JP2010244922A - Stopping method for indirect internal reforming type solid oxide fuel cell - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a stopping method for an indirect internal reforming type solid oxide fuel cell (SOFC) for attaining certain reforming and prevention of anode oxidation deterioration. <P>SOLUTION: The stopping method for a SOFC includes: (A) a step of measuring temperature T for a reforming catalyst layer; (C) a step of setting as T≥TrE if a fuel flow rate Fk(j) wherein Tr(j) is T or below and the Tr(j) is from Fk(1) to less than FkE in the fuel flow rate Fk(j), exists ; (C1) a step of defining the j giving the minimum Fk(j) as J and defining a supply fuel flow rate to a reformer as Fk(J); (C2) a step of comparing with the TrE by measuring the T; (C3) a step of moving to the step D by setting the supply fuel flow rate to the reformer at FkE if it is T≤TrE; (C4) a step of comparing the T with the Tr(J) if it is T>TrE; (C5) a step of returning to the step C2 if it is T>Tr(J); (C6) a step of increasing the J by 1 by increasing the supply fuel flow rate to the reformer to Fk(J+1) if it is T≤Tr(J); (C7) a step of returning to the step C2 if it is J≠M after the step C6 and moving to the step D if it is J=M; and (D) a step of waiting till anode temperature becomes under an oxidation deterioration point. Here, regarding a generated amount of reforming gas when anode temperature of the solid oxide fuel cell is at temperature of more than the oxidation deterioration point, a flow rate of a hydrocarbon fuel supplied to the reformer is expressed as FkE if the minimum flow rate necessary for preventing oxidation deterioration of the anode is all filled up, and a temperature condition of a reforming catalyst layer at the state is expressed as TrE. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a method for stopping an indirect internal reforming solid oxide fuel cell having a reformer in the vicinity of the fuel cell.

  Solid oxide electrolyte fuel cell (Solid Oxide Fuel Cell; hereinafter referred to as SOFC) systems are usually used to reform hydrocarbon fuels such as kerosene and city gas to generate reformed gas as hydrogen-containing gas. And a SOFC for electrochemically generating and reacting the reformed gas and air.

  The SOFC is usually operated at a high temperature of 550 to 1000 ° C.

  Various reactions such as steam reforming (SR), partial oxidation reforming (POX), and autothermal reforming (ATR) are used for reforming, but in order to use a reforming catalyst, catalytic activity is manifested. Need to be heated to temperature.

  Steam reforming is a very large endothermic reaction, and the reaction temperature is relatively high at 550 to 750 ° C., which requires a high-temperature heat source. Therefore, a reformer (internal reformer) is installed in the vicinity of the SOFC, and the reformer is heated indirectly using the heat generated by the radiant heat from the SOFC or the combustion heat of the SOFC anode off-gas (gas discharged from the anode) as a heat source. A modified SOFC is known (Patent Document 1).

  In addition, when power generation is stopped, a fuel cell that reduces the stack temperature while maintaining the fuel electrode layer side in a reduced state by supplying the fuel cell while reducing the flow rate of water and hydrogen or hydrocarbon fuel. The operation stop method is disclosed in Patent Document 2.

JP 2004-319420 A JP 2006-294508 A

  If the method described in Patent Document 2 is used, it is considered that the anode can be held in a reducing atmosphere when the fuel cell is stopped, and oxidation deterioration of the anode can be prevented.

  However, in the method described in Patent Document 2, when the SOFC anode is maintained in a reduced state using a hydrogen-containing gas obtained by reforming a hydrocarbon fuel, reliable reforming is not ensured. That is, unreformed hydrocarbon fuel may be discharged from the reformer and flow into the anode.

  In particular, when using a higher order hydrocarbon such as kerosene, if the higher order hydrocarbon leaks from the reformer and flows into the SOFC, the performance of the SOFC may deteriorate due to carbon deposition.

  An object of the present invention is to provide a method for stopping an indirect internal reforming SOFC that can prevent oxidative deterioration of an anode with a reformed gas while reliably reforming a hydrocarbon-based fuel.

