WO2011001909A1 - 燃料電池システムの負荷追従運転方法 - Google Patents
燃料電池システムの負荷追従運転方法 Download PDFInfo
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- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
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- H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
- H01M8/0612—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material
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- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
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- C01B2203/1041—Composition of the catalyst
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Definitions
- the present invention relates to a load following operation method for a fuel cell system that generates power using a reformed gas obtained by reforming a hydrocarbon fuel such as kerosene.
- a solid oxide electrolyte fuel cell (Solid Oxide Fuel Cell, hereinafter referred to as SOFC in some cases) system is usually used to reform hydrocarbon fuels such as kerosene and city gas to produce hydrogen-containing gas (reformed gas).
- a reformer for generating and SOFC for electrochemically generating and reacting reformed gas and air are included.
- SOFC is usually operated at a high temperature of 550-1000 ° C.
- SR steam reforming
- POX partial oxidation reforming
- ATR autothermal reforming
- Patent Documents 2 and 3 proposals regarding load following operation of the fuel cell system are made.
- hydrocarbon-based fuel is not reformed to a predetermined composition and the unreformed component is supplied to the SOFC, particularly when higher hydrocarbons such as kerosene are used as the hydrocarbon-based fuel, carbon deposition may occur. It may cause flow path blockage and anode deterioration.
- SOFC system may perform load following operation. That is, there is a case where operation is performed in which the amount of power generated by the SOFC system is changed in accordance with fluctuations in power demand. For example, when the power generation amount is increased, the supply amount of hydrocarbon fuel to the SOFC system may be increased. Even in such a case, carbon may be deposited. Therefore, it is desirable to reliably reform the hydrocarbon fuel even during load following operation. In the techniques disclosed in Patent Documents 2 and 3, improvement is still desired in that reliable reform is performed.
- P f ⁇ 1 (F)
- the maximum electrical output of the fuel cell represents a P M
- a plurality of reforming catalyst layer temperatures T j (j is an integer of 1 to N, where N is an integer of 2 or more), and a hydrocarbon fuel flow rate G j corresponding to each T j , Set
- each G j is a flow rate of the hydrocarbon-based fuel that can be reformed in the reforming catalyst layer at the corresponding reforming catalyst layer temperature T j , and each G j is larger than 0, and G j increases as j increases.
- A) a step of measuring the temperature T of the reforming catalyst layer, B) a reformable flow rate F R is the flow rate of the hydrocarbon-based fuel that can be reformed in the reforming catalyst layer temperature T, the step of employing a G j corresponding to the largest T j below the temperature T, C) wherein the reformable flow rate F R is, when the minimum value F min is smaller than, the step of stopping the power generation in the fuel cell, If D) the reformable flow rate F R is the said minimum value F min or more, Step fuel cell output demand value P D, wherein performs maximum electrical output P M or less value, if step d1, the fuel cell output demand value P D, performing step d2 if exceeds the maximum electrical output P M, d1) using the function F f (P), the hydrocarbon-based fuel required to the fuel cell output demand value P D supplied to the reforming catalyst layer in order to output the fuel cell flow f (P D ) If f (P D) is less than the reformable
- hydrocarbon fuel includes a hydrocarbon fuel having 2 or more carbon atoms.
- FIG. 1 It is a schematic diagram which shows an outline
- the fuel cell system used in the present invention includes a reformer that reforms a hydrocarbon-based fuel to produce a hydrogen-containing gas, and a high-temperature fuel cell.
- the reformer has a reforming catalyst layer.
- the hydrogen-containing gas obtained from the reformer is called reformed gas.
- the reforming catalyst layer is composed of a reforming catalyst that can promote the reforming reaction.
- a high-temperature fuel cell generates power using a hydrogen-containing gas (reformed gas) obtained from a reformer.
- FIG. 1 schematically shows an embodiment of an indirect internal reforming SOFC that can implement the present invention.
- an indirect internal reforming SOFC system will be described, but the present invention can also be applied to an external reforming SOFC system or MCFC system.
- the indirect internal reforming SOFC has a reformer 3 that reforms a hydrocarbon fuel to produce a reformed gas (hydrogen-containing gas).
- the reformer has a reforming catalyst layer 4.
- the indirect internal reforming SOFC has an SOFC 6 that generates electric power using the reformed gas, and also has a combustion region 5 in which anode off-gas discharged from the SOFC (particularly its anode) is combusted.
- the indirect internal reforming SOFC has a reformer, a solid oxide fuel cell, and a housing 8 that houses a combustion region.
- Indirect internal reforming SOFC refers to the housing (module container) 8 and the equipment contained therein.
- an igniter 7 that is an ignition means for igniting the anode off-gas is provided, and the reformer includes an electric heater 9.
- Each supply gas is preheated as necessary and then supplied to the reformer or SOFC.
- the indirect internal reforming SOFC is connected with a water vaporizer 1 equipped with an electric heater 2, and a pipe for supplying hydrocarbon fuel to the reformer is connected in the middle of the connecting pipe.
- the water vaporizer 1 generates water vapor by heating with the electric heater 2. Water vapor can be superheated appropriately in the water vaporizer or downstream thereof and then supplied to the reforming catalyst layer.
- air for partial oxidation reforming reaction
- air can be supplied to the reforming catalyst layer, but here, air can be supplied to the reforming catalyst layer after preheating with a water vaporizer.
- Water vapor can be obtained from the water vaporizer, and a mixed gas of air and water vapor can be obtained.
