Therefore, the power generation of the fuel cell 2 can be continuously performed without replacing the reformer 6, the life of the reformer 6 can be extended, and the number of replacement operations of the reformer 6 can be reduced. Since it can be reduced, maintainability can be improved.

  Note that the flow rate adjusting valves 10 and 11 may be any valve that can adjust the flow rate of the fuel gas flowing through the fuel gas supply pipes 8 and 9, for example, the flow rate of the fuel gas flowing through the fuel gas supply pipes 8 and 9. An electromagnetic valve that can adjust itself or a butterfly valve that can stop the fuel gas supplied to the manifold 4 via the fuel gas supply pipes 8 and 9 can be used as appropriate.

  By the way, when performing the steam reforming which is an efficient reforming reaction in the reformer 6, it is preferable to supply water to the vaporizing section 15 to vaporize it, and to mix the vaporized water and raw fuel. Therefore, the vaporization unit 15 includes a water supply port to which water for vaporization and mixing with raw fuel is supplied, and a water supply pipe is connected to the water supply port. Is preferred (not shown). Thereby, an efficient steam reforming reaction can be performed in the reforming unit 17, and the power generation efficiency can be improved.

  Here, since the steam reforming reaction is an endothermic reaction, when the reforming catalyst 19 is deteriorated, the degree of the steam reforming reaction is reduced, and the temperature of the reforming unit 17 is increased. Then, after supplying water to the reformer 6, when the temperature of the reforming unit 17 exceeds a predetermined temperature, it can be determined that the reforming catalyst 19 has deteriorated.

  Therefore, the reforming unit temperature measuring means 12 and 13 for measuring the temperature of each reforming unit 17 are arranged in each reforming unit 17. Thereby, the deterioration of the reforming catalyst 19 can be determined based on the temperature measured by the reforming unit temperature measuring means 12 and 13. For example, a thermocouple or a temperature sensor can be used as the reforming part temperature measuring means 12 and 13.

  FIG. 4 is an external perspective view showing another example of the cell stack device of the present invention, in which operating means 21 and 22 for operating the flow rate adjusting valves 10 and 11 are connected to the flow rate adjusting valves 10 and 11. Yes.

  Here, the fuel gas generated by the reforming reaction in the reforming unit 17 and flowing through the fuel gas supply pipes 8 and 9 may become high temperature. Therefore, it is preferable that the flow control valves 10 and 11 are members having high heat resistance.

  However, when using flow control valves 10 and 11 having high heat resistance (for example, butterfly valves), an operating means for operating the flow control valves 10 and 11 is provided separately, and by operating the operation means, It may be desirable to operate the flow control valves 10,11.

  Therefore, in the cell stack apparatus 20 shown in FIG. 4, operating means 21 and 22 for operating the flow rate adjusting valves 10 and 11 are connected to the flow rate adjusting valves 10 and 11, respectively. In this configuration, the fuel gas flow rate adjusting means includes the flow rate adjusting valves 10 and 11 and the operating means 21 and 22. And the flow control valves 10 and 11 can be operated by operating the operation means 21 and 22.

  Thereby, similarly to the above-described cell stack device 1, it is possible to suppress (prevent) the deterioration of the fuel cell 2 and to extend the life of the reformer 6 and to improve the maintainability. Can do. The operation means 21 and 22 only need to be able to operate the flow rate adjusting valves 10 and 11, for example, if the flow rate adjusting valves 10 and 11 are butterfly valves, the butterfly valves can be rotated. FIG. 4 shows a rod-shaped member capable of rotating.

  In addition, operation | movement of said flow regulating valve 10 and 11 and the operation means 21 and 22 is mentioned later.

  FIG. 5 is an external perspective view showing an example of the fuel cell module 23 (hereinafter sometimes referred to as a module) of the present invention in which the above-described cell stack device 20 is stored in the storage container 24. In FIG. 5, the reformer 6 is connected to the inner surface of the upper wall of the storage container 24, and the cell stack device 20 is shown with the reformer 6 removed.

  Further, in the module 23 shown in FIG. 5, a part (front and rear surfaces) of the storage container 24 is removed, and the cell stack device 20 (shown with the reformer 6 removed in FIG. 5) stored inside. The state taken out backward is shown. The operating means 21 and 22 are inserted from the outside of the storage container 24 and connected to the flow rate adjusting valves 10 and 11. Below, the storage container 24 which comprises the module 23 is demonstrated.