According to the present invention,
A reformer having a reforming catalyst layer for reforming hydrocarbon fuel to produce reformed gas;
A solid oxide fuel cell that generates electric power using the reformed gas; and
A combustion region for burning anode off-gas discharged from the solid oxide fuel cell;
A method for stopping an indirect internal reforming solid oxide fuel cell comprising: a reformer, a solid oxide fuel cell, and a housing that houses a combustion region;
The following conditions i to iv,
i) The anode temperature of the solid oxide fuel cell is steady,
ii) the anode temperature is below the oxidative degradation point;
iii) In the reformer, the hydrocarbon-based fuel is reformed, and a reformed gas having a composition suitable for supplying to the anode is generated,
iv) The amount of the reformed gas generated is equal to or higher than the minimum flow rate FrMin necessary for preventing the oxidative deterioration of the anode when the anode temperature of the solid oxide fuel cell is equal to or higher than the oxidative deterioration point.
The flow rate of the hydrocarbon-based fuel supplied to the reformer in a state where all of the above are satisfied is represented as FkE, and the temperature condition of the reforming catalyst layer in the state is represented as TrE,
A stepwise hydrocarbon-based fuel flow rate Fk (j) is determined in advance (where j is an integer of 1 to M, and M is an integer of 2 or more), where Fk (j) is The largest Fk (M) among Fk (j) s is equal to FkE, and Fk (j) is not changed in the reaction temperature range of the reforming method of the kind performed after the start of the stopping method. It is above the minimum value of the hydrocarbon fuel flow rate that can obtain the reformed gas with a flow rate of FrMin or higher by the quality method,
The flow rate of the hydrocarbon-based fuel that has been supplied to the reformer at the start of the stop method is expressed as Fk0,
The temperature of the reforming catalyst layer at which the flow rate of the reformed gas obtained when the hydrocarbon-based fuel at the flow rate Fk (j) is reformed in the reforming catalyst layer by the kind of reforming method performed after the start of the stopping method is FrMin. Knowing the condition Tr (j) in advance (where j is an integer greater than or equal to 1 and less than or equal to M−1)
When the anode temperature falls below the oxidative degradation point, the supply of hydrocarbon fuel to the reformer is stopped and the stopping method is terminated.
While the anode temperature is not below the oxidation degradation point,
A) a step of measuring the reforming catalyst layer temperature T and comparing the measured temperature T with TrE;
B) A step of sequentially performing the following steps B1 to B4 when T <TrE in step A,
B1) Step of heating the reforming catalyst layer
B2) a step of measuring the reforming catalyst layer temperature and comparing the measured temperature T with TrE;
B3) A process of returning to the process B1 when T <TrE in the process B2,
B4) When T ≧ TrE in step B2, the flow rate of the hydrocarbon-based fuel supplied to the reformer is changed from Fk0 to FkE, and the process proceeds to step D.
C) In the case of T ≧ TrE in step A,
Of the predetermined hydrocarbon fuel flow rate Fk (j), the corresponding temperature condition Tr (j) is equal to or lower than the reforming catalyst layer temperature T measured in step A and is equal to or higher than Fk (1) and smaller than FkE. If Fk (j) does not exist, the flow rate of the hydrocarbon-based fuel supplied to the reformer is changed from Fk0 to FkE, and the process proceeds to step D.
Of the predetermined hydrocarbon fuel flow rate Fk (j), the corresponding temperature condition Tr (j) is equal to or lower than the reforming catalyst layer temperature T measured in step A and is equal to or higher than Fk (1) and smaller than FkE. If Fk (j) is present, the following steps C1 to C7 are sequentially performed,
C1) The smallest Fk (j) out of the flow rates Fk (j) where the corresponding temperature condition Tr (j) is equal to or lower than the reforming catalyst layer temperature T measured in step A and is equal to or higher than Fk (1) and smaller than FkE. J is given as J,
Changing the flow rate of the hydrocarbon-based fuel supplied to the reformer from Fk0 to Fk (J);
C2) a step of measuring the reforming catalyst layer temperature and comparing the measured temperature T with TrE;
C3) Step T2, when T ≦ TrE, the flow rate of the hydrocarbon-based fuel supplied to the reformer is set to FkE, and the flow proceeds to Step D.
C4) a step of comparing T with Tr (J) when T> TrE in Step C2,
C5) If T> Tr (J) in step C4, returning to step C2,
C6) A step of increasing the flow rate of the hydrocarbon-based fuel supplied to the reformer from Fk (J) to Fk (J + 1) and increasing J by 1 when T ≦ Tr (J) in step C4.
C7) After step C6, J and M are compared. If J ≠ M, the process returns to step C2, and if J = M, the process moves to step D.
and,
D) A method for shutting down an indirect internal reforming solid oxide fuel cell is provided that includes waiting for the anode temperature to fall below the oxidation degradation point.

  The hydrocarbon fuel may include a hydrocarbon fuel having 2 or more carbon atoms.

  The concentration of the compound having 2 or more carbon atoms in the reformed gas is preferably 50 ppb or less on a mass basis.

  The present invention provides a method for stopping an indirect internal reforming SOFC that can prevent oxidative deterioration of an anode with a reformed gas while reliably reforming a hydrocarbon-based fuel.

