JP4855688B2 - Fuel cell power generation system - Google Patents

Description

  The present invention relates to a fuel cell power generation system, and more particularly, to a fuel cell power generation system in which deterioration of fuel cell performance is suppressed by adjusting the amount of oxygen supplied to a selective oxidation unit and the amount of oxygen mixed in reformed gas with a simple configuration. Is.

  With the growing awareness of global environmental conservation in recent years, fuel cell power generation systems that generate power with fuel cells that contribute to the suppression of carbon dioxide emissions are attracting attention. As a fuel cell power generation system, a fuel cell that generates hydrogen and oxygen by introducing hydrogen and oxygen, and a reformed gas that introduces a hydrocarbon-based fuel, reforms it, and supplies it to the fuel cell There is known a fuel processing device that generates a fuel. A fuel cell has a catalyst for promoting an electrochemical reaction, and this catalyst often has a property of being poisoned by carbon monoxide. Therefore, in the fuel processor, after reforming the hydrocarbon fuel, the carbon monoxide concentration is reduced by introducing air and reacting with the carbon monoxide in order to reduce the carbon monoxide concentration contained in the fuel. In general, the reformed gas is generated and supplied to the fuel cell. However, even if the reformed gas with a reduced carbon monoxide concentration is supplied to the fuel cell, the catalyst of the fuel cell and the carbon dioxide contained in the reformed gas cause a reverse shift reaction to generate carbon monoxide. Carbon monoxide may poison the fuel cell catalyst and reduce the performance of the fuel cell. To avoid fuel cell performance degradation due to the reverse shift reaction, a small amount of air is mixed into the reformed gas, and the carbon monoxide generated by the reverse shift reaction is combusted with the fuel cell catalyst to poison the catalyst. There is a way to avoid this.

Conventional fuel cell power generation systems are equipped with a selective oxidation air supply line that guides air to be introduced into the fuel processor and a bleed air supply line that guides a small amount of air mixed in the reformed gas. A valve and a blower were provided (see Patent Document 1). In addition, since it is necessary to adjust the air introduced into the fuel processing apparatus and the air mixed into the reformed gas to appropriate amounts, a mass flow controller serving both as a flow meter and a flow control valve has been used as a control valve.
JP 2004-207135 A

  However, since the mass flow controller is expensive, the cost is increased and the external dimensions are large, so that a large installation space is required. In addition, if a blower is provided separately for each line, there is a problem that noise is increased in addition to an increase in cost and space.

  In view of the above-described problems, the present invention has a simple configuration and adjusts the amount of oxygen supplied to the selective oxidation unit and the amount of oxygen mixed in the reformed gas, thereby suppressing a decrease in fuel cell performance. The purpose is to provide.

In order to achieve the above object, a fuel cell power generation system according to the invention described in claim 1 generates a reformed gas g rich in hydrogen by introducing a hydrocarbon fuel h as shown in FIG. The fuel processing apparatus 2 includes a reforming unit 21 that reforms a hydrocarbon-based fuel h to generate a mixed reformed gas r containing carbon monoxide and rich in hydrogen, and a monoxide contained in the mixed reformed gas r. A fuel processor 2 having a selective oxidation unit 23 for generating a reformed gas g by reducing the carbon concentration; a fuel cell 3 for generating power by introducing the reformed gas g; and a reformer generated by the fuel processor 2 A reformed gas line 16 that guides the gaseous gas g to the fuel cell 3; a pressure feeder 33 that pumps the oxygen-containing gas k, and a pressure feeder 33 that has a variable discharge flow rate ; First oxygen-containing gas k1 and second oxygen separated from oxygen-containing gas k A selective oxidizing gas supply line 12 for sending the first oxygen-containing gas k1 of the gas k2 to the selective oxidation unit 23; and a bleed gas supply line 18 for guiding the second oxygen-containing gas k2 to the reformed gas line 16. A bleed gas supply line 18 having a flow rate adjusting mechanism 51 for adjusting the flow rate of the second oxygen-containing gas k2 to be 1/6 to 1/7 of the flow rate of the first oxygen-containing gas k1. The flow rate of the first oxygen-containing gas k1 introduced into the selective oxidation unit 23 is 2 to 10 volumes of the flow rate of the reformed gas g calculated from the flow rate of the hydrocarbon-based fuel h introduced into the reforming unit 21; And a control device 4 that controls the discharge flow rate of the pressure feeder 33 so as to be% .

If comprised in this way, the selective oxidation gas supply which sends 1st oxygen containing gas to the selective oxidation part among the 1st oxygen containing gas and the 2nd oxygen containing gas which were branched from the oxygen containing gas pumped with a pressure feeder Line and a bleed gas supply line that guides the second oxygen-containing gas to the reformed gas line, so that the oxygen-containing gas can be supplied to the selective oxidation unit and the reformed gas line with a single pressure feeder. . Moreover, since the bleed gas supply line having a flow rate adjusting mechanism that adjusts the flow rate of the second oxygen-containing gas to be 1/6 to 1/7 of the flow rate of the first oxygen-containing gas, An appropriate flow rate of oxygen-containing gas can be supplied to the reformed gas line.