  FIG. 6 is a cross-sectional view schematically showing an example of the module 23. In the storage container 24 constituting the module 23, an outer frame of the storage container 24 is formed by an outer wall 25, and a power generation chamber 32 for storing the fuel cell 2 (cell stack 3) is formed therein.

  In such a storage container 24, air or exhaust gas is allowed to flow between the side portion along the arrangement direction of the fuel cells 2 constituting the cell stack 3 and the outer wall of the storage container 24 facing the side portion. The flow path is provided.

  Here, in the storage container 24, a first wall 26 is formed inside the outer wall 25 with a predetermined interval, and a second wall 27 is arranged inside the first wall 26 with a predetermined interval. Furthermore, a third wall 28 is arranged inside the second wall 27 with a predetermined interval.

  Thereby, the space formed by the outer wall 25 and the first wall 26 becomes the first flow path 29, and the space formed by the second wall 27 and the third wall 28 becomes the second flow path 30. Thus, the space formed by the first wall 26 and the second wall 27 becomes the third flow path 31.

  In the storage container 24 shown in FIG. 6, the upper end portion of the first wall 26 is connected to the second wall 27, and the second wall 27 is connected to the upper wall (outer wall 25) of the storage container 24. The upper end of the third wall 28 is connected to the second wall 27.

  In addition, an air supply pipe 33 for supplying air (oxygen-containing gas) into the storage container 24 is connected to the bottom of the storage container 24, and the air supplied from the air supply pipe 33 is an air introduction part 38. Flowing into. Since the air introduction part 38 is connected to the first flow path 29 by the air introduction port 39, the air flowing through the air introduction part 38 flows to the first flow path 29 through the air introduction port 39. The air that has flowed upward in the first flow path 29 flows into the second flow path 30 through the air circulation port 34 provided in the second wall 27. The air flowing downward through the second flow path 30 is supplied into the power generation chamber 32 through the air outlet 37 provided in the third wall 28.

  On the other hand, the exhaust gas discharged from the fuel cell 2 or the exhaust gas generated by burning excess fuel gas on the upper end side of the fuel cell 2 passes through the exhaust gas circulation port 35 provided in the second wall 27. 3 flows into the third flow path 31. The exhaust gas flowing downward through the third flow path 31 flows to the exhaust gas collection unit 40 through the exhaust gas collection port 41 and then passes through the exhaust gas exhaust pipe 42 connected to the exhaust gas collection unit 40 to the outside of the storage container 24. Exhausted.

  Therefore, the air supplied from the air introduction pipe 33 is heat-exchanged with the exhaust gas flowing through the exhaust gas collection unit 40 while flowing through the air introduction unit 38, and then flows through the third flow path 29 while flowing through the first flow path 29. Heat exchange with the exhaust gas flowing through the passage 31 is performed, and heat exchange is performed with the heat in the power generation chamber 32 while flowing through the second flow passage 30.

  6 shows an example in which the exhaust gas exhaust pipe 42 is located inside the air introduction pipe 33, but it is also possible to provide the air introduction pipe 33 so as to be located inside the exhaust gas exhaust pipe 42. Further, the air introduction pipe 33 and the exhaust gas exhaust pipe 42 can be provided with their positions shifted.

  Here, in the module 23 shown in FIG. 6, the heat insulating material 36 (the heat insulating material 36 is indicated by hatching in the drawing) is fixed to the second channel 27 side in the third flow path 31. Has been placed. Thereby, heat exchange between the air flowing through the second flow path 30 and the exhaust gas flowing through the third flow path 31 can be suppressed, and the temperature of the air flowing through the second flow path 30 is prevented from decreasing. it can.

  Thereby, it can suppress that the temperature of the air supplied to the fuel cell 2 falls, and since it can supply high temperature air to the fuel cell 2, it can be set as the module 23 with high electric power generation efficiency.

  The heat insulating material 36 disposed in the third flow path 31 is preferably larger than the outer shape of the side portion along the arrangement direction of the fuel cells 2 constituting the cell stack 3. Thereby, heat exchange between the air flowing through the second flow path 30 and the exhaust gas flowing through the third flow path 31 can be efficiently suppressed.