- Hydrocarbon fuel is mixed with hydrocarbon fuel and supplied to the reformer 3, particularly the reforming catalyst layer 4.
- hydrocarbon-based fuel can be appropriately vaporized and then supplied to the reforming catalyst layer.
- the reformed gas obtained from the reformer is supplied to the SOFC 6, particularly the anode thereof. Although not shown, air is appropriately preheated and supplied to the SOFC cathode.
- the combustible component in the anode off gas (gas discharged from the anode) is burned by oxygen in the cathode off gas (gas discharged from the cathode) at the SOFC outlet.
- ignition can be performed using the igniter 7.
- the outlets of both the anode and the cathode are opened in the module container 8.
- the combustion gas is appropriately discharged from the module container.
- Reformer and SOFC are accommodated in one module container and modularized.
- the reformer is disposed at a position where heat can be received from the SOFC. For example, if the reformer is disposed at a position where it receives heat radiation from the SOFC, the reformer is heated by heat radiation from the SOFC during power generation.
- the reformer is preferably disposed at a position where radiation heat can be directly transferred from the SOFC to the outer surface of the reformer. Therefore, it is preferable that a shielding object is not substantially disposed between the reformer and the SOFC, that is, a gap is provided between the reformer and the SOFC. Further, it is preferable to shorten the distance between the reformer and the SOFC as much as possible.
- the reformer 3 is heated by the combustion heat of the anode off gas generated in the combustion region 5. Further, when the SOFC is at a higher temperature than the reformer, the reformer is also heated by radiant heat from the SOFC.
- the reformer may be heated by heat generated by reforming. If the reforming is partial oxidation reforming or autothermal reforming (autothermal reforming) and the heat generation by the partial oxidation reforming reaction is greater than the endothermic reaction by the steam reforming reaction, Fever accompanies.
- a function F f () of an electric output P of a fuel cell and a flow rate F of a hydrocarbon-based fuel that needs to be supplied to the reforming catalyst layer in order to output the electric output P by the fuel cell in advance.
- F is uniquely determined for a certain electric output P, and one or a plurality of P can exist for a certain F.
- the current and the fuel utilization rate for a certain electric output P are determined in advance by preliminary experiments or simulations so that the power generation efficiency is as high as possible while maintaining the SOFC at a temperature at which power generation is preferable.
- F for a certain electric output P is uniquely determined.
- the flow rate of the hydrocarbon-based fuel with respect to a certain electric output P or less is made constant as shown in FIG. In this case, there are a plurality of Ps for a certain F.
- the flow rate of fluid supplied to the indirect internal reforming SOFC other than the hydrocarbon-based fuel, the input / output of electricity to the indirect internal reforming SOFC other than the output of the fuel cell, in advance are set to the electric output P.
- a steam / carbon ratio ratio of the number of moles of water molecules to the number of moles of carbon atoms in the gas supplied to the reforming catalyst layer
- the air flow rate supplied to the reformer should be determined so that the oxygen / carbon ratio (ratio of the number of moles of oxygen molecules to the number of moles of carbon atoms in the gas fed to the reforming catalyst layer) is a predetermined value. Can do.
- the SOFC is preferably maintained at a temperature capable of generating electricity. However, it can be determined by preliminary experiments and simulations so that the power generation efficiency is as high as possible. In this way, when the output of the fuel cell is set to a certain value P, these flow rates and electrical inputs / outputs can be determined using a previously obtained function.
- the P M the maximum electrical output of the fuel cell.
- P M is beforehand determined as a specification of the fuel cell system.
- a plurality of temperatures T j of the reforming catalyst layer (j is an integer of 1 or more and N or less, where N is an integer of 2 or more), a hydrocarbon fuel flow rate G j corresponding to each T j , Is set in advance.
- each G j is the flow rate of the hydrocarbon-based fuel that can be reformed in the reforming catalyst layer at the corresponding reforming catalyst layer temperature T j .
- Each G j is greater than zero. This means that for all j is 0 ⁇ G j. Further, as j increases, G j has the same value or increases. That is, G j ⁇ G j +1 (where j is an integer from 1 to N ⁇ 1).
- G j (G N ) when j is N is equal to or greater than F max . That is, G N ⁇ F max .
- GN is the flow rate of the hydrocarbon-based fuel that can be reformed in the assumed maximum temperature reforming catalyst layer, that is, the maximum value of the reformable hydrocarbon-based fuel. If G N ⁇ F max , the hydrocarbon fuel having a flow rate of F max cannot be reformed, so the fuel cell system is naturally designed so that G N ⁇ F max .
- the processes A to D are preferably performed repeatedly, that is, the process A, the process B, and the process C or D are repeated in this order, so that the reforming can be performed more reliably.
- the deterioration of the anode can be prevented more reliably.
- Step A is used to determine the reformable flow rate F R described later is carried out in order to know the temperature T of the reforming catalyst layer. It is preferable to start the process A within the shortest possible time from the start of the load following operation. It is preferable to start the process A immediately after starting the load following operation. If the temperature of the reforming catalyst layer is monitored (continuous measurement) before the start of the load following operation, the temperature may be monitored continuously.
- thermocouple An appropriate temperature sensor such as a thermocouple can be used for temperature measurement.
- the flow rate of the hydrocarbon-based fuel that can be reformed in the reforming catalyst layer at the temperature T corresponds to the largest T j below the temperature T.