It is a schematic diagram which shows the outline | summary of the indirect internal reforming type | mold SOFC which can apply this invention. It is a conceptual graph for demonstrating the method of this invention, (a) is the relationship between elapsed time and reformed gas flow rate, (b) is the relationship between elapsed time and temperature, (c) is the elapsed time and hydrocarbon system. The relationship of fuel flow is shown. It is a conceptual graph for demonstrating the method of this invention, (a) is the relationship between elapsed time and reformed gas flow rate, (b) is the relationship between elapsed time and temperature, (c) is the elapsed time and hydrocarbon system. The relationship of fuel flow is shown. It is a conceptual graph for demonstrating the method of this invention, (a) is the relationship between elapsed time and reformed gas flow rate, (b) is the relationship between elapsed time and temperature, (c) is the elapsed time and hydrocarbon system. The relationship of fuel flow is shown. It is a conceptual graph for demonstrating the method of this invention, (a) is the relationship between elapsed time and reformed gas flow rate, (b) is the relationship between elapsed time and temperature, (c) is the elapsed time and hydrocarbon system. The relationship of fuel flow is shown. It is a flowchart for demonstrating the method of this invention.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings, but the present invention is not limited thereto.

[Indirect internal reforming SOFC]
FIG. 1 schematically shows an embodiment of an indirect internal reforming SOFC that can implement the present invention.

  The indirect internal reforming SOFC has a reformer 3 that reforms a hydrocarbon-based 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 housing 8 that houses a reformer, a solid oxide fuel cell, and a combustion region.

  The indirect internal reforming SOFC refers to a casing (module container) 8 and equipment included therein.

  In the indirect internal reforming SOFC of the form shown in FIG. 1, 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 appropriately preheated as necessary and then supplied to the reformer or SOFC.

  A water vaporizer 1 including an electric heater 2 is connected to the indirect internal reforming SOFC, 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 is also supplied to the reforming catalyst layer. Here, air is preheated by a water vaporizer and then supplied to the reforming catalyst layer. Water vapor can be obtained from the water vaporizer, and a mixed gas of air and water vapor can be obtained.

  Steam or a mixed gas of air and steam is mixed with a hydrocarbon fuel and supplied to the reformer 3, particularly the reforming catalyst layer 4. When liquid fuel such as kerosene is used as the hydrocarbon-based fuel, the 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 to 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. For this purpose, 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.

  The 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.

  In the indirect internal reforming SOFC, the reformer is preferably arranged at a position where direct heat transfer from the SOFC to the outer surface of the reformer is possible. 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.

  Furthermore, 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.

[Reforming stoppage possible state]
In the present specification, a state where all of the following conditions i to iv are satisfied is referred to as a reforming stoppable state.
i) The anode temperature of the SOFC is steady.
ii) The anode temperature is lower than the oxidation deterioration point.
iii) In the reformer, the hydrocarbon-based fuel is reformed, and a reformed gas having a composition suitable for supply to the anode is generated.
iv) The amount of the reformed gas generated is equal to or higher than the minimum flow rate FrMin necessary for preventing the oxidative deterioration of the anode when the anode temperature of the SOFC is higher than the oxidative deterioration point.

<Conditions i and ii>
The anode temperature means the temperature of the anode electrode. When it is difficult to directly measure the temperature of the anode electrode directly, it can be the temperature of a stack component such as a separator in the vicinity of the anode. As the anode temperature measurement position, it is preferable to adopt a location where the temperature is relatively high, more preferably a location where the temperature is highest, from the viewpoint of safety control. The position where the temperature rises can be known through preliminary experiments and simulations.

  The oxidation deterioration point is a temperature at which the anode is oxidized and deteriorated. For example, the electrical conductivity of the anode material is measured by the direct current four-terminal method by changing the temperature in a reducing or oxidizing gas atmosphere, and in an oxidizing gas atmosphere. The minimum temperature at which the electrical conductivity at is lower than the value in the reducing gas atmosphere can be set as the oxidation deterioration point.

<Condition iii>
The condition iii means that the hydrocarbon-based fuel is reformed in the reformer and a reformed gas having a composition suitable for supplying to the anode is obtained. For example, when the hydrocarbon-based fuel contains a hydrocarbon-based fuel having 2 or more carbon atoms, the reformed gas is reducible, and the C2 + component (compound having 2 or more carbon atoms) in the reformed gas flows due to carbon deposition. This means that the concentration is below the concentration that does not cause a problem with respect to path blockage or anode deterioration. The concentration of the C2 + component at this time is preferably 50 ppb or less as a mass fraction in the reformed gas.

<Condition iv>
The minimum necessary reformed gas flow rate FrMin for preventing oxidative deterioration of the anode is the smallest flow rate among the flow rates at which the anode electrode is not oxidatively deteriorated due to diffusion of the cathode off-gas from the anode outlet to the inside of the anode. This reformed gas flow rate can be known in advance by performing experiments and simulations by changing the reformed gas flow rate while maintaining the anode temperature at or above the oxidation deterioration point.

