JP4911927B2 - Solid oxide fuel cell system - Google Patents

Description

  The present invention relates to a solid oxide fuel cell system including a solid oxide fuel cell that performs a fuel cell power generation reaction using a raw fuel gas composed of hydrocarbons.

  A solid oxide fuel cell using a solid electrolyte as a membrane for conducting oxide ions is known. In such a solid oxide fuel cell, zirconia doped with yttria as a solid electrolyte is generally used, and a fuel electrode for oxidizing fuel gas is provided on one side of such a solid electrolyte, An air electrode for reducing oxygen in the air is provided on the other side. In this solid oxide fuel cell, the operating temperature is as high as 700 to 1000 ° C., and hydrogen, carbon monoxide, hydrocarbons in the fuel gas and oxygen in the air undergo an electrochemical reaction at such a high temperature. Power generation is performed.

  In fuel cell systems that use hydrocarbons as fuel gas, steam is used to reform the fuel gas. Such steam reforming is widely used in phosphoric acid fuel cells and polymer electrolyte fuel cells. It has been. For example, when the fuel gas is methane and reforming is performed using water vapor, the reforming reaction is represented by the following reaction formula (1).

CH ₄ + H ₂ O → 3H ₂ + CO (1)
In the fuel cell system, a steam reforming catalyst is used to promote the steam reforming described above. However, the raw fuel gas contains an odorant and a sulfur compound as an impurity. There is a possibility that the odorant and the sulfur compound deteriorate the steam reforming catalyst. For this reason, in order to prevent the deterioration of the steam reforming catalyst, a desulfurization technique for reducing the odorant and the sulfur compound contained in the raw fuel gas to a low concentration has been proposed. One typical desulfurization technique is the addition of hydrogen to organic sulfur contained in raw fuel gas in the temperature range of 350 to 400 ° C. in the presence of a nickel (Ni) -molybdenum (Mo) catalyst. It decomposes (hydrocracking) and removes hydrogen sulfide (H ₂ S) produced by this decomposition by adsorbing it to zinc oxide (ZnO) in the temperature range of 350 to 400 ° C. It is called the law.

  A desulfurization method has also been proposed in which a desulfurization agent obtained by hydrogen reduction of a copper oxide-zinc oxide-aluminum oxide mixture is used as a desulfurization agent (see, for example, Patent Document 1). In Patent Document 1, the concentration of sulfur contained in the raw hydrocarbon is 5 vol. It can be desulfurized below ppb, and it has been shown that pre-reforming by steam reforming can be operated stably over a long period of time.

  Such a desulfurization agent can adsorb and remove the sulfur compound contained in the hydrocarbon gas even in the absence of hydrogen, but it can extend the life by adding hydrogen (for example, Patent Document 2). This patent document 2 also shows that nickel, iron, etc. may be added to copper and zinc as a desulfurizing agent, and the required amount of desulfurizing agent can be reduced by adding nickel, iron. ing.

JP-A-2-302301 JP 2003-17109 A

  By adding hydrogen in this way, the life of the desulfurization agent can be extended. However, since the raw fuel gas usually does not contain hydrogen, a method for adding hydrogen to the desulfurizer is generally from a reformer. A method is adopted in which a part of a fuel gas (a gas containing hydrogen, which is called crude hydrogen) supplied to the fuel cell is recycled and returned to the desulfurizer. In a phosphoric acid fuel cell and a polymer electrolyte fuel cell, a reformer and a carbon monoxide converter are installed independently, and fuel gas containing hydrogen is supplied to the fuel cell. The contained fuel gas, that is, crude hydrogen, is recycled through a relatively low temperature (for example, 250 ° C. or less) flow path, and in this connection, a structure for recycling the crude hydrogen and returning it to the desulfurizer can be easily added. it can. On the other hand, in the solid oxide fuel cell, the reforming of the fuel gas is performed in the high temperature portion, and the high temperature fuel gas is supplied as it is to the fuel electrode side of the fuel cell. The fuel gas is recycled through a flow path having a relatively high temperature (for example, 500 ° C. or more). In this connection, the branch pipe for extracting the fuel gas containing hydrogen is exposed to a high temperature for a long time. There are problems such as reliability of components related to the heat leakage and heat leakage due to the arrangement of branch pipes. In particular, in a solid oxide fuel cell system of a small size (for example, for home use or small-scale business), it is difficult to minimize heat leakage, and priority is given to making the structure of the high temperature part compact. Therefore, it has been difficult to apply a long-life desulfurization agent that requires the removal of new crude hydrogen from the high temperature part.

  An object of the present invention is to provide a solid oxide fuel cell system capable of easily and inexpensively supplying hydrogen to a desulfurizer in order to extend the life of the desulfurizing agent.

The solid oxide fuel cell system according to claim 1 of the present invention includes a desulfurizer for removing sulfur components contained in a raw fuel gas composed of hydrocarbons, and a raw fuel gas supplied to the desulfurizer. A booster for boosting the pressure, a mixer for mixing at least one of water, water vapor, and air with the desulfurized fuel gas, and a fuel gas reformer disposed downstream of the mixer. A reformer equipped with a fuel reforming catalyst, a fuel electrode and an air electrode, and a fuel gas fed to the fuel electrode side after the reforming reaction and an air fed to the air electrode side A solid oxide fuel cell system comprising: a solid oxide fuel cell that generates power by performing a fuel cell power generation reaction with
The desulfurizer is filled with a desulfurization agent containing copper and zinc, and a fuel gas supplied from the mixer to the reformer is interposed between the mixer and the reformer. A branch return channel is provided for guiding a part to the upstream side of the desulfurizer, a part of the branch return channel is defined by a double pipe structure, and the double pipe structure includes an inner pipe and an inner pipe. The hydrocarbon reforming catalyst is disposed at the end of the double-pipe structure, and the end of the outer tube is heated to 500 ° C. or more through the mounting opening of the high-temperature heat insulating plate. Of the total amount of fuel gas that is inserted into the high-temperature heat insulating section and fed from the mixer to the reformer, 1/200 to 1/20 of the total amount of fuel gas is fed into the inner pipe of the double pipe structure. characterized in that back through the annular space on the upstream side of the desulfurizer between said inner pipe after flowing the outer tube To.