  Further, in the fuel cell power generation system according to the second aspect of the present invention, for example, as shown in FIG. 1, in the fuel cell power generation system 1 according to the first aspect, the flow rate adjusting mechanism 51 is a fixed orifice.

  With this configuration, the flow rate of the second oxygen-containing gas can be adjusted in advance with a predetermined ratio to the flow rate of the first oxygen-containing gas with a simpler configuration.

Further, the fuel cell power generation system according to the invention described in claim 3 is introduced into the reforming unit 21 in the fuel cell power generation system 1 described in claim 1 or 2, as shown in FIG. A mass flow controller 32 for measuring the flow rate of the hydrocarbon-based fuel h is provided; the selective oxidizing gas supply line 12 measures the flow rate of the closing means 34 for stopping the flow of the first oxygen-containing gas k1 and the flow rate of the first oxygen-containing gas k1. to possess a flow measuring means 48, the control device 4, the flow signal of the hydrocarbon-based fuel h received from the mass flow controller 32 calculates the flow rate of the reformed gas g produced in fuel processor 2.

  If comprised in this way, since it has a closing means which stops the flow of the 1st oxygen content gas, it can prevent that fuel gas leaks outside when a device fails, and also the 1st oxygen content gas Since the flow rate measuring means for measuring the flow rate is provided, it can be confirmed whether or not the flow rate of the first oxygen-containing gas led to the selective oxidation unit is appropriate.

  A fuel cell power generation system according to a fourth aspect of the present invention is the fuel cell power generation system 1 according to any one of the first to third aspects, for example, as shown in FIG. An activated carbon filter 56 is provided on the suction side.

  If comprised in this way, since the activated carbon filter is provided in the suction side of a pressure feeder, when impurities are contained in oxygen content gas supplied to a selective oxidation part and a reformed gas line, an impurity is entered into a system. Bringing in can be suppressed.

  According to the present invention, since the bleed gas supply line that guides the second oxygen-containing gas having a flow rate of a predetermined ratio to the flow rate of the first oxygen-containing gas to the reformed gas line is provided, it is suitable for one pumping machine. An amount of oxygen-containing gas can be supplied to the selective oxidation unit and the reformed gas line, and with a simple configuration, the amount of oxygen supplied to the selective oxidation unit and the amount of oxygen mixed in the reformed gas are adjusted, A fuel cell power generation system that suppresses the deterioration of the performance of the fuel cell.

  Hereinafter, a fuel cell power generation system according to an embodiment of the present invention will be described with reference to the drawings. In each figure, the same or equivalent devices are denoted by the same reference numerals, and redundant description is omitted. In FIG. 1, a broken line represents a control signal.

  First, the configuration of the fuel cell power generation system 1 will be described with reference to FIG. FIG. 1 is a block diagram illustrating a fuel cell power generation system 1 according to an embodiment of the present invention. The fuel cell power generation system 1 includes a fuel processing device 2, a fuel cell 3, and a control device 4. In addition, a fuel supply line 11, a selective oxidizing gas supply line 12, and a process water supply line 13 are connected to the fuel processing apparatus 2. A reformed gas line 16 is provided between the fuel processor 2 and the fuel cell 3 to connect them. An oxidant gas line 19 is connected to the fuel cell 3. The selective oxidizing gas supply line 12 is branched from the oxygen-containing gas line 10. In addition, a bleed gas supply line 18 that is different from the selective oxidizing gas supply line 12 is branched from the oxygen-containing gas line 10, and is connected to the reformed gas line 16.

  The fuel processing apparatus 2 is an apparatus that introduces a hydrocarbon-based fuel h and process water p and reforms the fuel h to generate a reformed gas g rich in hydrogen. The reformed gas g rich in hydrogen is a gas to be supplied to the fuel cell 3 containing hydrogen in an amount of 40% by volume or more, typically about 75% by volume. The fuel processing apparatus 2 includes a reforming unit 21, a shift conversion unit 22, a selective oxidation unit 23, a steam generation unit 24, and a burner unit 25. Here, each part which comprises the fuel processing apparatus 2 is demonstrated.

  The reforming unit 21 is configured to introduce the fuel h and the reforming steam s and reform the fuel h into the mixed reformed gas r by a steam reforming reaction. The mixed reformed gas r contains hydrogen, carbon monoxide, and carbon dioxide. The mixed reformed gas r typically contains about 40% by volume or more and about 70% by volume of hydrogen, and about 10% by volume of carbon monoxide. The reforming unit 21 is filled with a reforming catalyst, and is configured to promote a steam reforming reaction. Typically, a nickel-based reforming catalyst or a ruthenium-based reforming catalyst is used as the reforming catalyst. The reformer 21 and the shifter 22 are connected so that the mixed reformed gas r generated in the reformer 21 is sent to the shifter 22. In the following description, “connected” includes the case of being connected via a flow path or the like. On the other hand, a fuel supply line 11 for introducing fuel h is connected to the reforming unit 21.