- G j is used. That is, among the preset T j , the largest T j is selected in the range below the measured temperature T. Then, the correspondence relationship between T j and G j set in advance, obtains a G j corresponding to the selected T j, for the G j and reformable flow rate F R.
- Reformable flow rate F R calculated in step B is, if the minimum value F min is smaller than, stopping the power generation in the fuel cell. That is, when F R ⁇ F min , it is considered that the minimum required reformed gas cannot be reformed, and the electric output of the fuel cell is set to zero. At this time, it is possible to raise the temperature of the reforming catalyst layer with a heater or a burner attached to the reformer until at least F R ⁇ F min . If F R ⁇ F min , step D and subsequent steps can be performed.
- step C it repeats the steps A and B while elevating the reforming catalyst layer, while F R that is determined by the steps A and B is F R ⁇ F min is The power generation is kept stopped (step C), and the step D can be performed when F R becomes F R ⁇ F min .
- Reformable flow rate F R determined in step B is, if the it is the minimum value F min or more, the step D.
- step D the fuel cell output demand value P D, the step d1 if the maximum electrical output P M or less of the fuel cell.
- P D ⁇ P M is taken to mean that the fuel cell output request value P D means that the fuel cell can output.
- the fuel cell output demand value P D, the step d2 if exceeds the maximum electrical output P M of the fuel cell.
- P D > P M is considered to mean that the electric output of the fuel cell is insufficient with respect to the fuel cell output required value P D.
- the calculated f (P D) is, if at reformable flow rate F R less decided step B, the electrical output of the fuel cell as a P D, the hydrocarbon-based fuel supplied to the reforming catalyst layer flow Is f (P D ).
- f (P D) ⁇ F R is a hydrocarbon-based fuel at the flow rate f (P D) required to output the electrical output of the fuel cell output demand value P D, it can be reformed in the reforming catalyst layer Is taken to mean. Therefore, the hydrocarbon-based fuel at the flow rate f (P D ) is supplied to the reforming catalyst layer, the obtained reformed gas is supplied to the fuel cell, and the electric output of the fuel cell output required value P D is supplied to the fuel cell. To output.
- F R is a hydrocarbon-based fuel in the fuel cell output demand value P D of the hydrocarbon-based fuel required to output the electrical output flow f (P D) is, in the reforming catalyst layer It is taken to mean that it cannot be modified.
- There may be only one value of P calculated from P f ⁇ 1 (F R ), or there may be a plurality of values.
- the electric output of the fuel cell is set to the value of P. If there are a plurality of values of a plurality of P, and P D below and largest value, the electrical output of the fuel cell. That is, when multiple values exist, reformable flow rate F of the hydrocarbon-based fuel of R is supplied to the reforming catalyst layer, the maximum electrical output obtained from the hydrocarbon fuel reformable flow rate F R Is output by a fuel cell.
- the process d2 is performed when P D > P M (the electric output of the fuel cell is insufficient with respect to the required fuel cell output value P D ).
- f (P M) is said if reformable flow rate F R less, the electrical output of the fuel cell and P M, the flow rate of the hydrocarbon-based fuel supplied to the reforming catalyst layer to f (P M) .
- f (P M) ⁇ F R considers the hydrocarbon-based fuel at the flow rate f (P M), to mean that it is possible reformed in the reforming catalyst layer.
- f (P M)> F R considers the hydrocarbon-based fuel at the flow rate f (P M), the means can not be reformed in the reforming catalyst layer.
- N 5, that is, five different T j are set.
- the temperature of the reforming catalyst layer measured in the step A determines the reformable flow rate F R in Step B.
- step D is not performed but step D is performed.
- the fuel cell output demand value P D is intended to vary in load following operation, F R is to vary the temperature of the reforming catalyst layer.
- step D is not performed but step D is performed.
- the value, the flow rate of the hydrocarbon-based fuel supplied to the reforming catalyst layer is set to F R i.e. 2 g / min.
- the flow rate f (P M ) of the hydrocarbon fuel is calculated. This value is 4.5 g / min.
- step D is performed without performing step C.
- the flow rate f (P M ) of the hydrocarbon fuel is calculated. This value is 4.5 g / min.
- the correlation between F and P is made extreme for the sake of explanation. However, in practice, it is considered that there are many cases where the correlation is close to that shown in FIG.
- the flow rate F of the hydrocarbon-based fuel is set to 1.5 g / min in order to maintain the SOFC at a preferable power generation temperature in a range where the electrical output P is small, that is, in a range where the electrical output P is 0 W or more and 300 W or less. It is constant.
- the hydrocarbon fuel is increased as the electrical output P increases. It is assumed that the flow rate F increases from 1.5 g / min to 4.5 g / min.
- step B How to set T j
- the minimum value of T j is preferably as small as possible. The lowest temperature among the temperatures at which the flow rate of the reformable hydrocarbon fuel exceeds zero can be achieved.
- N is preferably as large as possible within the allowable range of the memory of the control means.
- N is preferable to decrease the interval of T j as the temperature increases.
- G j of setting G j is a flow rate of the corresponding hydrocarbon-based fuel that can be reformed in the reforming catalyst layer in the reforming catalyst layer temperature T j (reformable flow rate). Accordingly, when the temperature of the reforming catalyst layer is the temperature T j , the flow rate G j of the hydrocarbon-based fuel that can be reformed in the reforming catalyst layer is obtained in advance, and the correspondence between T j and G j is set in advance. .