  The solid oxide fuel cell system according to claim 2 of the present invention is characterized in that the hydrocarbon reforming catalyst contains at least one of ruthenium, palladium, rhodium and nickel.

Furthermore, a solid oxide fuel cell system according to claim 3 of the present invention is a desulfurizer for removing sulfur components contained in a raw fuel gas composed of hydrocarbons, and desulfurized by the desulfurizer. A mixer for mixing water or water vapor with fuel gas, a reformer provided on the downstream side of the mixer and provided with a fuel reforming catalyst for reforming the fuel gas, a fuel electrode and air A solid oxide fuel cell having an electrode and generating electricity by performing a fuel cell power generation reaction between a fuel gas supplied to the fuel electrode side after the reforming reaction and air supplied to the air electrode side A solid oxide fuel cell system comprising:
The desulfurizer is filled with a desulfurizing agent containing copper and zinc, and on the upstream side of the reformer and the upstream side of the desulfurizer, a hydrocarbon reforming catalyst for reforming hydrocarbons. The upstream reformer is provided at a high temperature portion of 400 ° C. or more utilizing the exhaust heat of the solid oxide fuel cell, and the mixer is further provided in the mixer. A feed passage for guiding a part of the water or steam to be fed to the upstream side of the upstream reformer is provided, and the amount is 1/10 or less of the water or steam fed to the mixer Is fed to the upstream side of the upstream reformer through the feed flow path .

  According to the solid oxide fuel cell system of the first aspect of the present invention, the mixer mixes at least one of water, steam and air with the fuel gas desulfurized by the desulfurizer, and the reformer Reforms a fuel gas in which at least one of water, water vapor and air is mixed, and the reformed fuel gas is sent to the fuel electrode of the solid oxide fuel cell. When water or steam is mixed in the mixer, the fuel gas undergoes steam reforming in the reformer, and when air is mixed in the mixer, the fuel gas undergoes partial oxidation reforming in the reformer. When water or steam and air are mixed in the mixer, the combustion gas undergoes steam reforming and partial oxidation reforming in the reformer. The raw fuel gas made of hydrocarbon is, for example, one containing methane as a main component (for example, natural gas).

Further, a branch return passage for returning a part of the fuel gas to the upstream side of the desulfurizer is provided, and a part of the branch return passage is defined by a double pipe structure. Since a hydrocarbon reforming catalyst is disposed in the tank, a part of the fuel gas from the mixer is returned to the upstream side of the desulfurizer through the branch return flow path, and hydrocarbon reforming when flowing through the branch return flow path. The reforming of the fuel gas is promoted by the catalyst, and the fuel gas containing hydrogen generated by the reforming is supplied to the desulfurizer, thereby extending the life of the desulfurizing agent of the desulfurizer. In addition, since a booster is provided, by connecting the downstream side of the branch return flow path to the upstream side of the booster, the pressure difference between the downstream side of the mixer and the upstream side of the booster can be used to generate one fuel gas. The part can be returned and can be returned with a relatively simple configuration. In the reforming by the hydrocarbon reforming catalyst, when water or steam is mixed, steam reforming is performed, and when air is mixed, partial oxidation reforming is performed, and water or steam and air are mixed. In some cases, steam reforming and partial oxidation reforming are performed.

Since the end of the outer pipe of the double pipe structure of the branch return passage is inserted into the high temperature heat insulation part heated to 500 ° C. or more through the mounting opening of the high temperature heat insulation plate, desulfurization is performed using the exhaust heat of this fuel cell. The fuel gas returned to the upstream side of the vessel can be heated to promote reforming by the hydrocarbon reforming catalyst , and can be arranged with a relatively simple structure. In addition, there is only one entrance to the high temperature heat insulating part, and heat leakage from the high temperature part can be reduced. Further, since 1/2000 to 1/20 of the total amount of fuel gas fed from the mixer to the reformer is returned to the upstream side of the desulfurizer through the branch return passage, desulfurization of the desulfurizer is performed. Hydrogen necessary for extending the life of the agent can be supplied to the desulfurizer. If the branch return amount of the fuel gas is less than 1/200, a sufficient amount of hydrogen cannot be supplied to the desulfurizer, and there is a possibility that the life of the desulfurizing agent cannot be extended. If it exceeds / 20, the fuel gas is wasted, the power of the booster and the loss of heat increase, and there is a possibility that condensation occurs in the desulfurizer when the operation is stopped. The amount of return of the fuel gas is preferably about 1/100 to 1/20 of the total feed amount in consideration of the progress of the reforming reaction by the hydrocarbon reforming catalyst.

  Furthermore, since the thing containing copper and zinc is used as a desulfurization agent, the sulfur component contained in the raw fuel gas can be lowered to the ppb level, and thereby the power generation state of the solid oxide fuel cell can be prolonged. Can be stabilized over time.