  The shift unit 22 introduces the mixed reformed gas r from the reforming unit 21, causes the carbon monoxide contained in the mixed reformed gas r to undergo a shift reaction with moisture contained in the mixed reformed gas r, and produces carbon dioxide. And hydrogen. The shift unit 22 is filled with a shift catalyst and is configured to promote the shift reaction. As the shift catalyst, typically, an iron-chromium shift catalyst, a copper-zinc shift catalyst, a platinum shift catalyst, or the like is used. The shift converter 22 and the selective oxidation section 23 are connected so that the mixed reformed gas r converted in the shift section 22 is sent to the selective oxidation section 23.

  The selective oxidation unit 23 introduces the mixed reformed gas r transformed from the transformation unit 22, introduces the first oxygen-containing gas k1 from the outside of the system, and remains in the transformed mixed reformed gas r. By the selective oxidation reaction of carbon oxide and the first oxygen-containing gas k1, the carbon monoxide concentration is further reduced from the modified reformed reformed gas r to generate a reformed gas g rich in hydrogen. Yes. As described above, the reformed gas g is a gas containing hydrogen of 40% or more, typically about 75%. The carbon monoxide concentration in the reformed gas g is about 10 ppm or less. The selective oxidation unit 23 is filled with a selective oxidation catalyst. Typically, a platinum-based selective oxidation catalyst, a ruthenium-based selective oxidation catalyst, a platinum-ruthenium-based selective oxidation catalyst, or the like is used as the selective oxidation catalyst. A selective oxidation gas supply line 12 for introducing the first oxygen-containing gas k1 and a reformed gas line 16 for sending the reformed gas g to the fuel cell 3 are connected to the selective oxidation unit 23. .

  The steam generation unit 24 is configured to introduce process water p and evaporate it with heat to generate steam. As heat for evaporating the process water p, it is preferable to use heat generated during the shift reaction in the shift unit 22 or heat generated during the selective oxidation reaction in the selective oxidation unit 23. A heating means such as an electric heater may be provided to use heat generated therefrom. A process water supply line 13 for introducing process water p from outside the system is connected to the water vapor generating unit 24. Further, the steam generating unit 24 is connected to a reforming steam supply line 15 for sending the reforming steam s generated by the steam generating unit 24 to the reforming unit 21. When the reforming steam supply line 15 on the reforming section 21 side is connected to the fuel supply line 11 closest to the reforming section 21, the reforming section is in a state where the fuel h and the reforming steam s are mixed. 21 is suitable. However, the reforming steam supply line 15 may be directly connected to the reforming unit 21.

  The burner unit 25 is configured to introduce a part of the fuel h and the combustion air k4, burn the fuel h, and generate reforming heat to be supplied to the reforming unit 21. Since the reforming reaction in the reforming unit 21 is an endothermic reaction, the reforming unit 21 requires reforming heat. The burner unit 25 has a burner for burning the fuel h. The burner unit 25 is also configured to introduce and burn the anode off gas fa discharged from the fuel cell 3. The anode off gas fa contains hydrogen that was not used for the electrochemical reaction in the fuel cell 3. Typically, the burner unit 25 introduces the fuel h when the fuel cell power generation system 1 is started, burns the fuel h to generate reforming heat, the fuel cell 3 is operated, and the anode off gas fa from the fuel cell 3 is operated. Is discharged, the anode off gas fa is introduced and combusted to generate reforming heat. The combustion exhaust gas e generated after combustion in the burner unit 25 is discharged from the burner unit 25 via the combustion exhaust gas line 26. A combustion gas supply line 14 for introducing the fuel h, an anode offgas line 17 for introducing the anode offgas fa, and a combustion air line 27 for introducing the combustion air k4 are connected to the burner section 25. ing. In addition, a combustion exhaust gas line 26 for discharging the combustion exhaust gas e is connected to the burner portion 25.

  As the fuel h introduced into the reforming unit 21, a gaseous hydrocarbon fuel such as city gas, LPG, digestion gas or the like is typically used. However, liquid hydrocarbon fuels such as methanol, GTL (Gas to Liquid) and kerosene may be used. When a liquid hydrocarbon fuel is used as the fuel h, it is preferable to vaporize it before introducing it into the reforming section 21. The fuel h introduced into the reforming unit 21 and the fuel h introduced into the burner unit 25 may be of the same type or different types.

  Up to this point, the configuration of the fuel processor 2 has been described in detail, but the description will return to the configuration of the fuel cell power generation system 1 again.

  The fuel cell 3 introduces the reformed gas g and the oxidant gas k3, and generates water and heat by generating electricity through an electrochemical reaction between hydrogen in the reformed gas g and oxygen in the oxidant gas k3. It is configured as follows. The fuel cell 3 is typically a polymer electrolyte fuel cell.

  As shown in FIG. 2A, the fuel cell 3 is configured by stacking a plurality of cells CL. A stack of a plurality of cells CL is referred to as a stack, and in the following description, this may be referred to as a “fuel cell stack”. As shown in FIG. 2B, the single cell CL is configured by sandwiching a solid polymer film 301 between a fuel electrode 302 and an oxidant electrode 303 and further sandwiching it between separators 304. The above-described reformed gas g is introduced into the fuel electrode 302, and the oxidant gas k3 is introduced into the oxidant electrode 303. The DC power generated by the fuel cell 3 is transmitted to the power conditioner 5, converted to AC power by the power conditioner 5, and then transmitted to the power load outside the system.