  In addition to the third flow path 31, the heat insulating material 36 prevents the heat in the storage container 24 from being extremely dissipated and the temperature of the fuel cell 2 (cell stack 3) is lowered to prevent the amount of power generation from being reduced. In FIG. 6, in addition to the third flow path 31, the bottom of the manifold 4, both side surfaces of the fuel cell 2 (cell stack 3), and the upper wall (outer wall 25) of the storage container 24. ) And the reformer 6.

  Here, in the heat insulating material 36 arranged on both side surfaces of the cell stack 3 (fuel cell 2), a hole for allowing air to flow to the fuel cell 2 side is provided corresponding to the air blowing port 37. It has been.

  The air supplied from the air outlet 37 into the power generation chamber 32 flows from the lower end side of the fuel cell 2 toward the upper end side, so that the fuel cell 2 can efficiently generate power.

  By storing the cell stack device 20 in the power generation chamber 32 of the storage container as described above, the module 23 with improved power generation efficiency can be obtained.

  And in this invention, it can be set as the fuel cell apparatus of this invention by accommodating the module 23 mentioned above and the auxiliary machine for operating the cell stack apparatus 20 in an exterior case. The exterior case is divided into upper and lower parts by a partition member, the module 23 is accommodated in the upper room, and the auxiliary equipment for operating the cell stack device 20 is accommodated in the lower room. It can be.

  FIG. 7 is a configuration diagram showing an example of a configuration of a fuel cell system including the fuel cell device of the present invention.

  The fuel cell device of the present invention corresponds to a power generation unit that generates power in FIG. 7, and includes a hot water storage unit for storing hot water after heat exchange, and a circulation pipe for circulating water between these units. A battery system is configured.

  The fuel cell system shown in FIG. 7 includes the above-described fuel cell 2, raw fuel supply means 43 that supplies raw fuel such as natural gas and kerosene, and oxygen-containing gas supply for supplying oxygen-containing gas to the fuel cell 2. Means 44, a reformer 6 for steam reforming with raw fuel and steam, and a heat exchanger 54 for exchanging heat between the exhaust gas and water generated by the power generation of the fuel cell 2 are provided.

  Further, in the fuel cell system shown in FIG. 7, the reformer temperature measurement for measuring the temperatures of the plurality of fuel cells 2, the reformer 6, and the reformers 17 of the reformer 6 described above. Means 12, 13, fuel gas supply pipes 8, 9, flow rate adjusting valves 10, 11 for adjusting the flow rate of the fuel gas flowing through the fuel gas supply pipes 8, 9 are housed in the housing container 24, and the module 23 is configured. In FIG. 7, it is indicated by a two-dot chain line.

  The operating means 21 and 22 for operating the flow rate adjusting valves 10 and 11 are arranged so as to extend outward from the storage container 24 constituting the module 23. Therefore, in FIG. A description will be given by arranging it outside the frame.

  Further, a control device 53 for controlling the operations of the reforming part temperature measuring means 12 and 13 and the operating means 21 and 22 (flow rate adjusting valves 10 and 11) and the operation of an alarm device 58 described later is arranged.

  Further, in the fuel cell device (power generation unit) shown in FIG. 7, the condensed water treatment device 60 for treating the condensed water generated by the heat exchange in the heat exchanger 54, the condensation generated in the heat exchanger 54. A condensed water supply pipe 61 for supplying water to the condensed water treatment device 60 is provided, and the condensed water processed into pure water by the condensed water treatment device 60 is stored in the water tank 50 and then water. It is supplied to the reformer 6 by a pump 59.

  On the other hand, when the amount of condensed water supplied to the condensed water treatment device 60 is small or when the purity of condensed water after being treated by the condensed water treatment device 60 is low, water supplied from the outside (such as tap water) ) Can be processed into pure water and supplied to the reformer 6. In FIG. 7, each external water treatment device is provided as means for processing the water supplied from the outside into pure water.

  Here, as each external water treatment device for supplying water supplied from the outside to the reformer 6, the activated carbon filter device 47 for purifying the water, the reverse osmosis membrane device 48, and the purified water are purified. Among the devices of the ion exchange resin device 49 for making water, at least the ion exchange resin device 49 (preferably all devices) is provided. The pure water generated by the ion exchange resin device 49 is stored in the water tank 50. In the fuel cell device (power generation unit) shown in FIG. 7, a water supply valve 46 for adjusting the amount of water supplied from the outside is provided. Further, the condensed water treatment device 60 and the water tank 50 are connected by a tank connecting pipe 59. In the case where only condensed water is supplied to the reformer 6, the condensed water treatment device 60 and the reformer 6 can be connected via the water pump 51.