- T j the flow rate G j of the hydrocarbon-based fuel that can be reformed in the reforming catalyst layer
- the flow rate of the hydrocarbon-based fuel that can be reformed in the reforming catalyst layer is such that when the hydrocarbon-based fuel at that flow rate is supplied to the reforming catalyst layer, the composition of the gas discharged from the reforming catalyst layer is the fuel cell.
- the reformable flow rate in the reforming catalyst layer can be an arbitrary flow rate that is not more than the maximum value of the flow rate at which the supplied hydrocarbon fuel can be decomposed to the C1 compound (compound having 1 carbon atom). That is, the reforming catalyst layer is modified until the C2 + component (the component having 2 or more carbon atoms) in the reforming catalyst layer outlet gas has a concentration that does not cause a problem with respect to channel blockage or anode deterioration due to carbon deposition.
- the flow rate can be set to an arbitrary flow rate that is not more than the maximum value of the supply flow rate of the hydrocarbon-based fuel to the reforming catalyst layer.
- the reformable flow rate can be the maximum value, or can be a value obtained by dividing the maximum value by a safety factor (a value exceeding 1; for example, 1.4).
- the concentration of the C2 + component at this time is preferably 50 ppb or less as a mass fraction in the reformed gas.
- the reforming catalyst layer outlet gas only needs to be reducible. It is allowed that methane is contained in the reforming catalyst layer outlet gas. In the reforming of hydrocarbon-based fuels, methane usually remains in equilibrium. Even when the reforming catalyst layer outlet gas contains carbon in the form of methane, CO, or CO 2 , carbon deposition can be prevented by adding steam as necessary. When methane is used as the hydrocarbon-based fuel, reforming may be advanced so that the reforming catalyst layer outlet gas becomes reducible.
- the partial pressure of oxidizing O 2 , H 2 O, CO 2 and the like contained in the reforming catalyst layer outlet gas can be made lower than the equilibrium partial pressure in the oxidation reaction of the anode electrode.
- the O 2 partial pressure contained in the reforming catalyst layer outlet gas is less than 1.2 ⁇ 10 ⁇ 14 atm (1.2 ⁇ 10 ⁇ 9 Pa) , less than 1.7 ⁇ 10 2 partial pressure ratio of H 2 O for H 2, the partial pressure ratio of CO 2 to CO may be less than 1.8 ⁇ 10 2.
- the reformable flow rate depends on the temperature of the reforming catalyst layer. Therefore, the reformable flow rate in the reforming catalyst layer is obtained based on the temperature of the reforming catalyst layer.
- the reformable flow rate G j can be obtained by experiments in advance as a function of the temperature T j of the reforming catalyst layer. In addition, it is possible to obtain a reformable flow rate after dividing the function obtained by experiments by the safety factor or correcting the temperature to the safe side.
- the unit of G j is, for example, g / min or mol / s.
- the reformable flow rate G j can be a function of only the temperature T j .
- the reformable flow rate G j may be a function having variables other than T j such as the catalyst layer volume and the gas component concentration, in addition to the temperature T j . In that case, when the reformable flow rate G j is calculated, a variable other than T j is obtained as appropriate, and the reformable flow rate G j is calculated from the variable other than T j and the measured T j. it can.
- the temperature measurement portion of the reforming catalyst layer may be one point or a plurality of points.
- a representative temperature such as an average value of a plurality of points can be used.
- the flow rate of fuel that can be reformed in at least a part of the plurality of divided regions may be calculated, and the total value of the calculated flow rates may be used as the flow rate of fuel that can be reformed in the reforming catalyst layer.
- the temperature T of the reforming catalyst layer during actual operation in step A it is desirable to measure the temperature of the reforming catalyst layer in the same manner as in the preliminary experiment for obtaining G j . That is, it is desirable to measure the temperature of the reforming catalyst layer at the same location as in the preliminary experiment.
- the representative temperature it is desirable that the same representative temperature is set as the temperature T of the reforming catalyst layer in the process A.
- the shortage of the fuel cell electrical output with respect to the power load can be supplied from the system power supply.
- Fuel cell output demand value P D may be the value of the power load measured by an appropriate power meter. Alternatively, in the case of other generators and battery and interconnection, a portion of the measured electric power load may be a fuel cell output demand value P D.
- the flow rate of the fluid supplied to the indirect internal reforming SOFC other than the hydrocarbon fuel and the indirect internal reformation other than the output of the SOFC according to the necessity.
- the input / output of electricity to the type SOFC can be determined by calculating from the function of the electric output P obtained in advance.
- the present invention is particularly effective when the hydrocarbon fuel supplied to the reforming catalyst layer includes a hydrocarbon fuel having 2 or more carbon atoms. According to the present invention, even during load following operation, the concentration of the compound having 2 or more carbon atoms in the reformed gas can be reduced to 50 ppb or less on the mass basis. Can be more reliably prevented.
- an appropriate instrumentation control device including a computing means such as a computer can be used.
- the hydrocarbon-based fuel is appropriately selected from compounds or mixtures thereof containing carbon and hydrogen (may contain other elements such as oxygen) known in the field of high-temperature fuel cells as a reformed gas raw material.
- Compounds having carbon and hydrogen in the molecule such as hydrocarbons and alcohols can be used.
- hydrocarbon fuel such as methane, ethane, propane, butane, natural gas, LPG (liquefied petroleum gas), city gas, gasoline, naphtha, kerosene, light oil, etc.
- alcohol such as methanol and ethanol
- ether such as dimethyl ether, etc.