  The reformed gas g and the oxidant gas k3 introduced into the fuel cell 3 are not all used in the electrochemical reaction, and the reformed gas g not used in the reaction is used as the anode off-gas fa as the fuel electrode. The oxidant gas k3 that has been discharged from the reactor and not used for the reaction is discharged from the air electrode as the cathode offgas fc.

  The fuel cell 3 and the selective oxidation unit 23 of the fuel processor 2 are connected by a reformed gas line 16. The fuel cell 3 and the burner unit 25 of the fuel processor 2 are connected by an anode off gas line 17. The fuel cell 3 is connected to an oxidant gas line 19 for introducing the oxidant gas k3. In addition, a cathode offgas line 20 for discharging the cathode offgas fc is connected to the fuel cell 3. Furthermore, the fuel cell 3 is connected to a cooling water line (not shown) for removing heat generated by the electrochemical reaction.

  The fuel supply line 11 is a flow path that guides the hydrocarbon-based fuel h to the reforming unit 21. A blower 31 is disposed in the fuel supply line 11. However, when the fuel h is liquid, the blower 31 is replaced with a pump. A mass flow controller 32 is disposed in the fuel supply line 11 between the blower 31 and the reforming unit 21. The mass flow controller 32 has both the function of a flow meter and the function of a flow control valve. A signal cable is laid between the mass flow controller 32 and the control device 4. The mass flow controller 32 is configured so that the flow rate of the fuel h passing through the mass flow controller 32 can be transmitted to the control device 4 as a signal i1, and the valve opening degree can be adjusted by receiving the signal i2 from the control device 4. Has been.

  A desulfurizer 58 is disposed in the fuel supply line 11 between the blower 31 and the mass flow controller 32. The desulfurizer 58 is configured to adsorb and remove sulfur compounds contained in the fuel h to prevent sulfur poisoning of each catalyst in the fuel processing device 2 and the cells of the fuel cell 3. A combustion gas supply line 14 is branched from the fuel supply line 11 between the desulfurizer 58 and the mass flow controller 32. The other end of the combustion gas supply line 14 is connected to the burner unit 25. A mass flow controller 38 is disposed in the combustion gas supply line 14. A signal cable is laid between the mass flow controller 38 and the control device 4. The mass flow controller 38 can transmit the flow rate of the fuel h passing through the inside thereof to the control device 4 as a signal i3, and can receive the signal i4 from the control device 4 and adjust the valve opening degree. Has been.

  The selective oxidation gas supply line 12 is a flow path that guides the first oxygen-containing gas k <b> 1 from outside the system to the selective oxidation unit 23. The first oxygen-containing gas k1 is typically air. In the following description, the first oxygen-containing gas k1 may be referred to as selective oxidation air k1. The selective oxidizing gas supply line 12 is branched from the oxygen-containing gas line 10, and the oxygen-containing gas line 10 has an activated carbon filter 56, a pressure feeder 33, and a flow rate from upstream to downstream where the oxygen-containing gas k flows. The total 48 and the electromagnetic on-off valve 34 are arranged in the order shown here.

  The activated carbon filter 56 is configured to adsorb impurities (NOx, SOx, etc.) contained in the selective oxidation air k1 and filter the selective oxidation air k1. The activated carbon filter 56 is configured by accommodating an activated carbon sheet in a rectangular parallelepiped case. The activated carbon sheet is made by processing fiber activated carbon into a sheet shape. The activated carbon accommodated in the rectangular parallelepiped case may be, for example, granular or raw fiber other than the sheet shape. However, an activated carbon sheet made by processing fiber activated carbon into a sheet shape having a large geometric surface area from the viewpoint of adsorption speed is preferable. Here, the “sheet form” includes a woven or non-woven fabric or a felt form of fiber activated carbon. Furthermore, it is preferable that the activated carbon sheet is processed into a pleat shape, or a plurality of the activated carbon sheets are stacked and accommodated in a rectangular parallelepiped case.

  The pressure feeder 33 is a device that pumps the oxygen-containing gas k, and typically uses a blower. However, a fan may be used when the required static pressure is low. A power cable (not shown) is connected to the pressure feeder 33, and the pressure feeder 33 is configured such that the number of rotations is controlled in accordance with the power received. The power received by the pressure feeder 33 is typically adjusted by the control device 4 by sending a control signal to the power board (not shown), but for convenience, the pressure feeder 33 is shown in FIG. 4 to receive the signal i5. In the following description, for the sake of convenience, it is assumed that the control signal i5 is exchanged between the pressure feeder 33 and the control device 4.

  The flow meter 48 is a device that measures the flow rate of the selective oxidation air k <b> 1 flowing through the selective oxidation gas supply line 12. A signal cable is laid between the flow meter 48 and the control device 4 so that the flow rate of the selected oxidized air k1 measured by the flow meter 48 can be transmitted to the control device 4 as a signal i6. Yes. The electromagnetic on-off valve 34 is a valve that shuts off the flow of the selective oxidation air k1 flowing through the selective oxidation gas supply line 12. A signal cable is laid between the electromagnetic open / close valve 34 and the control device 4, and the control device 4 can transmit the signal i 7 to the electromagnetic open / close valve 34 to cause the electromagnetic open / close valve 34 to open and close. It is configured.