  In addition, each external water treatment device and condensate treatment device for treating water supplied to the reformer 6 are surrounded by a one-dot chain line. In addition, the water supply apparatus 45 including the water supply pipe 45, the tank connection pipe 59, and the condensed water supply pipe 61 that connect the reformer 6 and each water treatment apparatus is shown.

  Further, the fuel cell device shown in FIG. 7 is provided at the outlet of the power conditioner 52 and the heat exchanger 54 for switching the DC power generated in the fuel cell 2 to AC power and supplying it to an external load. An outlet water temperature sensor 55 for measuring the water temperature of the water flowing through the outlet 54 (circulated water stream) is provided, and a power generation unit is configured together with the circulation pump 56. And each apparatus which comprises these electric power generation units can be set as a fuel cell apparatus with easy installation, carrying, etc. by accommodating in an exterior case. Although not shown, it is also possible to provide a raw fuel humidifier for humidifying the raw fuel between the raw fuel supply means 43 and the reformer 6. The hot water storage unit includes a hot water storage tank 58 for storing hot water after heat exchange.

  The arrows in the figure indicate the flow directions of the raw fuel, the oxygen-containing gas, and water, and the broken line indicates the main signal path transmitted to the control device 58 or the main signal transmitted from the control device 58. Signal paths are shown.

  Here, an operation method of the fuel cell system shown in FIG. 7 will be described. In performing steam reforming to generate fuel gas used for power generation of the fuel cell 2, main water (pure water) used in the reformer 6 is supplied to the fuel cell 2 in the heat exchanger 54. Condensed water generated by heat exchange between exhaust gas generated during operation and water flowing through the circulation pipe 57 is used. The condensed water generated in the heat exchanger 54 flows through the condensed water supply pipe 61 and is supplied to the condensed water treatment device 60. Condensed water (pure water) processed by the condensed water processing means (ion exchange resin or the like) provided in the condensed water processing apparatus 60 is supplied to the water tank 50 via the tank connecting pipe 59. The water stored in the water tank 50 is supplied to the reformer 6 by the water pump 51, steam reforming is performed with the raw fuel supplied from the raw fuel supply means 43, and the generated fuel gas is the fuel gas. It is supplied to the fuel cell 2 through the supply pipes 8 and 9 and the manifold 4. In the fuel cell 2, power generation is performed using the fuel gas and the oxygen-containing gas supplied from the oxygen-containing gas supply unit 44. By the above series of operations, the water self-sustained operation can be performed by effectively using the condensed water.

  On the other hand, when the amount of condensed water produced is small, or when the purity of condensed water treated by the condensed water treatment device 60 is low, water (such as tap water) supplied from the outside can also be used.

  In this case, first, based on a signal transmitted from the control device 58, the water supply valve 46 (for example, an electromagnetic valve) is opened, and water supplied from the outside such as tap water passes through the water supply pipe 45 to activate the activated carbon filter. Supplied to the device 47. The water treated by the activated carbon filter device 47 is subsequently supplied to the reverse osmosis membrane device 48. The water treated by the reverse osmosis membrane device 48 is continuously supplied to the ion exchange resin device 49, and pure water generated by being treated by the ion exchange resin device 49 is stored in the water tank 50. The pure water stored in the water tank 50 is used for power generation of the fuel cell 3 by the above-described operation.

  When partial oxidation reforming or autothermal reforming is performed in the reformer 6, oxygen-containing gas supply means 44 that supplies an oxygen-containing gas to the fuel cell 2 (module 23) is provided in the reformer 6. An oxygen-containing gas may be supplied.

  By the way, in the case where the reformer 6 has the shape of the reformer 6 having the vaporization section 15 and the reforming sections 11 each having the reforming catalyst on both sides as described above, the reforming of one reforming section 17 is performed. When it is determined that the catalyst 19 has deteriorated, the fuel cell 2 may be deteriorated by supplying the low-purity fuel gas generated in one reforming unit 17 to the fuel cell 2. . In addition, when the reforming catalyst 19 provided in the other reforming unit 17 can normally perform the reforming reaction, the reforming reaction of the one reforming unit 11 is continued, By controlling the fuel gas supplied to the manifold 4 to stop, the life of the reformer 6 can be extended and the maintainability can be improved.