The anodic oxidation degradation can be judged by, for example, measuring the electrical conductivity of the anode electrode in an experiment and comparing it with an anode electrode that has not undergone oxidation degradation. Alternatively, the gas composition partial pressure of the anode can be calculated by simulation using an equation including an advection diffusion term, and can be determined by comparison with the equilibrium partial pressure in the oxidation reaction of the anode electrode. For example, when the anode electrode material is Ni, the equilibrium partial pressure of oxygen in the anode electrode oxidation reaction represented by the following formula is 1.2 × 10 ⁻¹⁴ atm (1.2 × 10 ⁻⁹ Pa) at 800 ° C. If the calculated value of the oxygen partial pressure of the anode is smaller than this value, it can be determined that the anode electrode is not oxidized and deteriorated. Even when the anode temperature is other than 800 ° C., the maximum value of the oxygen partial pressure at which the anode electrode is not oxidized and deteriorated can be found by equilibrium calculation. If the calculated value of the oxygen partial pressure of the anode is smaller than that value, the anode electrode is oxidized. It can be judged that it does not deteriorate.

  The reformed gas flow rate (the amount of reformed gas generated by the reformer) supplied to the SOFC to prevent oxidative deterioration of the anode can be combusted when the reformed gas passes through the SOFC and is discharged from the anode. The flow rate is preferably as follows. When the smallest flow rate among the combustible reformed gas flow rates is larger than the above-mentioned minimum required reformed gas flow rate, the smallest flow rate among the combustible reformed gas flow rates is referred to as “required minimum flow rate” in the condition iv. Thus, the reformed gas flow rate can be obtained. Whether combustion is possible can be determined by, for example, sampling the gas in the combustion gas discharge line by experiment and performing composition analysis, or calculating by simulation.

  The flow rate of the hydrocarbon-based fuel supplied to the reformer (particularly the reforming catalyst layer) in a state where the reforming can be stopped is represented as FkE.

  FkE can be obtained in advance by experiments or simulations. Water flow (including steam) for steam reforming or autothermal reforming supplied to the reformer, air flow for autothermal reforming or partial oxidation reforming, cathode air flow, fuel and air flow for supplying to the burner , The flow rate of the fluid supplied to the indirect internal reforming SOFC, such as the flow rate of the fluid such as water or air supplied to the heat exchanger; the reformer, the evaporator of water or liquid fuel, the SOFC, the fluid supply piping The electric input / output to the indirect internal reforming SOFC, such as the electric heater output for heating etc., the electric input extracted from the thermoelectric conversion module, etc., is changed, that is, the operating conditions of the indirect internal reforming SOFC are changed. Thus, FkE can be known by conducting an experiment or simulation and searching for FkE that regularly satisfies the conditions i to iv. FkE may be any value as long as the conditions i to iv are satisfied, but it is preferable to use the smallest FkE from the viewpoint of thermal efficiency. The operation condition of the indirect internal reforming SOFC including the FkE is determined in advance as the operation condition in a state where the reforming can be stopped.

  The temperature condition of the reforming catalyst layer in a state where the reforming can be stopped is represented as TrE. TrE can be known together with FkE in the process of searching for FkE, and the temperature condition of the reforming catalyst layer corresponding to one FkE used is TrE.

[Flow rate Fk (j) of different hydrocarbon fuels]
M different stepwise hydrocarbon fuel flow rates Fk (j) are determined in advance. Here, j is an integer of 1 or more and M or less, and M is an integer of 2 or more.

  However, Fk (j) increases as j increases. That is, Fk (j) <Fk (j + 1). Also, the largest Fk (M) among Fk (j) is set equal to FkE.

  At this time, the steam / carbon ratio and / or the oxygen / carbon ratio corresponding to each Fk (j) can be set for each Fk (j). In addition, when a gas that does not contribute to the reaction is supplied to the reforming catalyst layer, the flow rate can be set for each Fk (j). The steam / carbon ratio and / or oxygen / carbon ratio set corresponding to each Fk (j) and the gas flow rate that does not contribute to the reaction may be the same value for all Fk (j), and each Fk (j) Different values may be used.

  The “steam / carbon ratio” refers to the 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. “Oxygen / carbon ratio” refers to the ratio of the number of moles of oxygen molecules to the number of moles of carbon atoms in the gas supplied to the reforming catalyst layer.

Further, Fk (j) is set to be equal to or higher than the minimum value (Fk ^min (j)) of the hydrocarbon-based fuel flow rate at which a reformed gas having a flow rate equal to or higher than FrMin can be obtained by the type of reforming method performed after the stop method starts. .