In the solid oxide fuel cell system according to claim 2 of the present invention, since the hydrocarbon reforming catalyst contains at least one of ruthenium, palladium, rhodium and nickel, the upstream side of the desulfurizer The reforming of the fuel gas returned to the fuel can be promoted, and a catalyst suitable for such reforming is obtained. Also, carbon monoxide shift reaction (CO + H ₂ O → CO ₂ + H ₂ ) is promoted in order to remove carbon monoxide contained in the fuel gas returned to the upstream side of the desulfurizer after reforming and increase the concentration of hydrogen. In this case, in addition to the catalyst containing at least one of ruthenium, palladium, rhodium and nickel, a catalyst containing copper and / or chromium may be used, and copper and / or chromium are contained. For example, the catalyst can be coated on the inner surface of a pipe or the like that defines the branch return channel.

Furthermore, according to the solid oxide fuel cell system according to claim 3 of the present invention, the upstream reformer filled with the hydrocarbon reforming catalyst is provided on the upstream side of the desulfurizer and is fed to the mixer. Since an amount of 1/10 or less of the water or steam to be supplied is supplied to the upstream side of the upstream reformer through the feed flow path , steam reforming of the raw fuel gas with water or steam in this upstream reformer And hydrogen can be generated by such reforming. Since the supply amount of water or steam is 1/10 or less of the amount supplied to the reformer, hydrogen of about 0.05 to several vol% is supplied to the desulfurizer. Thus, the life of the desulfurizing agent can be extended. The amount of water or steam supplied to the upstream reformer is preferably 1/200 to 1/20 of the amount supplied to the reformer.

  This upstream reformer is provided at a location where the temperature becomes 400 ° C. or higher using the exhaust heat of the solid oxide fuel cell, and is provided at such a high temperature location to reduce the exhaust heat of the solid oxide fuel cell. The steam reforming in the upstream reformer can be performed effectively. If the temperature is too high, carbon is precipitated due to thermal decomposition of hydrocarbons. For example, in the case of natural gas mainly composed of methane, it is preferably installed at a site of 600 ° C. or lower.

  When water is fed to the upstream reformer, it is desirable to feed a part of the feed flow path through the high temperature part, and thus the upstream in the state of steam by passing through the high temperature part. It can be fed to the side reformer.

  Hereinafter, an embodiment of a solid oxide fuel cell system according to the present invention will be described with reference to the accompanying drawings. FIG. 1 is a system diagram schematically showing the solid oxide fuel cell system of the first embodiment, and FIG. 2 is a sectional view showing a double tube structure in the solid oxide fuel cell system of FIG. It is.

  In FIG. 1, the illustrated solid oxide fuel cell system includes a solid oxide fuel cell 2, a desulfurizer 4, a reformer 6, and a combustion unit 8. The solid oxide fuel cell 2 includes a solid electrolyte 10, and for example, zirconia doped with yttria is used as the solid electrolyte 10. A fuel electrode 12 is provided on one side (left side in FIG. 1) of the solid electrolyte 10, and an air electrode 14 is provided on the other side (right side in FIG. 1). The fuel electrode 12 oxidizes the reformed fuel gas, the air electrode 14 reduces oxygen in the air, and power generation is performed by fuel cell power generation reaction by oxidation on the fuel electrode 12 side and reduction on the air electrode 14 side.

  The desulfurizer 4 is for removing sulfur components, and raw fuel gas composed of hydrocarbons, for example, methane (for example, natural gas) as a main component (for example, natural gas) is sent to the desulfurizer 4 through the fuel supply channel 16. The sulfur component contained in the raw fuel gas is removed in the desulfurizer 4. The fuel gas supply channel 16 is provided with a booster composed of, for example, a booster blower 17, and the raw fuel gas supplied to the desulfurizer 4 is pressurized and supplied to the desulfurizer 4.

  In this desulfurizer 4, it is important to use a desulfurizing agent containing copper and zinc. This desulfurizing agent exhibits its desulfurization ability to the maximum in a temperature range of 200 to 300 ° C. Therefore, it is desirable to dispose the desulfurizer 4 in a portion that falls within such a temperature range in the solid oxide fuel cell system. In this way, the desulfurizer 4 can be kept in a predetermined temperature range by utilizing the exhaust heat of the solid oxide fuel cell system. By using a desulfurizing agent containing copper and zinc, the sulfur component in the fuel gas can be desulfurized to the ppb level, and as a result, the power generation state of the solid oxide fuel cell system can be stabilized over a long period of time. For such a desulfurizing agent, refer to JP-A-2-302303.

  The reformer 6 is for performing a reforming reaction of the desulfurized fuel gas. In this embodiment, the steam reforming of the fuel gas is performed under a steam reforming reaction catalyst (not shown). The fuel gas supply flow path 18 for supplying the desulfurized fuel gas to the reformer 6 is provided with a pure water mixing unit 20 that functions as a mixer, and the pure water from the pure water pump 22 is supplied with pure water. The pure water mixing unit 20 is supplied through the flow path 24, and is mixed with the fuel gas flowing through the fuel gas supply flow path 18 in the pure water mixing unit 20. Further, an evaporator 26 is disposed on the downstream side of the pure water mixing unit 20, the pure water mixed with the fuel gas is evaporated in the evaporator 26, and the fuel gas containing water vapor is supplied to the fuel gas supply passage. 18 to the reformer 6. Note that a water vapor supply means for supplying water vapor to the fuel gas flowing through the fuel gas supply passage 18 may be provided, and the water vapor from this water vapor supply means may be supplied. In this case, the pure water pump 22 and the evaporator 26 can be omitted.