  The bleed gas supply line 18 branches from the oxygen-containing gas line 10 on the downstream side of the pressure feeder 33. A check valve 59 is disposed in the oxygen-containing gas line 10 immediately upstream of the branching portion. The bleed gas supply line 18 is a flow path that guides the second oxygen-containing gas k 2 to the reformed gas line 16. The second oxygen-containing gas k2 is typically air. In the following description, the second oxygen-containing gas k2 may be referred to as bleed air k2. By introducing the bleed air k2 into the reformed gas line 16, it becomes possible to treat the carbon monoxide generated by the reverse shift reaction in the fuel cell 3 described later. For this reason, the bleed air k2 may be mixed directly into the fuel cell 3 in the vicinity of the connecting portion between the reformed gas line 16 and the fuel cell 3, instead of being strictly mixed into the reformed gas line 16. . Thus, even when the bleed air k2 is directly introduced into the fuel cell 3 in the vicinity of the connection portion between the reformed gas line 16 and the fuel cell 3, the bleed air (second oxygen-containing gas) k2 is used as the reformed gas line 16. It is included in the concept of leading to The bleed gas supply line 18 is provided with a flow rate adjusting mechanism 51 and an electromagnetic on-off valve 42.

  The flow rate adjusting mechanism 51 is a device that adjusts the flow rate of the bleed air k2 to a flow rate of a predetermined ratio with respect to the flow rate of the selectively oxidized air k1. As a predetermined ratio, the flow rate of the bleed air k2 is preferably about 1/6 to 1/7 of the selective oxidation air k1. The flow rate adjusting mechanism 51 is typically a fixed orifice, but may be a Venturi tube. Alternatively, it may be a mechanism that removes the handle of the valve after adjustment as a manual valve (a needle valve is preferable in consideration of the flow rate), and fixes the flow rate ratio of the bleed air k2 to the selective oxidation air k1. When the bleed air k2 can be set to an appropriate flow rate due to the length of the bleed gas supply line 18, unit frictional resistance, curved portion resistance, etc., the bleed gas supply line 18 also serves as a flow rate adjusting mechanism.

  The electromagnetic open / close valve 42 is a valve that blocks the flow of bleed air k <b> 2 flowing through the bleed gas supply line 18. A signal cable is laid between the electromagnetic open / close valve 42 and the control device 4 so that the control device 4 can transmit the signal i8 to the electromagnetic open / close valve 42 to cause the electromagnetic open / close valve 42 to open / close. It is configured.

  The process water supply line 13 is a flow path that guides the process water p to the water vapor generation unit 24. The process water supply line 13 is provided with a pump 35 and a process water shut-off valve 36 from upstream to downstream where the process water p flows. The pump 35 feeds the process water p to the water vapor generator 24, and the process water shutoff valve 36 is configured to shut off the process water p flowing through the process water supply line 13.

  The reformed gas line 16 is a flow path that guides the reformed gas g generated by the selective oxidation unit 23 to the fuel cell 3 as described above. A reformed gas line three-way valve 61 is disposed upstream of the connecting portion 53 of the reformed gas line 16 with the bleed gas supply line 18. A signal cable is laid between the reformed gas line three-way valve 61 and the control device 4. The reformed gas line three-way valve 61 is configured to receive the signal i9 from the control device 4 and to switch the flow path.

  The anode off gas line 17 is a flow path that guides the anode off gas fa discharged from the fuel cell 3 to the burner unit 25. An anode off gas line shut-off valve 62 is disposed on the anode off gas line 17. The anode off gas line shutoff valve 62 is configured to shut off the anode off gas fa flowing through the anode off gas line 17. A signal cable is laid between the anode off-gas line shut-off valve 62 and the control device 4, and the control device 4 sends a signal i 10 to the anode off-gas line shut-off valve 62 to open and close the anode off-gas line shut-off valve 62. It is comprised so that it can be made. A bypass line 63 is connected to the anode off gas line 17 on the downstream side of the anode off gas cutoff valve 62. The other end of the bypass line 63 is connected to the reformed gas line three-way valve 61.

  The oxidant gas line 19 is a flow path that guides the oxidant gas k3 humidified by a humidifier (not shown) to the oxidant electrode of the fuel cell 3. The oxidant gas k3 is typically air. The oxidant gas line 19 is provided with a blower 43 and an oxidant gas shut-off valve 44 from upstream to downstream where the oxidant gas k3 flows. The blower 43 pumps the oxidant gas k3 to the fuel cell 3, and the oxidant gas shut-off valve 44 is configured to shut off the oxidant gas k3 flowing through the oxidant gas line 19. A power cable (not shown) is connected to the blower 43, and the blower 43 is configured such that the rotational speed is controlled in accordance with the power to be received. The power received by the blower 43 is typically adjusted by the power board by the control device 4 sending a control signal to a power board (not shown), but for convenience, the blower 43 is connected to the power board from the control device 4 in FIG. The signal i11 is shown to be received. In the following description, for the sake of convenience, it is assumed that the control signal i11 is exchanged between the blower 43 and the control device 4.