This minimum value Fk ^min (j) can be determined by preliminary experiment or simulation. For example, as a reforming method, a type of reforming method that is performed after the start of the stop method is adopted, the flow rate of the hydrocarbon fuel and the temperature of the reforming catalyst layer are changed, and the flow rate of steam and / or oxygen is changed to that of the hydrocarbon fuel. The flow rate is determined from the steam / carbon ratio and / or oxygen carbon ratio corresponding to Fk (j). When supplying a gas that does not contribute to the reaction to the reforming catalyst layer, the flow rate corresponds to Fk (j). Fk ^min (j) can be obtained by measuring or calculating the reformed gas flow rate to obtain the minimum value of the hydrocarbon-based fuel flow rate at which the reformed gas flow rate becomes FrMin. Examples of the reforming method include steam reforming, autothermal reforming, and partial oxidation reforming. Or, for example, the reaction rate other than the reaction accompanied by a decrease in the hydrocarbon fuel (raw fuel) supplied to the reforming catalyst layer is much faster than the reaction accompanied by the decrease in the raw fuel, and the components other than the raw fuel instantly have an equilibrium composition. If it regarded as reaching the, Fk ^min the (j) can be determined by equilibrium calculation due Gibbs energy minimization method. For example, using Fk (j), a steam / carbon ratio corresponding to Fk (j) and / or an oxygen carbon ratio, and a gas flow rate when supplying a gas that does not contribute to the reaction, the reforming catalyst layer is used. The gas composition to be supplied is obtained, and the gas composition excluding the maximum value (allowable raw fuel composition) of the raw fuel composition suitable for supplying to the anode is obtained. Using the determined composition and total pressure, or the partial pressure of each component, changing the flow rate and temperature of the raw fuel, performing equilibrium calculation, and calculating the gas flow rate for the equilibrium composition. By adding the gas flow rate for the allowable raw fuel composition to the calculated gas flow rate for the equilibrium composition, among the reformed gas compositions suitable for supply to the anode, the flow rate of the reformed gas having the highest raw fuel flow rate And the minimum value of the raw fuel flow rate at which the reformed gas flow rate is equal to or higher than FrMin can be defined as Fk ^min (j).

In the present invention, it is assumed that there is one or more Fk (j) that is smaller than FkE and greater than or equal to Fk ^min (j). When one or more such Fk (j) does not exist, the process A is performed, the process B is performed when T <TrE in the process A, and the modification is performed when T ≧ TrE in the process A. The flow rate of the hydrocarbon-based fuel supplied to the vessel can be changed from Fk0 to FkE, and the process D can be performed.

In the present invention, it is assumed that Fk (j) smaller than FkE can be reformed when the reforming catalyst layer temperature is TrE. When one or more such Fk (j) does not exist, the process A is performed, the process B is performed when T <TrE in the process A, and the modification is performed when T ≧ TrE in the process A. The flow rate of the hydrocarbon-based fuel supplied to the vessel can be changed from Fk0 to FkE, and the process D can be performed. In addition, when the reforming catalyst layer temperature is TrE, whether or not Fk (j) smaller than FkE can be reformed is determined, for example, by previously using a hydrocarbon-based fuel at a flow rate Fk (j) in the reforming catalyst layer. It is possible to know the temperature condition T _R (j) that can be reformed at the time of reforming and to compare T _R (j) with TrE. At this time, if TrE ≧ T _R (j), it can be determined that Fk (j) smaller than FkE can be reformed when the reforming catalyst layer temperature is TrE. This T _R (j) can be obtained by preliminary experiments or simulations. For example, as a reforming method, a reforming method of a type performed after the stop method is started is adopted, the flow rate of the hydrocarbon fuel is Fk (j), and the steam and / or oxygen flow rate is set to the flow rate of the hydrocarbon fuel and Fk (j ), The flow rate obtained from the steam / carbon ratio and / or oxygen carbon ratio, and when supplying a gas that does not contribute to the reaction to the reforming catalyst layer, the flow rate corresponding to Fk (j) is supplied and reformed. Knowing by changing the temperature of the catalyst layer, analyzing or calculating the concentration of the reformed gas component, and determining the temperature of the minimum reformed catalyst layer to obtain the reformed gas with a composition suitable for supply to the anode Can do.

  Fk (j) can be set, for example, at equal intervals.

  From the viewpoint of thermal efficiency, it is preferable to increase M as much as possible and to reduce the interval between Fk (j). For example, M is increased as much as possible and the interval of Fk (j) is decreased within the allowable range of memory consumption of the flow rate control unit and within the range exceeding the accuracy of the boosting unit and the flow rate control / measurement unit. it can.

  The flow rate of the hydrocarbon-based fuel that has been supplied to the reformer at the start of the stop method is represented as Fk0.