  The reformer 6 is supplied with fuel gas containing steam that has been desulfurized, and a part of the fuel gas is steam reformed by steam under the above-described fuel reforming catalyst. The quality fuel gas is fed to the fuel electrode 12 side of the solid oxide fuel cell 2 through the reformed fuel gas feed channel 28.

  The combustion unit 8 is disposed on the downstream side of the solid oxide fuel cell 2, and the reaction fuel gas discharged from the fuel electrode 12 side of the fuel cell 2 and the air discharged from the air electrode 14 side are fed. Hydrogen gas remaining in the reaction gas is combusted by oxygen in the air, and the combustion exhaust gas is discharged to the outside through the exhaust gas discharge passage 30. In this embodiment, the solid oxide fuel cell 2, the reformer 6, and the combustion unit 8 are installed in the high temperature heat insulating unit 32 at 500 to 1000 ° C., and are configured to be kept in a high temperature state. Yes.

  A regenerator 34 is disposed in the exhaust gas discharge passage 30, and the regenerator 34 heats the air supplied to the air electrode 14 side of the solid oxide fuel cell 2. That is, the air from the supply blower 36 as the air supply means is supplied to the regenerator 34 through the air supply flow path 38, and in the regenerator 34, the air and the combustion exhaust gas flowing through the exhaust gas discharge flow path 30. Heat exchange is performed between them, and the air heated by the heat exchange is supplied to the air electrode 14 side of the solid oxide fuel cell 2 through the air supply passage 40.

  This solid oxide fuel cell system is further configured so that a part of the fuel gas (fuel gas containing water vapor) fed to the reformer 6 is returned to the upstream side of the desulfurizer 4. ing. 1 and 2, in this embodiment, the downstream portion of the evaporator 26 in the fuel gas supply passage 18 and the upstream portion of the booster blower 17 in the fuel gas supply passage 16 are branched back flow. They are connected via a path 42. Since the fuel gas flowing through the fuel gas feed channel 18 is boosted by the booster blower 17, the fluid pressure in the fuel gas feed channel 18 is higher than the fluid pressure in the fuel gas feed channel 16. By connecting as described above via the flow path 42, a part of the fuel gas fed from the evaporator 26 to the reformer 6 passes through the branch return flow path 42, that is, upstream of the booster blower 17, that is, the desulfurizer. 4 is returned to the upstream side.

  The return amount of the fuel gas returned through the branch return flow path 42 is 1/200 to 1/20 of the total feed amount fed to the reformer 6, and by returning such an amount, As will be described later, a desired amount of hydrogen can be supplied to the desulfurizer 4, thereby extending the life of the desulfurizing agent. In order to obtain such a return amount, a throttle member (so-called orifice) for limiting the return flow rate is provided at the branch portion of the branch return channel 42.

  A part of the branch return channel 42 is defined by a double tube structure 44. The double-pipe structure 44 includes an elongated inner tube 46 and an outer tube 48 that covers the outer peripheral side of the inner tube 46, and one end side of the inner tube 46 passes through one end wall 50 of the outer tube 48 and the other end wall. 52, the space on the inner peripheral side of the inner tube 46 defines the inner flow path 54, and the space between the outer peripheral side of the inner tube 46 and the inner peripheral side of the outer tube 48 defines the outer flow path 56. ing. In this double pipe structure 44, the other end side of the inner pipe 46 communicates with the fuel gas supply flow path 18, and a connection portion 58 provided near the one end wall 50 of the outer pipe 48 communicates with the fuel gas supply flow path 16. Then, the fuel gas from the fuel gas supply channel 18 is returned to the fuel gas supply channel 16 through the inner channel 54 and the outer channel 56 as indicated by arrows in FIG.

  In this embodiment, a hydrocarbon reforming catalyst 60 for causing a reforming reaction of fuel gas is provided in the inner channel 54 and the outer channel 56 of the double pipe structure 44. The hydrocarbon reforming catalyst 60 contains at least one of palladium, rhodium and nickel. By using such a hydrocarbon reforming catalyst 60, the inner flow path 54 and the outer flow of the double pipe structure 44 are used. When flowing through the path 56, the fuel gas containing steam is steam reformed, and the reformed fuel gas containing hydrogen by the steam reforming is returned to the fuel gas supply channel 16.

  A carbon monoxide shift catalyst (not shown) is further provided to promote the carbon monoxide shift reaction of the hydrocarbon-reformed fuel gas. This carbon monoxide conversion catalyst may contain, for example, copper or chromium, and the hydrocarbon reforming catalyst 60 described above may be filled with this carbon monoxide conversion catalyst, or the branch return passage 42 is defined. The inner peripheral surface of the pipe to be coated may be coated. The fuel gas subjected to steam reforming is further subjected to carbon monoxide conversion using a carbon monoxide conversion catalyst, whereby the hydrogen concentration in the fuel gas can be increased, and a desired hydrogen amount can be obtained with a small return amount. Can be sent to.

  In this embodiment, a part of the double tube structure 44 described above, specifically, the other side portion (the right portion in FIG. 2) of the outer tube 48 is disposed in the high temperature heat insulating portion 32 of the solid oxide fuel cell system. Is done. A high temperature heat insulating plate 62 for defining the high temperature heat insulating portion 32 is provided, and the solid oxide fuel cell 2 is disposed in the high temperature heat insulating portion 32 (maintained at about 500 to 1000 ° C.) inside the high temperature heat insulating plate 62. Is done. A mounting opening 64 is provided at a predetermined portion of the high temperature heat insulating plate 62, and the other end portion of the outer tube 48 is inserted through the mounting opening 64. By inserting in this way, a part of the double tube structure 44, that is, The other side of the outer tube 48 is heated to 500 ° C. or higher by using the exhaust heat of the solid oxide fuel cell 2, and the portion where steam reforming is performed by the steam reforming catalyst 60 in this way is 500 ° C. or higher. This steam reforming reaction can be further promoted by maintaining the high temperature state. In addition, the double tube structure 44 can make the mounting opening 64 of the high-temperature heat insulating plate 62 one, thereby reducing heat leakage from the high-temperature heat insulating portion 32.