With continued reference to FIG. 1, the operation of the fuel cell power generation system 1 will be described.
When the blower 31 is activated when the fuel cell power generation system 1 is activated, the fuel h is first introduced into the desulfurizer 58 of the fuel supply line 11. The sulfur compound is adsorbed and removed from the fuel h by the desulfurizer 58. The desulfurized fuel h flows in the fuel supply line 11 toward the reforming unit 21 and in the combustion gas supply line 14 toward the burner unit 25. At startup, the mass flow controller 32 receives the signal i2 from the control device 4 and the valve is closed, and the mass flow controller 38 receives the signal i4 from the control device 4 and the valve is open. Therefore, immediately after startup, the fuel h is supplied only to the burner unit 25.

  When the fuel h and the combustion air k4 are introduced into the burner portion 25, the burner is ignited, and the fuel h is burned to generate heat. When reforming heat is generated in the burner unit 25, the signal 4 is transmitted from the control device 4 to the mass flow controller 32, the valve of the mass flow controller 32 is opened, and the fuel h is introduced into the reforming unit 21. On the other hand, the pump 35 is started, and the process water p is introduced into the water vapor generating unit 24. The process water p is received and vaporized by the steam generation unit 24 to become reforming steam s. At the time of start-up, since there is no heat generation from the transformation unit 22 and the selective oxidation unit 23, vaporization heat for vaporizing the process water p is generated by the heating device provided in the water vapor generation unit 24. The reforming steam s generated by the steam generation unit 24 is introduced into the reforming unit 21.

When the fuel h and the reforming steam s are introduced into the reforming unit 21, the reforming unit 21 obtains reforming heat from the burner unit 25 and performs a steam reforming reaction as shown in the following equation (1). The mixed reformed gas r is generated.
CH ₄ + H ₂ O → 3H ₂ + CO (1)
In the present embodiment, methane is used as the fuel h. Further, during the steam reforming reaction, the temperature of the reforming unit 21 reaches about 550 to 800 ° C. The mixed reformed gas r contains about 70% by volume of hydrogen, about 10% by volume of carbon monoxide, and other gases not shown in the above formula (1).

The mixed reformed gas r generated in the reforming section 21 is then sent to the shift section 22 where a shift reaction with water vapor as shown in the following equation (2) is performed, and the mixed reformed gas r in the mixed reformed gas r The carbon monoxide concentration is reduced.
CO + H ₂ O → H ₂ + CO ₂ (2)
During the shift reaction, the temperature of the shift section 22 is about 160 ° C. to 280 ° C. The shift reaction is an exothermic reaction, and heat generated by the shift reaction is supplied to the water vapor generating unit 24. When the heat generated in the transformation unit 22 can cover the vaporization heat of the process water p, the heating unit of the water vapor generating unit 24 is stopped, and when it cannot cover the heating unit, the heating unit is also used. The carbon monoxide concentration in the mixed reformed gas r is reduced to about 5000 to 10000 ppm by the shift reaction in the shift section 22.

The mixed reformed gas r transformed by the transformation unit 22 is then sent to the selective oxidation unit 23. In addition to the mixed reformed gas r, selective oxidation air k1 is introduced into the selective oxidation unit 23 via the selective oxidation gas supply line 12, and a selective oxidation reaction as shown in the following equation (3) is performed. The reformed gas g is produced in which the carbon monoxide concentration in the mixed reformed gas r is further reduced.
2CO + O ₂ → 2CO ₂ (3)
During the selective oxidation reaction, the temperature of the selective oxidation unit 23 is about 100 ° C to 250 ° C. By the selective oxidation reaction in the selective oxidation unit 23, the carbon monoxide concentration in the reformed gas g becomes about 10 ppm or less. The reformed gas g generated in the selective oxidation unit 23 flows through the reformed gas line 16 toward the fuel cell 3.

  The selective oxidation air k <b> 1 introduced into the selective oxidation unit 23 is air purified by the activated carbon filter 56 and is introduced by the pressure feeder 33. The flow rate of the selectively oxidized air k <b> 1 introduced into the selective oxidation unit 23 is measured by the flow meter 48. The flow rate of the selected oxidized air k1 measured by the flow meter 48 is transmitted to the control device 4 as a signal i6, and it is determined whether or not the flow rate is appropriate. Whether or not the flow rate of the selectively oxidized air k1 introduced into the selective oxidation unit 23 is appropriate is determined based on the flow rate of the fuel h introduced into the reforming unit 21. The flow rate of the fuel h introduced into the reforming unit 21 is measured by the mass flow controller 32 and transmitted to the control device 4 as a signal i1. The control device 4 calculates the conversion rate at which the reformed gas g is generated in the fuel processing device 2 from the flow rate of the fuel h introduced into the reforming unit 21, and the generated reformed gas g Then, it is determined whether or not the flow rate of the selected oxidized air k1 measured by the flow meter 48 is appropriate, and the signal i5 is transmitted to the pressure feeder 33 so that the flow rate of the selected oxidized air k1 is appropriate. Control the number of revolutions. As a result, the selective oxidation air k1 having an appropriate flow rate is supplied to the selective oxidation unit 23. The flow rate of the selective oxidation air k1 introduced into the selective oxidation unit 23 is typically 2 to 10% by volume of the flow rate of the reformed gas g, but the lower limit is preferably 2.5% by volume, more preferably It is adjusted to 3% by volume, and the upper limit is preferably 6% by volume, more preferably 5% by volume.