  In the present invention, the temperature condition Tr (j) of the reforming catalyst layer in which the flow rate of the reformed gas obtained when reforming the hydrocarbon-based fuel having the flow rate Fk (j) in the reforming catalyst layer is FrMin is known in advance. (J is an integer of 1 or more and M-1 or less). This temperature condition Tr (j) can be obtained by preliminary experiments or simulations. For example, as a reforming method, a reforming method of a type performed after the stop method is started is adopted, the flow rate of the hydrocarbon fuel is Fk (j), and the steam and / or oxygen flow rate is set to the flow rate of the hydrocarbon fuel and Fk (j ) In the case of supplying a gas that does not contribute to the reaction to the reforming catalyst layer, the flow rate is set to a flow rate corresponding to Fk (j) Tr (j) can be known by changing the temperature of the reforming catalyst layer, measuring or calculating the reforming gas flow rate, and determining the temperature of the reforming catalyst layer at which the reforming gas flow rate becomes FrMin. Or, for example, the reaction rate other than the reaction accompanied by a decrease in the hydrocarbon fuel (raw fuel) supplied to the reforming catalyst layer is much faster than the reaction accompanied by the decrease in the raw fuel, and the components other than the raw fuel instantly have an equilibrium composition. Can be obtained by equilibrium calculation by the Gibbs energy minimization method or the like. For example, using Fk (j), a steam / carbon ratio corresponding to Fk (j) and / or an oxygen carbon ratio, and a gas flow rate when supplying a gas that does not contribute to the reaction, the reforming catalyst layer is used. The gas composition to be supplied is obtained, and the gas composition excluding the maximum value (allowable raw fuel composition) of the raw fuel composition suitable for supplying to the anode is obtained. Using the determined composition and total pressure, or the partial pressure of each component, and Fk (j), the temperature is changed and the equilibrium calculation is performed to calculate the gas flow rate for the equilibrium composition. By adding the gas flow rate for the allowable raw fuel composition to the calculated gas flow rate for the equilibrium composition, among the reformed gas compositions suitable for supply to the anode, the flow rate of the reformed gas having the highest raw fuel flow rate Is calculated, a temperature at which the reformed gas flow rate becomes FrMin is obtained, and this temperature can be set to Tr (j).

  Specifically, when a certain type of reforming has been performed before the start of the stop method, the same type of reforming (for example, steam reforming) can be performed after the start of the stop method. In this case, when the type of reforming is performed by the reformer, the reforming gas flow rate obtained by reforming the hydrocarbon-based fuel at the flow rate Fk (j) in the reforming catalyst layer is FrMin. Let the temperature condition of the catalyst layer be Tr (j). For example, when the steam reforming is performed before the start of the stop method, the steam reforming can be continued after the start of the stop method. When the steam reforming is performed in the reformer, the flow rate Fk (j) The temperature condition of the reforming catalyst layer from which the reformed gas having the flow rate FrMin is obtained from the hydrocarbon-based fuel is Tr (j).

  Alternatively, if a certain type of reforming (first type of reforming) has been performed before the start of the stopping method, a different type of reforming (second type of reforming) is started. Can be done later. In this case, the reforming catalyst layer having a reformed gas flow rate FrMin obtained by reforming the hydrocarbon-based fuel at the flow rate Fk (j) when performing the second type reforming in the reformer. The temperature condition is Tr (j). For example, when autothermal reforming has been performed before the start of the stop method, switching to steam reforming can be performed after the start of the stop method. At this time, when steam reforming is performed, the temperature condition of the reforming catalyst layer from which the reformed gas at the flow rate FrMin is obtained from the hydrocarbon-based fuel at the flow rate Fk (j) is Tr (j).

  In the present invention, in order to determine the flow rate of the hydrocarbon-based fuel supplied to the reforming catalyst layer, the measured value of the reforming catalyst layer temperature is compared with the TrE or the temperature condition Tr (j). For this purpose, the reforming catalyst layer temperature is measured. For example, the reforming catalyst layer temperature can be monitored (continuously measured).

  When the temperature of the reforming catalyst layer is monitored before the start of the stop method, the temperature may be continuously monitored as it is.

  Note that when the reforming method is changed before and after the start of the stopping method, the above-described FkE and TrE are determined for the stoppable state when the reforming after the reforming method is changed. Further, the aforementioned FrMin is determined for the stoppable state when the reforming after the reforming method is changed.

  If the anode temperature falls below the oxidative deterioration point, reducing gas is no longer necessary, so the supply of hydrocarbon fuel to the reformer can be stopped and the stopping method can be terminated. Therefore, the temperature monitoring of the reforming catalyst layer may be continued until the anode temperature falls below the oxidation deterioration point.