  In particular, when steam reforming is performed in the reformer 6 (the reforming unit 11), the steam reforming reaction is an endothermic reaction. Therefore, when the reforming catalyst 19 deteriorates, the degree of the steam reforming reaction decreases. As a result, the temperature of the reforming unit 17 increases. Then, after supplying water to the reformer 6, when the temperature of the reforming unit 17 exceeds a predetermined temperature, it can be determined that the reforming catalyst 19 has deteriorated.

  Therefore, when the temperature of one reforming unit 17 transmitted from the reforming unit temperature measuring means 12 and 13 for measuring the temperature of each reforming unit 17 exceeds a predetermined temperature, the control device 58 It is determined that the reforming catalyst 19 has deteriorated, and a signal for operating the operation means 21 and 22 is transmitted so as to suppress (stop) the fuel gas supplied to the manifold 4 from one reforming portion 17. . As a result, the flow rate adjusting valves 10 and 11 are operated, the supply of the fuel gas from the reforming unit 17 in which the reforming catalyst 19 has deteriorated can be suppressed, and the deterioration of the fuel cell 2 can be suppressed.

  Although it is possible to continuously supply the fuel gas from the reforming unit 17 where the reforming catalyst 19 has deteriorated at a flow rate that has little influence on the fuel battery cell 2, the fuel cell 2 deteriorates. When the reforming catalyst 19 included in one reforming unit 17 is determined to be deteriorated, the control device 58 supplies the manifold 4 from the one reforming unit 17. It is preferable to send a signal for operating the operating means 21 and 22 so as to stop the fuel gas.

  Specifically, for example, the control device 58 improves the temperature when the temperature of the reforming unit 17 (the reforming unit 17 on the left side in FIG. 4) transmitted from the reforming unit temperature measuring means 12 becomes 800 ° C. or higher. It is determined that the quality catalyst 19 has deteriorated. In this case, the control device 58 transmits a signal for operating the operating means 21 and operates the flow rate adjusting valve 10 to control the fuel gas supplied from the left reforming unit 17 to the manifold 4 to be stopped. Thereby, it can stop that fuel gas with a low purity degree is supplied to fuel cell 2, and it can control that fuel cell 2 deteriorates.

  On the other hand, if the temperature of the reforming unit 17 (the reforming unit 17 on the right side in FIG. 4) transmitted by the reforming unit temperature measuring means 13 in this case is less than 800 ° C., the reforming catalyst 19 deteriorates. It is determined that it is not, and a signal for operating the operating means 22 is not transmitted.

  As a result, when the reforming catalyst 19 of one reforming part 17 deteriorates and the reforming catalyst 19 of the other reforming part 17 does not deteriorate, the fuel gas generated by the other reforming part 17 The fuel cell 2 can be continuously operated by supplying to the fuel cell 2. Therefore, the life of the reformer 6 can be extended and the maintainability can be improved.

  However, when the reforming reaction is performed by only one reforming unit 17, the reforming efficiency is lower than when the reforming reaction is performed by both reforming units 17, and the power generation efficiency of the fuel cell 2 is reduced. May decrease.

  Therefore, the alarm device 58 indicating the replacement time of the reformer 6 is provided, and the control device 53 operates the flow rate adjusting valves 10 and 11 so as to stop the supply of the fuel gas (or the operation means 21, It is preferable to control the alarm device 58 to be activated when the system 22 is activated. Thereby, the replacement time of the reformer 6 can be properly grasped.

  As the alarm device 58, for example, a buzzer or a lamp indicating the replacement time of the reformer 6 can be used as appropriate, and the replacement time of the reformer 6 is indicated on a liquid crystal display or the like provided in the fuel cell device. Display may be performed.

  Furthermore, if it is determined that the reforming catalyst 19 provided in both reforming sections 17 is deteriorated, the fuel cell device may break down if the operation is continued as it is. Therefore, when the temperature of each reforming unit 17 measured by the reforming unit temperature measuring means 12 and 13 is equal to or higher than a predetermined temperature (for example, 800 ° C. or higher), the control device 53 determines the fuel cell. It is preferable to control to stop the operation of the apparatus. Thereby, it can suppress that a fuel cell apparatus fails.