  The air fed by the pressure feeder 33 is divided downstream of the check valve 59 and flows through the bleed gas supply line 18 as bleed air k2. The bleed air k2 passes through the fixed orifice 51 and the electromagnetic on-off valve 42 and then flows into the reformed gas line 16. As described above, the bleed air k2 flowing into the reformed gas line 16 is adjusted to a flow rate of about 1/6 to 1/7 of the flow rate of the selective oxidation air k1 by the fixed orifice 51. In other words, the flow rate of the bleed air k2 flowing into the reformed gas line 16 is typically 0.3 to 1.5% by volume with respect to the flow rate of the reformed gas g, but the lower limit is preferably 0.00. The volume is adjusted to 4% by volume, more preferably 0.5% by volume, and the upper limit is preferably 1.0% by volume, more preferably 0.8% by volume.

  When the reformed gas g is not supplied to the fuel cell 3, the electromagnetic on-off valve 42 is closed and the bleed air k 2 does not flow into the reformed gas line 16. When the fuel cell power generation system 1 is started, the composition of the reformed gas g generated by the fuel processing device 2 is not stable, so that the reformed gas g is not introduced into the fuel cell 3. The control device 4 transmits a signal i9 to the reformed gas line three-way valve 61, and the reformed gas line three-way valve so that the reformed gas g whose composition is not stable bypasses the fuel cell 3 and flows to the bypass line 63. Switch 61 valves. At that time, the control device 4 transmits a signal i8 to the electromagnetic on-off valve 42 to close the electromagnetic on-off valve 42 so that the bleed air k2 does not flow into the reformed gas line 16. Further, the control device 4 sends a signal i10 to the anode off-gas line shut-off valve 62 to close the anode off-gas line shut-off valve 62 so that the reformed gas g having an unstable composition does not flow into the fuel cell 3. Yes. The reformed gas g whose composition is not stable is guided to the burner section 25 through the bypass line 63 and burned in the burner section 25 to generate reforming heat.

  When the composition of the reformed gas g generated in the fuel processing device 2 becomes stable, the control device 4 sends a signal i9 to the reformed gas line three-way valve 61, and the reformed gas g is introduced into the fuel cell 3. Then, the reformed gas line three-way valve 61 is switched. As a result, the reformed gas g is introduced into the fuel electrode of the fuel cell 3. On the other hand, the control device 4 activates the blower 43 by transmitting a signal i11 to the blower 43. As a result, the humidified oxidant gas k3 is introduced into the oxidant electrode of the fuel cell 3. The blower 43 is appropriately adjusted in speed by a signal i11 from the control device 4, and uses an oxidant gas k3 having a flow rate corresponding to the flow rate of the reformed gas g introduced into the fuel cell 3 as an oxidant electrode of the fuel cell 3. Pump.

In the fuel cell 3, an electrochemical reaction is performed by hydrogen in the reformed gas g introduced into the fuel electrode and oxygen in the oxidant gas k3 introduced into the oxidant electrode. In the electrochemical reaction, the reaction shown in the following formula (4) is performed on the fuel electrode side, and the reaction shown in the following formula (5) is performed on the oxidant electrode side.
2H ₂ → 4H ⁺ + 4e ⁻ (4)
O ₂ + 4H ⁺ + 4e ⁻ → 2H ₂ O (5)
Electricity is generated by this electrochemical reaction, heat is generated, and moisture is generated. In further explanation, electric power can be obtained when electrons on the fuel electrode side move to the oxidant electrode side through the external electric circuit. Hydrogen ions on the fuel electrode side pass through the solid polymer membrane and move to the oxidant electrode side, and combine with oxygen to generate moisture. This electrochemical reaction is an exothermic reaction.

  Since the electrode catalyst of the fuel cell 3 is poisoned by carbon monoxide, the concentration of carbon monoxide in the reformed gas g is reduced by the fuel processing device 2. The carbon dioxide in the reformed gas g undergoes a reverse shift reaction, and a trace amount of carbon monoxide is generated. When carbon monoxide is generated by the reverse shift reaction, the electrode catalyst is gradually poisoned by carbon monoxide, and the performance of the fuel cell 3 is reduced. When the reformed gas g is introduced into the fuel cell 3, the control device 4 sends a signal i 8 to the electromagnetic open / close valve 42 to open the electromagnetic open / close valve 42, and bleed air k 2 is supplied to the reformed gas line 16. Let it be introduced. By introducing bleed air k2 into the reformed gas line 16 and burning the carbon monoxide generated at the electrode and the bleed air k2 with the catalyst on the electrode, poisoning of the electrode catalyst due to carbon monoxide is avoided. Yes.

  The electric power generated by the fuel cell 3 is direct-current power, which is transmitted to the power conditioner 5 and converted into alternating-current power, and then transmitted to the power load outside the system and consumed. Further, of the reformed gas g introduced into the fuel cell 3, the gas that has not been used for the electrochemical reaction is discharged from the fuel cell 3 as the anode off-gas fa. The anode off gas fa contains hydrogen and is introduced into the burner section 25 through the anode off gas line 17 where it is burned to generate reforming heat. On the other hand, of the oxidant gas k3 introduced into the fuel cell 3, the gas not used for the electrochemical reaction and the moisture (water vapor) generated by the electrochemical reaction are discharged from the fuel cell 3 as the cathode offgas fc. . The cathode off-gas fc is exhausted out of the system after heat recovery as necessary.