  The operation of the fuel cell system described above will be described as follows. The raw fuel gas (for example, natural gas) made of hydrocarbons is pressurized by the booster blower 17 and then supplied to the desulfurizer 4 through the fuel gas supply channel 16. At this time, a part of the fuel gas fed to the reformer 6 is returned to the fuel gas supply channel 16 through the branch return channel 42, so that the returned fuel gas (steam reforming is performed). Is mixed with the raw fuel gas and fed, and the life of the desulfurizing agent in the desulfurizer 4 can be kept long by the action of hydrogen in the returned fuel gas.

  The desulfurized fuel gas is supplied to the reformer 6 through the fuel gas supply flow path 18, and at the time of this supply, pure water from the pure water pump 22 is supplied in the pure water mixing section 20, The pure water supplied in the evaporator 26 is steamed, and the fuel gas containing the steam is fed through the fuel gas feed channel 18.

  A part of the fuel gas flowing through the fuel gas supply passage 18 (for example, an amount of about 1/100) is returned to the fuel gas supply passage 16 through the branch return passage 42, and when it is returned, the hydrocarbon reforming is performed. Steam reforming is performed by the catalyst 60 and the fuel gas containing hydrogen is returned to the fuel gas supply channel 16. The remainder of the fuel gas is fed to the reformer 6, and the reformed fuel gas steam-reformed by the reformer 6 is fed to the fuel electrode 12 side of the solid oxide fuel cell 2, The air from the feed blower 36 is heated by the regenerator 34 and then fed to the air electrode 14 side. In the solid oxide fuel cell 2, a fuel cell power generation reaction is performed using the reformed fuel gas and oxygen in the air. The reaction fuel gas used for the power generation reaction on the fuel electrode 12 side is sent to the combustion section 8 downstream of the solid oxide fuel cell 2 and air from the air electrode 14 side of the solid oxide fuel cell 2. Is also fed to the combustion section 8, and these reaction fuel gas and air are mixed and burned.

  The combustion exhaust gas combusted in the combustion unit 8 is discharged to the outside through the exhaust gas discharge passage 30, and the exhaust heat is discharged to the air electrode 14 of the solid oxide fuel cell 2 in the regenerator 34 before being discharged to the outside. Used to heat the air supplied to the side.

  This solid oxide fuel cell system has the following structure as compared with the fuel gas return structure in the solid polymer fuel cell system disclosed in Patent Document 2 applied to the solid oxide fuel cell system. Has characteristics. First, in the fuel cell system assumed from the prior art, a part of the fuel gas is returned from the downstream side of the reformer. Therefore, the fluid pressure on the downstream side of the reformer is changed to the upstream side of the booster. Therefore, the pressure loss of the reformer itself and the flow path to the solid oxide fuel cell (fuel gas supply flow path and reformed fuel gas supply flow path) must be reduced. It is necessary to make it smaller. On the other hand, in the fuel cell system described above, a part of the fuel gas is returned upstream of the reformer 6, so that the pressure loss of the reformer 6 and the reformed fuel gas supply flow path 28 is Irrelevant, a part of the fuel gas can be returned to the fuel gas supply passage 16 with the booster blower 17 having a small capacity.

  Secondly, in the fuel cell system assumed from the prior art, in connection with the above, the branch part of the fuel gas, that is, the connection part of the branch return flow path becomes a high temperature part of about 500 to 800 ° C. In order to ensure sufficient durability for the piping for defining the branch return flow path, it is necessary to use an expensive material having sufficient heat resistance. On the other hand, in the fuel cell described above, since the branch portion of the fuel gas is upstream of the reformer 6, the temperature of the connection portion of the branch return passage 42 is about 350 ° C., which is sufficiently durable. Therefore, it is possible to keep the manufacturing cost low without requiring an expensive material.

  In the embodiment described above, a part of the branch return channel 42 is constituted by the double pipe structure 44, but instead of such a double pipe structure 44, a U-shaped pipe structure as shown in FIG. You may make it do. 3, the illustrated U-shaped pipe structure 72 includes a U-shaped pipe 74, one end side (upper side in FIG. 3) communicates with the fuel gas supply passage, and the other end side (lower side in FIG. 3). Is connected to the fuel gas supply flow path, and a part of the fuel gas supplied to the reformer is returned to the upstream side of the booster blower as indicated by an arrow. The U-shaped portion 76 of the U-shaped pipe 74 is disposed in the high-temperature heat insulating portion 32 of the fuel cell system through the high-temperature heat insulating plate 62, and the hydrocarbon reforming catalyst 60 is provided on the inner peripheral surface of the U-shaped portion 76. It is done. Even when such a U-shaped pipe 74 is used, the U-shaped part 76 provided with the hydrocarbon reforming catalyst 60 is disposed in the high-temperature heat insulating part 32, so that the hydrocarbon is heated at a high temperature of 500 ° C. or higher. The reforming reaction by the reforming catalyst 60 can be promoted, and the fuel gas returned through the branch return channel 42 can be steam reformed and returned to the fuel gas supply channel.