- kerosene and LPG are preferred because they are readily available. Moreover, since it can be stored independently, it is useful in areas where city gas lines are not widespread. Furthermore, a high-temperature fuel cell power generator using kerosene or LPG is useful as an emergency power source. In particular, kerosene is preferable because it is easy to handle.
- High-temperature fuel cell The present invention can be suitably applied to a system including a high-temperature fuel cell that may cause channel blockage or anode deterioration due to carbon deposition.
- fuel cells include SOFC and MCFC.
- the SOFC it can be appropriately selected from known SOFCs of various shapes such as a flat plate type and a cylindrical type.
- oxygen ion conductive ceramics or proton ion conductive ceramics are generally used as an electrolyte.
- MCFC can be selected from known MCFCs as appropriate.
- the SOFC or MCFC may be a single cell, but in practice, a stack in which a plurality of single cells are arranged (in the case of a cylindrical type, it may be called a bundle, but the stack referred to in this specification also includes a bundle) Is preferably used. In this case, one or more stacks may be used.
- the indirect internal reforming SOFC is superior in that it can increase the thermal efficiency of the system.
- the indirect internal reforming SOFC includes a reformer that produces a reformed gas containing hydrogen from a hydrocarbon-based fuel using a steam reforming reaction, and the SOFC.
- a steam reforming reaction can be performed, and autothermal reforming accompanied by a partial oxidation reaction in the steam reforming reaction may be performed.
- the partial oxidation reaction does not occur after the start-up is completed.
- the steam reforming becomes dominant after the start-up is completed, so that the reforming reaction becomes an endothermic by overall.
- the reformer and SOFC are accommodated in one module container and modularized.
- the reformer is disposed at a position that receives heat radiation from the SOFC. By doing so, the reformer is heated by heat radiation from the SOFC during power generation.
- the SOFC can be heated by burning the anode off-gas discharged from the SOFC at the cell outlet.
- the reformer is preferably disposed at a position where radiation heat can be directly transferred from the SOFC to the outer surface of the reformer. Therefore, it is preferable that a shielding object is not substantially disposed between the reformer and the SOFC, that is, a gap is provided between the reformer and the SOFC. Further, it is preferable to shorten the distance between the reformer and the SOFC as much as possible.
- Each supply gas is preheated as necessary and then supplied to the reformer or SOFC.
- an appropriate container that can accommodate the SOFC and the reformer can be used.
- the material for example, an appropriate material having resistance to the environment to be used, such as stainless steel, can be used.
- the container is appropriately provided with a connection port for gas exchange and the like.
- the module container has airtightness so that the inside of the module container does not communicate with the outside (atmosphere).
- the combustion region is a region where the anode off gas discharged from the SOFC anode can be combusted.
- the anode outlet can be opened in the housing, and the space near the anode outlet can be used as a combustion region.
- This combustion can be performed using, for example, a cathode off gas as the oxygen-containing gas.
- the cathode outlet can be opened in the housing.
- An ignition means such as an igniter can be appropriately used to burn the combustion fuel or anode off gas.
- the reformer produces a reformed gas containing hydrogen from a hydrocarbon fuel.
- any of steam reforming, partial oxidation reforming, and autothermal reforming accompanied by a partial oxidation reaction in the steam reforming reaction may be performed.
- the reformer is appropriately equipped with a steam reforming catalyst having steam reforming ability, a partial oxidation reforming catalyst having partial oxidation reforming ability, and a self-thermal reforming catalyst having both partial oxidation reforming ability and steam reforming ability. Can be used.
- a structure known as a reformer can be appropriately adopted.
- a structure having a region for accommodating the reforming catalyst in a sealable container and having an inlet for fluid necessary for reforming and an outlet for reforming gas can be appropriately adopted.
- the material of the reformer can be appropriately selected and adopted from materials known as reformers in consideration of resistance in the use environment.
- the shape of the reformer can be an appropriate shape such as a rectangular parallelepiped or a circular tube.
- Any of the steam reforming catalyst, partial oxidation reforming catalyst, and autothermal reforming catalyst used in the reformer can be a known catalyst.
- Examples of the partial oxidation reforming catalyst include platinum-based catalysts
- examples of the steam reforming catalyst include ruthenium-based and nickel-based catalysts
- examples of the autothermal reforming catalyst include rhodium-based catalysts.
- the temperature at which the partial oxidation reforming reaction can proceed is, for example, 200 ° C. or more, and the temperature at which the steam reforming reaction can proceed is, for example, 400 ° C. or more.
- steam reforming steam is added to reforming raw materials such as kerosene.
- the reaction temperature of the steam reforming can be performed, for example, in the range of 400 ° C. to 1000 ° C., preferably 500 ° C. to 850 ° C., more preferably 550 ° C. to 800 ° C.
- the amount of steam introduced into the reaction system is defined as the ratio of the number of moles of water molecules to the number of moles of carbon atoms contained in the hydrocarbon fuel (steam / carbon ratio), and this value is preferably 1 to 10, more preferably It is 1.5-7, more preferably 2-5.
- the space velocity (LHSV) at this time is A / B when the flow rate in the liquid state of the hydrocarbon fuel is A (L / h) and the catalyst layer volume is B (L).
- This value is preferably set in the range of 0.05 to 20 h ⁇ 1 , more preferably 0.1 to 10 h ⁇ 1 , still more preferably 0.2 to 5 h ⁇ 1 .
- an oxygen-containing gas is added to the reforming raw material in addition to steam.
- the oxygen-containing gas may be pure oxygen, but air is preferred because of its availability.