  When the pressure feeder 33 fails, the signal i7 is transmitted from the control device 4 to the electromagnetic opening / closing valve 34, and the electromagnetic opening / closing valve 34 is closed. The mixed reformed gas r to which the selective oxidized air k1 is not supplied contains high-concentration carbon monoxide, but when the electromagnetic on-off valve 34 is closed, the mixed reformed gas r containing high-concentration carbon monoxide. It is possible to prevent r from leaking out of the system.

  As described above, according to the present invention, it is possible to provide the fuel cell power generation system 1 that suppresses the deterioration in performance with a simple configuration. The present inventors have a substantially constant ratio between the flow rate of the selective oxidation air k1 introduced into the selective oxidation unit 23 and the flow rate of the bleed air k2 introduced into the reformed gas line 16, and the fuel introduced into the reforming unit 21. When the flow rate of the selective oxidization air k1 introduced into the selective oxidation unit 23 fluctuates due to the fluctuation of the flow rate of h, the flow rate of the necessary bleed air k2 also fluctuates at a substantially constant ratio, and the present invention has been completed. It is. According to the present invention, the ratio of the flow rates of the selective oxidation air k1 introduced into the selective oxidation unit 23 and the bleed air k2 introduced into the reformed gas line 16 can be adjusted with a simple configuration.

  In the above description, the fuel processing device 2 has been described as having the shift unit 22 (paragraph 0017). However, the carbon monoxide concentration in the reformed gas g can be reduced to a predetermined concentration only by the selective oxidation unit 23. If possible, the metamorphic portion 22 may not be provided. If the transformation part 22 is not provided, the fuel processing apparatus 2 can be made compact.

  In the above description, the fuel cell 3 has been described as a polymer electrolyte fuel cell (paragraph 0025), but may be a fuel cell other than a polymer electrolyte fuel cell such as a phosphoric acid fuel cell.

1 is a schematic block diagram illustrating a fuel cell power generation system according to an embodiment of the present invention. It is a typical perspective view explaining the structure of the fuel cell which comprises a fuel cell power generation system. (A) shows the configuration of the fuel cell stack, and (b) shows the configuration of a single cell.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Fuel cell power generation system 2 Fuel processing apparatus 3 Fuel cell 12 Selective oxidizing gas supply line 16 Reformed gas line 18 Bleed gas supply line 21 Reforming part 23 Selective oxidizing part 33 Pressure feeder 34 Closing means 48 Flow rate measuring means 51 Flow rate adjusting mechanism 56 activated carbon filter g reformed gas h fuel k oxygen-containing gas k1 first oxygen-containing gas k2 second oxygen-containing gas r mixed reformed gas

Claims (4)

A fuel processing device that introduces a hydrocarbon-based fuel to produce a reformed gas rich in hydrogen, and that reforms the hydrocarbon-based fuel to produce a mixed reformed gas containing carbon monoxide and rich in hydrogen. A fuel processor having a mass part and a selective oxidation part that reduces the concentration of carbon monoxide contained in the mixed reformed gas to generate the reformed gas;
A fuel cell for generating power by introducing the reformed gas;
A reformed gas line for guiding the reformed gas generated in the fuel processor to the fuel cell;
A pumping machine for pumping an oxygen-containing gas toward the selective oxidation unit and the reformed gas line, the pumping machine having a variable discharge flow rate ;
A selective oxidant gas supply line for sending the first oxygen-containing gas out of the first oxygen-containing gas and the second oxygen-containing gas branched from the oxygen-containing gas pumped by the pump;
A bleed gas supply line for guiding the second oxygen-containing gas to the reformed gas line, wherein a flow rate of the second oxygen-containing gas is 1/6 to 1 with respect to a flow rate of the first oxygen-containing gas. A bleed gas supply line having a flow rate adjusting mechanism for adjusting the flow rate to / 7 ;
The flow rate of the first oxygen-containing gas introduced into the selective oxidation unit is 2 to 10% by volume of the flow rate of the reformed gas calculated from the flow rate of the hydrocarbon fuel introduced into the reforming unit. And a control device for controlling the discharge flow rate of the pressure feeder to be
Fuel cell power generation system. The flow control mechanism is a fixed orifice;
The fuel cell power generation system according to claim 1. A mass flow controller for measuring the flow rate of the hydrocarbon fuel introduced into the reforming section;
The selective oxidation gas supply line, possess a flow measuring means for measuring the flow rate of the closure means and said first oxygen-containing gas to stop the flow of said first oxygen-containing gas;
The control device calculates a flow rate of the reformed gas generated in the fuel processing device from a flow rate signal of the hydrocarbon fuel received from the mass flow controller;
The fuel cell power generation system according to claim 1 or 2. An activated carbon filter is provided on the suction side of the pump;
The fuel cell power generation system according to any one of claims 1 to 3.

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