  Next, a solid oxide fuel cell system according to a second embodiment will be described with reference to FIG. FIG. 4 is a system diagram schematically showing the solid oxide fuel cell system of the second embodiment. In the second embodiment, the same members as those in the first embodiment described above are the same as those in the first embodiment. A reference number is assigned and description thereof is omitted.

  In FIG. 4, the solid oxide fuel cell system according to the second embodiment includes a solid oxide fuel cell 2, a desulfurizer 4, a reformer 6, and a combustion unit 8 as described above, and a fuel gas. An upstream reformer 82 is provided in the supply flow path 16, and the raw fuel gas flowing through the fuel gas supply flow path 16 flows to the desulfurizer 4 through the upstream reformer 82 and is desulfurized in the desulfurizer 4. The fuel gas is fed to the reformer 6 through the fuel gas feed channel 18.

  The pure water pump 22 is connected to the evaporator 84 via the pure water supply flow path 24, and the discharge side of the evaporator 84 is connected to the first water vapor of the fuel gas supply flow path 18 via the first water vapor flow path 86. In addition to being connected to the mixing unit 88, it is connected to the second water vapor mixing unit 92 of the fuel gas supply channel 16 via the second water vapor channel 90. Accordingly, the pure water from the pure water pump 22 is converted into water vapor in the evaporator 84, and this water vapor is supplied to the fuel gas supply flow path 18 through the first water vapor flow path 86 and also through the second water vapor flow path 90. The fuel gas is supplied to the fuel gas supply channel 16.

  In this embodiment, an amount of 1/10 or less of the steam fed from the evaporator 84 to the reformer 6 is fed to the upstream side of the upstream reformer 82 through the second steam feed channel 90. By supplying such an amount of water vapor, it is possible to supply about 0.05 to several vol% of hydrogen to the desulfurizer 4, thereby extending the life of the hydrocarbon reforming catalyst. Can be achieved. The amount of steam supplied from the evaporator 84 to the upstream reformer 82 is preferably about 1/200 to 1/20 of the amount of steam supplied from the evaporator 84 to the reformer 6.

  Further, in the upstream reformer 82, part of the raw fuel gas is reformed using steam and converted into hydrogen. The upstream reformer 82 is preferably disposed in the high temperature heat insulating portion 32 that is maintained at 400 ° C. or higher by the heat generated by the solid oxide fuel cell 2. By providing in such a high temperature part, the reforming reaction by a catalyst can be advanced. The hydrogen concentration supplied to the desulfurizer 4 should be about 0.05 vol%. Therefore, it is not necessary to use a noble metal catalyst such as ruthenium or platinum having high steam reforming activity, but rather the steam reforming is not high. A catalyst that does not easily cause carbon deposition due to the presence of a sulfur compound is suitable, and a metal oxide catalyst or metal sulfide catalyst that is less expensive than a noble metal can be used.

  The other structure of this solid oxide fuel cell system is substantially the same as the fuel cell system shown in FIGS. 1 and 2 (the branch return flow path and the related structure are omitted), and the description thereof is omitted. Is omitted.

  When the operation of the fuel cell system described above is outlined, the raw fuel gas made of hydrocarbons flows through the fuel gas supply flow path 16, and the pure water supplied from the pure water pump 22 to the evaporator 84 becomes steam. 2 is fed to the fuel gas supply channel 16 through the steam feed channel 90, and the raw fuel gas containing water vapor is supplied to the upstream reformer 82. Thus, when it flows to the upstream reformer 82, a part of the raw fuel gas is steam reformed using steam, and the fuel gas containing hydrogen is supplied to the desulfurizer 4 by steam reforming. The desulfurization process is performed. At this time, hydrogen is contained in the fuel gas, and the life of the desulfurization agent of the desulfurizer 4 can be kept long by the action of this hydrogen.

  The desulfurized fuel gas flows through the fuel gas feed channel 18, and the water vapor evaporated in the evaporator 84 flows through the first water vapor feed channel 86, and the fuel gas containing water vapor is sent to the reformer 6. In the reformer 6, steam reforming is performed using steam, and the reformed fuel gas subjected to steam reforming is supplied to the fuel of the solid oxide fuel cell 2 through the reformed fuel gas supply passage 28. The air is supplied to the electrode 12 side, and the air from the supply blower 36 is heated by the regenerator 34 and then supplied to the air electrode 14 side. In the solid oxide fuel cell 2, as described above, the fuel cell power generation reaction is performed using the reformed fuel gas and oxygen in the air, and power can be generated in the same manner as described above.

  In the second embodiment, the water vapor generated by the evaporator 84 is supplied to the fuel gas supply flow path 18 through the first water vapor supply flow path 86 and the water vapor is supplied to the second water vapor supply flow path. 90, the fuel gas supply flow path 16 is fed to the fuel gas supply flow path 16; however, instead of such a configuration, an evaporator 84 is disposed in the first water vapor feed flow path 86 and the pure water from the pure water pump 22 is disposed. A part of the water vapor is supplied to the evaporator 26, and the water vapor evaporated by the evaporator 84 is supplied to the fuel gas supply flow path 18 through the first water vapor supply flow path 86, and from the pure water pump 22. The remaining portion of the pure water may be flowed through the second water vapor feed channel 90, evaporated while flowing through the second water vapor feed channel 90, and fed to the fuel gas supply channel 16 as water vapor. In such a case, as shown in FIG. 3, a part of the second water vapor supply channel 90 is disposed in the high-temperature heat insulating portion 32 of the solid oxide fuel cell 2, and the exhaust heat of the solid oxide fuel cell 2 is removed. The pure water flowing through the second water vapor feeding flow path 90 can be evaporated and vaporized.