- An oxygen-containing gas can be added so that the endothermic reaction accompanying the steam reforming reaction is balanced, and a heat generation amount capable of maintaining the temperature of the reforming catalyst layer and SOFC or raising the temperature thereof can be obtained.
- the addition amount of the oxygen-containing gas is preferably 0.005 to 1, more preferably 0.01 to 0.00 as the ratio of the number of moles of oxygen molecules to the number of moles of carbon atoms contained in the hydrocarbon fuel (oxygen / carbon ratio). 75, more preferably 0.02 to 0.6.
- the reaction temperature of the autothermal reforming reaction is set in the range of, for example, 400 ° C. to 1000 ° C., preferably 450 ° C. to 850 ° C., more preferably 500 ° C. to 800 ° C.
- the space velocity (LHSV) at this time is preferably 0.05 to 20 h ⁇ 1 , more preferably 0.1 to 10 h ⁇ 1 , further preferably 0.2 to 5 h ⁇ 1. Is selected within the range.
- the amount of steam introduced into the reaction system is preferably 1 to 10, more preferably 1.5 to 7, and still more preferably 2 to 5 as a steam / carbon ratio.
- an oxygen-containing gas is added to the reforming raw material.
- the oxygen-containing gas may be pure oxygen, but air is preferred because of its availability.
- the amount added is appropriately determined in terms of heat loss and the like.
- the amount is preferably 0.1 to 3, more preferably 0.2 to 0.7, as the ratio of the number of moles of oxygen molecules to the number of moles of carbon atoms contained in the hydrocarbon fuel (oxygen / carbon ratio).
- the reaction temperature of the partial oxidation reaction can be set, for example, in the range of 450 ° C. to 1000 ° C., preferably 500 ° C. to 850 ° C., more preferably 550 ° C. to 800 ° C.
- the space velocity (LHSV) at this time is preferably selected in the range of 0.1 to 30 h ⁇ 1 .
- steam can be introduced, and the amount thereof is preferably 0.1 to 5, more preferably 0.1 to 3, more preferably 1 to 3 as the steam / carbon ratio. 2.
- the present invention can be applied to, for example, a stationary or mobile power generation system, and a high-temperature fuel cell system used for a cogeneration system.
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Abstract
Description
1)炭化水素系燃料を改質して水素を含有する改質ガスを製造する、改質触媒層を有する改質器と、該改質ガスを用いて発電を行う高温型燃料電池とを有する燃料電池システムの負荷追従運転方法であって、
予め、該燃料電池の電気出力Pと、該電気出力Pを燃料電池で出力するために改質触媒層に供給することが必要な炭化水素系燃料の流量Fとの関数F=f(P)およびP=f-1(F)を求めておき、
ただし、P=f-1(F)はF=f(P)の逆関数であり、
該燃料電池の最大電気出力をPMと表し、
Pが0以上PM以下の範囲にあるときの、関数F=f(P)によって定まる炭化水素系燃料の流量の最小値をFminと表し、
かつ、予め、改質触媒層の複数の温度Tj(jは1以上N以下の整数、ただしNは2以上の整数)と、各Tjに対応する炭化水素系燃料の流量Gjと、を設定しておき、
ただし、各Gjは対応する改質触媒層温度Tjにおいて改質触媒層において改質可能な炭化水素系燃料の流量であり、各Gjは0より大きく、jの増加に伴ってGjは同じ値であるか増加し、
A)改質触媒層の温度Tを測定する工程、