  In this case, the control device 53 can also control the control device 58 to operate so as to indicate the replacement time of the reformer 6 (or the state where the operation of the fuel cell device is stopped).

  In order to stop the fuel cell device, first, the control device 53 transmits a signal for reducing the amount of raw fuel supplied to the reformer 6 to the raw fuel supply means 43. As the raw fuel supply amount decreases, the temperature of the module 23 decreases. When the temperature of the module 23 decreases to the first temperature, the control device 53 performs control to stop the operation of the raw fuel supply means 43 and the operation of the water supply device X (water pump 51). Thereby, the temperature of the module 23 further decreases. When the temperature of the module 23 decreases to a second temperature lower than the first temperature, the control device 53 performs control to stop the operation of the oxygen-containing gas supply unit 44. Thereby, the fuel cell device can be stopped. The temperature of the module 23 can be the center temperature of the cell stack 3 when the cell stack 3 composed of a plurality of fuel cells 2 is stored in the storage container 24. The first temperature and the second temperature can be appropriately set based on the structure of the module 23, the reformer 6 and the like. For example, the first temperature is 300 to 500 ° C., and the second temperature is 50 to 50 ° C. It can be 150 degreeC.

  Although the present invention has been described in detail above, the present invention is not limited to the above-described embodiments, and various modifications and improvements can be made without departing from the scope of the present invention. .

  For example, the control of the operation of the flow rate adjusting valves 10 and 11 of the control device 53 has been described for the case where steam reforming is performed in the reformer 6, but the same applies to the case where partial reforming reforming is performed in the reformer 6. Can be controlled. In this case, the operation control conditions of the flow rate adjusting valves 10 and 11 can be appropriately set in consideration of the supply amount of the oxygen-containing gas supplied to the reforming unit 6 and the like.

1, 20: Cell stack device 2: Fuel cell 3: Cell stack 4: Manifold 6: Reformer 7: Raw fuel supply pipe 8, 9: Fuel gas supply pipe 10, 11: Flow rate adjusting valves 12, 13: Modified Material temperature measuring means 15: vaporization part 17: reforming part 19: reforming catalyst 21, 22: operation means 23: fuel cell module 24: storage container

Claims (7)

  A cell stack in which a plurality of hollow flat fuel cells having gas flow paths are arranged and electrically connected in a standing state, and a lower end of the fuel cells are fixed and the fuel cell A cell stack device comprising a manifold for supplying fuel gas to a cell and a reformer disposed above the cell stack, wherein the reformer is disposed at a central portion of a cylindrical container, A vaporization section provided with a raw fuel supply port through which raw fuel is supplied is provided, and a reforming catalyst for reforming the raw fuel flowing from the vaporization section into fuel gas is provided on both sides of the container. A fuel gas flow rate adjusting means for adjusting the flow rate of the fuel gas to the fuel gas supply pipe having a reforming section, the reforming section and the manifold being connected by a fuel gas supply pipe Characterized by comprising That cell stack device.   The cell stack apparatus according to claim 1, wherein the vaporization unit includes a water supply port to which water for vaporization and mixing with the raw fuel is supplied.   The cell stack apparatus according to claim 2, wherein a reforming unit temperature measuring means for measuring the temperature of the reforming unit is arranged in each reforming unit.   A fuel cell module comprising the cell stack device according to claim 3 housed in a housing container.   5. A fuel cell device comprising the fuel cell module according to claim 4 and a control device for controlling the operation of the fuel gas flow rate adjusting means, wherein the control device measures the reformer temperature. When the temperature of one of the reforming parts measured by the means becomes equal to or higher than a predetermined temperature, the fuel gas flow rate adjusting means is arranged to stop the fuel gas supplied from the one reforming part to the manifold. A fuel cell device that controls the operation of the fuel cell.   In addition to providing an alarm device for indicating the replacement time of the reformer, the control device actuates the fuel gas flow rate adjusting means so as to stop the fuel gas supplied to the manifold from the one reforming section. 6. The fuel cell device according to claim 5, wherein the alarm device is controlled so as to be activated. 5. A fuel cell device comprising the fuel cell module according to claim 4 and a control device for controlling the operation of the fuel gas flow rate adjusting means, wherein the control device measures the reformer temperature. The fuel cell device is controlled so as to stop the operation of the fuel cell device when the temperature of each of the reforming portions measured by the means becomes equal to or higher than a predetermined temperature.

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