  Further, in this embodiment, all the raw fuel gas from the fuel gas supply passage 16 is supplied to the desulfurizer 4 through the upstream reformer 82. However, instead of such a configuration, the fuel gas supply flow A part of the raw fuel gas flowing through the passage 16 is caused to flow to the desulfurizer 4 through the upstream reformer 82, and the remaining part of the fuel gas flowing through the fuel gas supply channel 16 is not passed through the upstream reformer 82. 4 may be sent.

  As mentioned above, although one embodiment of the solid oxide fuel cell system according to the present invention has been described, the present invention is not limited to this embodiment, and various modifications or corrections can be made without departing from the scope of the present invention. Is possible.

  For example, in the first embodiment described above, pure water is supplied to the fuel gas after the desulfurization treatment and steam reforming is performed by the reformer 6, but instead of pure water (or steam), or In addition to this, air may be supplied. When air is added instead of pure water (steam), the fuel gas containing air is partially oxidized by the fuel reforming catalyst in the reformer 6 and the hydrocarbon reforming catalyst 60 in the branch return passage 42. When reforming is performed and air is supplied in addition to pure water (steam), the fuel gas containing steam and air is carbonized in the fuel reforming catalyst in the reformer 6 and the branch return passage 42. Steam reforming and partial oxidation reforming are performed by the hydrogen reforming catalyst 60.

  In order to confirm the desulfurization effect in the solid oxide fuel cell system according to the first embodiment of the present invention, the following test was performed. In Example 1, the solid oxide fuel cell system shown in FIG. 1 is used, and city gas having the composition shown in Table 1 is supplied as raw fuel gas at 3.5 liters / min. The pressure was increased and supplied.

そして、この都市ガスに純水を供給し、改質器の入口におけるスチーム／カーボン比を２．０とした。脱硫器については約２３０℃の高温部に設置し、脱硫剤として銅及び亜鉛を含むものを３５０ｍｌ用いた。また、改質器及び燃焼器については７００〜９００℃の高温部に設置し、改質器にはアルミナ担体にルテニウムを担持した触媒を用い、改質器において水蒸気改質した改質燃料ガスを固体酸化物形燃料電池の燃料極に供給し、空気をその空気極に供給して燃料電池反応を行った。

Then, pure water was supplied to the city gas, and the steam / carbon ratio at the reformer inlet was set to 2.0. About the desulfurizer, it installed in the high temperature part of about 230 degreeC, and 350 ml of things containing copper and zinc were used as a desulfurization agent. The reformer and combustor are installed in a high temperature part of 700 to 900 ° C., and the reformer uses a catalyst in which ruthenium is supported on an alumina carrier, and the reformed fuel gas reformed by steam in the reformer is used. The fuel cell reaction was carried out by supplying the fuel electrode of a solid oxide fuel cell and supplying air to the air electrode.

  Further, about 1/100 of the total amount of fuel gas fed to the reformer was returned to the upstream side of the booster blower through the branch return passage. A part of the branch return flow path was constituted by a double pipe structure shown in FIG. 2, and the end of this double pipe structure was installed in a high-temperature heat insulating part at about 690 ° C. As the hydrocarbon reforming catalyst, alumina carrying 1.0% by weight of ruthenium was used, and this reforming catalyst was filled in a double tube, and the length of the packed catalyst layer was 220 mm.

  The composition of the fuel gas at the outlet part of the branch return channel when the solid oxide fuel cell system described above is operated (that is, the connection part with the fuel gas supply channel) is as shown in Table 2, It was confirmed that the fuel gas containing water vapor was steam reformed and contained a large amount of hydrogen.

この稼働状態において、脱硫器の出口部における硫黄量を、検出下限１０ｐｐｂの分析装置を用いて分析したが、５０００時間経過後においても硫黄を検出することができなかった。この実験結果から、炭化水素改質触媒を備えた分岐戻し流路を設けるという簡単な構成でもって、長時間にわたって安定して脱硫を行うことが確認できた。燃料ガスに含まれた硫黄が改質器や固体酸化物形燃料電池の燃料極側にスリップすると、スリップした硫黄が改質器や固体酸化物形燃料電池に用いられているニッケルやルテニウムの表面を覆い、それらの性能が低下するが、燃料ガス中の硫黄成分を脱硫することによって、このような性能低下が起こらず、固体酸化物形燃料電池システムを安定して稼働させることが可能となる。

In this operating state, the amount of sulfur at the outlet of the desulfurizer was analyzed using an analyzer with a detection lower limit of 10 ppb, but sulfur could not be detected even after 5000 hours had elapsed. From this experimental result, it was confirmed that desulfurization was stably performed over a long period of time with a simple configuration in which a branch return passage provided with a hydrocarbon reforming catalyst was provided. When sulfur contained in the fuel gas slips to the fuel electrode side of the reformer or solid oxide fuel cell, the slipped sulfur surface of nickel or ruthenium used in the reformer or solid oxide fuel cell However, by desulfurizing the sulfur component in the fuel gas, such a decrease in performance does not occur and the solid oxide fuel cell system can be stably operated. .

  In order to confirm the desulfurization effect in the solid oxide fuel cell system according to the second embodiment of the present invention, the following test was further performed. In Example 2, the solid oxide fuel cell system shown in FIG. 4 is used, the same city gas as Example 1 is supplied at 3.5 liters / min as the raw fuel gas, and the supplied city gas is supplied by a booster blower. The pressure was increased and supplied. An upstream reformer was disposed upstream of the desulfurizer, and 30 ml of the reforming catalyst was charged in the upstream reformer. This upstream reformer was disposed at a high temperature portion of the solid oxide fuel cell via a heat insulating material. This high temperature portion was about 460 ° C. during rated power generation of the solid oxide fuel cell.