B)温度Tの改質触媒層において改質可能な炭化水素系燃料の流量である改質可能流量FRとして、前記温度T以下で最も大きいTjに対応するGjを採用する工程、
C)前記改質可能流量FRが、前記最小値Fminより小さい場合、燃料電池における発電を停止する工程、
D)前記改質可能流量FRが、前記最小値Fmin以上である場合に、
燃料電池出力要求値PDが、前記最大電気出力PM以下であれば工程d1を行ない、燃料電池出力要求値PDが、前記最大電気出力PMを超えていれば工程d2を行なう工程、
d1)前記関数F=f(P)を用いて、燃料電池出力要求値PDを燃料電池で出力するために改質触媒層に供給することが必要な炭化水素系燃料の流量f(PD)を算出し、
f(PD)が前記改質可能流量FR以下であれば、燃料電池の電気出力をPDとし、改質触媒層に供給する炭化水素系燃料の流量をf(PD)とし、
f(PD)が前記改質可能流量FRを超えていれば、燃料電池の電気出力を、P=f-1(FR)から計算されるPの値のうちのPD未満で最大の値とし、改質触媒層に供給する炭化水素系燃料の流量をFRとする工程、
d2)前記関数F=f(P)を用いて、前記最大電気出力PMを燃料電池で出力するために改質触媒層に供給することが必要な改質触媒層に供給する炭化水素系燃料の流量f(PM)を算出し、
f(PM)が、前記改質可能流量FR以下であれば、燃料電池の電気出力をPMとし、改質触媒層に供給する炭化水素系燃料の流量をf(PM)とし、
f(PM)が、前記改質可能流量FRを超えていれば、燃料電池の電気出力を、P=f-1(FR)から計算されるPの値のうちの最大の値とし、改質触媒層に供給する炭化水素系燃料の流量をFRとする工程
を有する燃料電池システムの負荷追従運転方法。
図1に、本発明を実施することのできる間接内部改質型SOFCの一形態を模式的に示す。ここでは、間接内部改質型SOFCシステムについて説明するが、本発明は外部改質型SOFCシステムあるいはMCFCシステムについても適用可能である。
本発明では、予め、燃料電池の電気出力Pと、電気出力Pを燃料電池で出力するために改質触媒層に供給することが必要な炭化水素系燃料の流量Fとの関数F=f(P)およびP=f-1(F)を求めておく。P=f-1(F)はF=f(P)の逆関数である。ただし、或る電気出力Pに対して一義的にFが定まり、或るFに対して一もしくは複数のPが存在することができる。例えば、SOFCを好ましく発電可能な温度に維持しつつもできるだけ発電効率が高くなるよう、予備実験やシミュレーションなどにより、或る電気出力Pに対する電流と燃料利用率を予め定めておくことで、必然的に或る電気出力Pに対するFが一義的に定まる。また、例えば、電気出力が小さいときにもSOFCを好ましく発電可能な温度に維持するために、図6に示すように或る電気出力P以下に対する炭化水素系燃料の流量を一定値にする場合があるが、その場合には或るFに対して複数のPが存在する。
0≦P≦PMおよびFmin≦F≦Fmaxの範囲で定まればよい。
実際に負荷変動運転を行なう際には、改質触媒層の温度を測定する工程Aを行なう。この測定は、負荷追従運転を行う間継続して行なうことができる。
工程Bでは、温度T(工程Aで測定した温度)の改質触媒層において改質可能な炭化水素系燃料の流量(改質可能流量FR)として、温度T以下で最も大きいTjに対応するGjを採用する。つまり、予め設定したTjのうち、測定した温度T以下の範囲で最も大きいTjを選ぶ。そして、予め設定したTjとGjとの対応関係から、選んだTjに対応するGjを求め、このGjを改質可能流量FRとする。
工程Bで求めた改質可能流量FRが、前記最小値Fminより小さい場合、燃料電池における発電を停止する。つまり、FR<Fminのとき、最低限必要な改質ガスを改質できないとみなし、燃料電池の電気出力をゼロにする。このとき、少なくともFR≧Fminとなるまで、改質器に付設されたヒータやバーナなどで改質触媒層を昇温することができる。FR≧Fminとなったら、工程D以降を行うことができる。より具体的には、工程Cで発電を停止し、改質触媒層を昇温しながら工程AおよびBを繰り返し行い、工程AおよびBによって決められたFRがFR<Fminの間は発電を停止したままにし(工程C)、FRがFR≧Fminとなったら工程Dを行うことができる。
工程Bで決めた改質可能流量FRが、前記最小値Fmin以上である場合に、工程Dを行なう。
前記関数F=f(P)を用いて、燃料電池出力要求値PDを燃料電池で出力するために改質触媒層に供給することが必要な炭化水素系燃料の流量f(PD)を算出する。
前述のように、PD>PM(燃料電池出力要求値PDに対して、燃料電池の電気出力が不足)の場合に、工程d2を行なう。
以下、図2~5を用い、或る一つの燃料電池システムの負荷追従運転を行なう際に、様々な条件において、どのように運転するかについて具体例を挙げて説明する。ただし、本発明はこれによって限定されるものではない。
燃料電池出力要求値PD=600W、工程Aで測定した改質触媒層温度T=660℃の場合を考える。また、燃料電池の最大電気出力PM=1000W、0≦P≦PMの範囲で関数F=f(P)によって定まる炭化水素系燃料の流量の最小値Fmin=1g/minとする(図2参照)。
PD=900W、T=640℃の場合を考える(図3参照)。
PD=1200W、T=680℃の場合を考える(図4参照)。PM=1000W、Fmin=1g/minはケース1と同様である。
PD=1200W、T=640℃の場合を考える(図5参照)。PM=1000W、Fmin=1g/minはケース1と同様である。
・Tjの設定の仕方
触媒層の測定温度TがTjのうちの最小値より小さい場合、工程Bが実施不可能となるため、Tjの最小値は、できるだけ小さい方が好ましく、例えば、改質可能な炭化水素系燃料の流量がゼロを超える温度のうちの最低温度することができる。
Gjは対応する改質触媒層温度Tjにおいて改質触媒層において改質可能な炭化水素系燃料の流量(改質可能流量)である。したがって、改質触媒層の温度が温度Tjのときの、改質触媒層において改質可能な炭化水素系燃料の流量Gjを予め求め、TjとGjとの対応関係を予め設定する。以下、Gjの求め方について、説明する。
負荷追従運転の間、必ずしも同じ種類の改質を行う必要はない。より詳しくは、負荷追従運転の間、炭化水素系燃料の流量を段階的に変更して改質を行なうことができるが、各段階において必ずしも同じ種類の改質を行なう必要はない。