  An appropriate temperature sensor such as a thermocouple can be used for measuring the reforming catalyst layer temperature.

  In the present invention, the following steps A to D are performed while the anode temperature is not below the oxidation deterioration point. When the anode temperature falls below the oxidative deterioration point, the supply of hydrocarbon fuel to the reformer can be stopped and the stopping method can be terminated regardless of the implementation status of steps A to D. When the supply of hydrocarbon fuel to the reformer is stopped, water for steam reforming or autothermal reforming (including steam), autothermal reforming or partial oxidation reforming to be supplied to the reformer Supply of fluid supplied to indirect internal reforming SOFC, such as air, cathode air, fuel and air supplied to burner, fluid such as water and air supplied to heat exchanger, reformer and water and liquid fuel It is possible to stop the input / output of electricity to the indirect internal reforming SOFC, such as the electric heater output for heating the evaporator, cell stack, fluid supply piping, etc., the electric input taken out from the thermoelectric conversion module, etc. .

  FIG. 6 is a flowchart showing steps A to D in the stopping method of the present invention. In addition to the procedure shown in this flowchart, the anode temperature is monitored, and when the anode temperature falls below the oxidative deterioration point of the anode, the hydrocarbon fuel is supplied to the reformer regardless of the steps A to D. To stop.

  In addition, although the stop method has process AD, it is not necessary to actually perform all of process AD, and what is necessary is just to perform a part of process AD depending on the case.

[Process A]
In the stopping method according to the present invention, first, the reforming catalyst layer temperature T is measured. Then, the magnitude relationship between this temperature T and the aforementioned TrE is examined.

[Process B]
In step A, when T <TrE, the following steps B1 to B4 are sequentially performed. Note that “T <TrE” means that a hydrocarbon-based fuel having a flow rate of FkE cannot be reformed.

・ Process B1
First, step B1 is performed. That is, a step of raising the temperature of the reforming catalyst layer is performed.

  For example, the temperature of the reforming catalyst layer is raised using an appropriate heat source such as a heater or a burner attached to the reformer.

・ Process B2
And process B2 is performed. That is, a step of measuring the reforming catalyst layer temperature T and comparing the values of T and TrE is performed.

・ Process B3
If T <TrE in step B2, the process returns to step B1. That is, steps B1 to B3 are repeated while T <TrE. During this time, the temperature of the reforming catalyst layer rises.

  In performing steps B2 and B3, the temperature rise in step B1 may be temporarily stopped, but step B1 may be continued while steps B2 and B3 are performed.

・ Process B4
If T ≧ TrE in step B2, the flow rate of hydrocarbon-based fuel supplied to the reformer (represented as Fk) is changed from Fk0 to FkE, and the step of moving to step D is performed. “T ≧ TrE” means that a hydrocarbon-based fuel having a flow rate of FkE or less can be reformed.

  At this time, when changing the reforming method before and after the start of the stop method, the fuel flow is changed from Fk0 to FkE and the reforming method is changed. By this method, it is possible to prevent oxidative deterioration of the anode by the reformed gas while reliably reforming the hydrocarbon fuel.

[Process C]
In step A, if T ≧ TrE, step C is performed. “T ≧ TrE” means that a hydrocarbon-based fuel having a flow rate of FkE or less can be reformed. In this case, of the predetermined hydrocarbon fuel flow rate Fk (j), the corresponding temperature condition Tr (j) is equal to or lower than the reforming catalyst layer temperature T measured in step A and equal to or higher than Fk (1) and FkE. If there is no smaller flow rate Fk (j) (hereinafter, this flow rate Fk (j) is referred to as “selective flow rate”), the flow rate of the hydrocarbon-based fuel supplied to the reformer is changed from Fk0 to FkE. Move to D. At this time, when the reforming method is changed before and after the stop method is started, the reforming method can be changed while changing the fuel flow rate from Fk0 to FkE.

  For example, considering j = 2, if Tr (2) is equal to or lower than the reforming catalyst layer temperature T measured in step A and Fk (1) ≦ Fk (2) <FkE, the selective flow rate Fk ( 2) will exist. If there is no such selective flow rate, the above operation is performed.

  On the other hand, in step A, when T ≧ TrE, if the above-mentioned selective flow rate Fk (j) is present among the predetermined hydrocarbon fuel flow rate Fk (j), the following steps C1 to C7 are sequentially performed. Do.

・ Process C1
J that gives the smallest Fk (j) of the selective flow rates is represented as J, and the flow rate of the hydrocarbon-based fuel supplied to the reformer is changed from Fk0 to Fk (J). At this time, when the reforming method is changed before and after the start of the stop method, the flow rate Fk of the hydrocarbon-based fuel is changed from Fk0 to Fk (J), and the reforming method is changed.