  The desulfurizer was the same as in the example, and was installed in a high temperature portion of about 230 ° C., and 350 ml of a desulfurizing agent containing copper and zinc was used. The reformer and combustor are installed in a high temperature part of 700 to 900 ° C., and the reformer uses a catalyst in which ruthenium is supported on an alumina carrier, and the reformed fuel gas reformed by steam in the reformer is used. The fuel cell reaction was carried out by supplying the fuel electrode of a solid oxide fuel cell and supplying air to the air electrode.

  Pure water is supplied from a pure water pump during power generation of the solid oxide fuel cell system, and about 49/50 of the pure water supplied from the pure water pump is converted into water vapor through the first water vapor channel. In addition, about 1/50 of water is supplied as steam to the fuel gas supply channel through the second steam channel, and is sent to the upstream reformer through this fuel gas supply channel. To be paid.

  The solid oxide fuel cell system was operated continuously for 5000 hours under the operating conditions described above, and the amount of sulfur at the outlet of the desulfurizer was detected after 5000 hours. However, sulfur could not be detected. Even after 5000 hours, the raw fuel gas supplied to the desulfurizer contained 0.8 vol% hydrogen.

  From the results of Example 2, it is possible to easily and inexpensively provide a desulfurizer with a simple configuration in which an upstream reformer is provided on the upstream side of the desulfurizer, without requiring a new pump, flow meter, control, or the like. It was confirmed that the life of the desulfurizing agent can be extended.

1 is a system diagram schematically illustrating a first embodiment of a solid oxide fuel cell system according to the present invention. FIG. Sectional drawing which shows the double tube | pipe structure in the solid oxide fuel cell system of FIG. Sectional drawing which shows the example which applied U-shaped piping. The system diagram which shows 2nd Embodiment of the solid oxide fuel cell system according to this invention simply.

Explanation of symbols

DESCRIPTION OF SYMBOLS 2 Solid oxide fuel cell 4 Desulfurizer 6 Reformer 8 Combustion part 12 Fuel electrode 14 Air electrode 16 Fuel gas supply flow path 17 Booster blower 18 Fuel gas supply flow path 20 Pure water mixing part 28 Reformed fuel gas supply Supply flow path 32 High temperature heat insulating part 36 Supply blower 38 Air supply flow path 40 Air supply flow path 42 Branch return flow path 44 Double pipe structure 46 Inner pipe 48 Outer pipe 60 Hydrocarbon reforming catalyst 82 Upstream reformer 86 1st water vapor channel 90 2nd water vapor channel

Claims (3)

A desulfurizer for removing sulfur components contained in the raw fuel gas composed of hydrocarbons, a booster for increasing the pressure of the raw fuel gas fed to the desulfurizer, water in the desulfurized fuel gas, A mixer for mixing at least one of water vapor and air; a reformer provided on the downstream side of the mixer and provided with a fuel reforming catalyst for reforming fuel gas; a fuel electrode; A solid oxide fuel having an air electrode and generating power by performing a fuel cell power generation reaction between a fuel gas fed to the fuel electrode side after the reforming reaction and air fed to the air electrode side A solid oxide fuel cell system comprising a battery,
The desulfurizer is filled with a desulfurization agent containing copper and zinc, and a fuel gas supplied from the mixer to the reformer is interposed between the mixer and the reformer. A branch return channel is provided for guiding a part to the upstream side of the desulfurizer, a part of the branch return channel is defined by a double pipe structure, and the double pipe structure includes an inner pipe and an inner pipe. The hydrocarbon reforming catalyst is disposed at the end of the double-pipe structure, and the end of the outer tube is heated to 500 ° C. or more through the mounting opening of the high-temperature heat insulating plate. Of the total amount of fuel gas that is inserted into the high-temperature heat insulating section and fed from the mixer to the reformer, 1/200 to 1/20 of the total amount of fuel gas is fed into the inner pipe of the double pipe structure. characterized in that back through the annular space on the upstream side of the desulfurizer between said inner pipe after flowing the outer tube Solid oxide fuel cell system. The solid oxide fuel cell system according to claim 1, wherein the hydrocarbon reforming catalyst contains at least one of ruthenium, palladium, rhodium and nickel. A desulfurizer for removing sulfur components contained in the raw fuel gas composed of hydrocarbons, a mixer for mixing water or steam with the fuel gas desulfurized in the desulfurizer, and a downstream of the mixer A fuel gas which is disposed on the side and has a fuel reforming catalyst for reforming the fuel gas, a fuel electrode and an air electrode, and is fed to the fuel electrode side after the reforming reaction And a solid oxide fuel cell system that generates power by performing a fuel cell power generation reaction between the air and the air fed to the air electrode side,
The desulfurizer is filled with a desulfurizing agent containing copper and zinc, and on the upstream side of the reformer and the upstream side of the desulfurizer, a hydrocarbon reforming catalyst for reforming hydrocarbons. The upstream reformer is provided at a high temperature portion of 400 ° C. or more utilizing the exhaust heat of the solid oxide fuel cell, and the mixer is further provided in the mixer. A feed passage for guiding a part of the water or steam to be fed to the upstream side of the upstream reformer is provided, and the amount is 1/10 or less of the water or steam fed to the mixer Is supplied to the upstream side of the upstream reformer through the supply flow path .

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