炭化水素系燃料としては、改質ガスの原料として高温型燃料電池の分野で公知の、分子中に炭素と水素を含む(酸素など他の元素を含んでもよい)化合物もしくはその混合物から適宜選んで用いることができ、炭化水素類、アルコール類など分子中に炭素と水素を有する化合物を用いることができる。例えばメタン、エタン、プロパン、ブタン、天然ガス、LPG(液化石油ガス)、都市ガス、ガソリン、ナフサ、灯油、軽油等の炭化水素燃料、また、メタノール、エタノール等のアルコール、ジメチルエーテル等のエーテル等である。
本発明は、炭素析出による流路閉塞やアノード劣化が生じる可能性のある高温型燃料電池を備えるシステムに好適に適用することができる。このような燃料電池としては、SOFCやMCFCがある。
改質器は、炭化水素系燃料から水素を含む改質ガスを製造する。
改質器で用いる水蒸気改質触媒、部分酸化改質触媒、オートサーマル改質触媒のいずれも、それぞれ公知の触媒を用いることができる。部分酸化改質触媒の例としては白金系触媒、水蒸気改質触媒の例としてはルテニウム系およびニッケル系、オートサーマル改質触媒の例としてはロジウム系触媒を挙げることができる。
以下、水蒸気改質、オートサーマル改質、部分酸化改質のそれぞれにつき、改質器における負荷追従運転時の条件について説明する。
本発明で用いる高温型燃料電池システムにおいて、高温型燃料電池システムの公知の構成要素は、必要に応じて適宜設けることができる。具体例を挙げれば、炭化水素系燃料に含まれる硫黄分を低減する脱硫器、液体を気化させる気化器、各種流体を加圧するためのポンプ、圧縮機、ブロワなどの昇圧手段、流体の流量を調節するため、あるいは流体の流れを遮断/切り替えるためのバルブ等の流量調節手段や流路遮断/切り替え手段、熱交換・熱回収を行うための熱交換器、気体を凝縮する凝縮器、スチームなどで各種機器を外熱する加熱/保温手段、炭化水素系燃料や可燃物の貯蔵手段、計装用の空気や電気系統、制御用の信号系統、制御装置、出力用や動力用の電気系統などである。
2 水気化器に付設された電気ヒータ
3 改質器
4 改質触媒層
5 燃焼領域
6 SOFC
7 イグナイター
8 モジュール容器
9 改質器に付設された電気ヒータ
Claims (4)
- 炭化水素系燃料を改質して水素を含有する改質ガスを製造する、改質触媒層を有する改質器と、該改質ガスを用いて発電を行う高温型燃料電池とを有する燃料電池システムの負荷追従運転方法であって、
予め、該燃料電池の電気出力Pと、該電気出力Pを燃料電池で出力するために改質触媒層に供給することが必要な炭化水素系燃料の流量Fとの関数F=f(P)およびP=f-1(F)を求めておき、
ただし、P=f-1(F)はF=f(P)の逆関数であり、
該燃料電池の最大電気出力をPMと表し、
Pが0以上PM以下の範囲にあるときの、関数F=f(P)によって定まる炭化水素系燃料の流量の最小値をFminと表し、
かつ、予め、改質触媒層の複数の温度Tj(jは1以上N以下の整数、ただしNは2以上の整数)と、各Tjに対応する炭化水素系燃料の流量Gjと、を設定しておき、
ただし、各Gjは対応する改質触媒層温度Tjにおいて改質触媒層において改質可能な炭化水素系燃料の流量であり、各Gjは0より大きく、jの増加に伴ってGjは同じ値であるか増加し、
A)改質触媒層の温度Tを測定する工程、
B)温度Tの改質触媒層において改質可能な炭化水素系燃料の流量である改質可能流量FRとして、前記温度T以下で最も大きいTjに対応するGjを採用する工程、
C)前記改質可能流量FRが、前記最小値Fminより小さい場合、燃料電池における発電を停止する工程、
D)前記改質可能流量FRが、前記最小値Fmin以上である場合に、
燃料電池出力要求値PDが、前記最大電気出力PM以下であれば工程d1を行ない、燃料電池出力要求値PDが、前記最大電気出力PMを超えていれば工程d2を行なう工程、
d1)前記関数F=f(P)を用いて、燃料電池出力要求値PDを燃料電池で出力するために改質触媒層に供給することが必要な炭化水素系燃料の流量f(PD)を算出し、
f(PD)が前記改質可能流量FR以下であれば、燃料電池の電気出力をPDとし、改質触媒層に供給する炭化水素系燃料の流量をf(PD)とし、
f(PD)が前記改質可能流量FRを超えていれば、燃料電池の電気出力を、P=f-1(FR)から計算されるPの値のうちのPD未満で最大の値とし、改質触媒層に供給する炭化水素系燃料の流量をFRとする工程、
d2)前記関数F=f(P)を用いて、前記最大電気出力PMを燃料電池で出力するために改質触媒層に供給することが必要な改質触媒層に供給する炭化水素系燃料の流量f(PM)を算出し、
f(PM)が、前記改質可能流量FR以下であれば、燃料電池の電気出力をPMとし、改質触媒層に供給する炭化水素系燃料の流量をf(PM)とし、
f(PM)が、前記改質可能流量FRを超えていれば、燃料電池の電気出力を、P=f-1(FR)から計算されるPの値のうちの最大の値とし、改質触媒層に供給する炭化水素系燃料の流量をFRとする工程
を有する燃料電池システムの負荷追従運転方法。 - 負荷追従運転の間、前記工程A~Dを繰り返して行なう請求項1記載の方法。
- 前記炭化水素系燃料が、炭素数が2以上の炭化水素系燃料を含む請求項1または2記載の方法。
- 前記改質ガス中の、炭素数2以上の化合物の濃度が、質量基準で50ppb以下である請求項3記載の方法。
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US13/379,759 US8865358B2 (en) | 2009-07-02 | 2010-06-25 | Method for load following operation of fuel cell system |
CN201080029700.3A CN102473944B (zh) | 2009-07-02 | 2010-06-25 | 燃料电池系统的负荷跟踪运转方法 |
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US8865358B2 (en) | 2014-10-21 |
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