・ Process C2
The reforming catalyst layer temperature is measured, and the measured temperature T is compared with TrE.

・ Process C3
When T ≦ TrE in Step C2, the flow rate of the hydrocarbon-based fuel supplied to the reformer is set to FkE, and the process proceeds to Step D.

・ Process C4
If T> TrE in step C2, T is compared with Tr (J).

・ Process C5
If T> Tr (J) in step C4, the process returns to step C2. That is, if T> TrE in step C2 and T> Tr (J) in step C4, steps C2, C3 and C5 are repeated. During this time, the reforming catalyst layer temperature decreases. Therefore, in any case, T ≦ Tr (J).

・ Process C6
When T ≦ Tr (J) in Step C4, the flow rate of the hydrocarbon-based fuel supplied to the reformer is increased from Fk (J) to Fk (J + 1), and J is increased by 1.

・ Process C7
After Step C6, J and M are compared. If J ≠ M, the process returns to Step C2, and if J = M, the process goes to Step D.

  After Step C, if the state is T ≧ TrE, the operation condition is set to the operation condition in which the reforming can be stopped, and the unreformed hydrocarbon fuel is shifted to the reforming stoppable state without flowing into the anode. be able to. However, generally, the higher the reforming catalyst layer temperature T is, the larger the reformed gas flow rate is in the temperature range preferable for reforming. Therefore, while T ≧ TrE, the reformed gas flow rate becomes FrMin or more, and excess hydrocarbon fuel. Will be supplied.

  On the other hand, after Step C, a reformed gas having a flow rate of FrMin or higher can be generated, and among the flow rates of hydrocarbon fuel smaller than FkE, a hydrocarbon fuel having a flow rate as small as possible is supplied to the reformer, so that FrMin or higher The hydrocarbon fuel supplied to the reformer can be made as small as possible while the reformer generates a reformed gas flow of the above flow rate. However, if the supply of hydrocarbon fuel with a flow rate as small as possible is continued among the flow rates of hydrocarbon fuel that can generate reformed gas with a flow rate higher than FrMin, the temperature of the reforming catalyst layer will decrease, resulting in T <TrE. Of hydrocarbon fuel flow that can generate reformed gas with a flow rate higher than FrMin, hydrocarbon fuel with a flow rate as small as possible may not be reformable, and the operating conditions can be stopped Under these operating conditions, there is a case where it is not possible to shift to a state in which reforming can be stopped without allowing unreformed hydrocarbon fuel to flow into the anode.

  Therefore, when T ≦ TrE, the operation condition is set to the operation condition in which the reforming can be stopped, so that the unreformed hydrocarbon fuel can be shifted to the reforming stoptable state without flowing into the anode. .

  Further, when T> TrE, by supplying a hydrocarbon-based fuel having a flow rate as small as possible out of the flow rate of the hydrocarbon-based fuel capable of generating a reformed gas of FrMin or higher to the reformer, FrMin or higher While generating the reformed gas flow rate in the reformer, the hydrocarbon fuel supplied to the reformer can be made as small as possible.

[Process D]
In step D, the process waits for the anode temperature to fall below the oxidation deterioration point. During this time, the flow rate of the hydrocarbon fuel is maintained at FkE, the flow rate of water for steam reforming or autothermal reforming (including steam) supplied to the reformer, air for autothermal reforming or partial oxidation reforming. The flow rate of the fluid supplied to the indirect internal reforming SOFC, such as the flow rate, the cathode air flow rate, the fuel and air flow rate supplied to the burner, the flow rate of the fluid such as water and air supplied to the heat exchanger, the reformer and water Input and output of electricity to the indirect internal reforming SOFC, such as an electric heater output for heating an evaporator of liquid fuel, a cell stack, a fluid supply pipe, etc., an electric input taken from a thermoelectric conversion module, etc. The operating condition is maintained in a predetermined reforming stoppable state. That is, the operating conditions of the indirect internal reforming SOFC in a predetermined reforming stoppable state are maintained. Since the anode temperature decreases with time, the anode temperature eventually falls below the oxidation degradation point. The anode temperature can be appropriately monitored (continuously measured) using a temperature sensor such as a thermocouple.

  The monitoring of the anode temperature is preferably started immediately after starting the shutdown method. If these temperatures are monitored before the stop method is started, the temperature may be continuously monitored even when the stop method is performed.

  When the anode temperature falls below the oxidative deterioration point, the supply of hydrocarbon fuel to the reformer can be stopped to end the stopping method.

[Case 1]
An example of the stopping method of the present invention will be described with reference to FIG. 2A to 2C, the horizontal axis represents the elapsed time from the time when the stopping method of the present invention is started. In FIG. 6A, the vertical axis is the flow rate of the reformed gas obtained from the reformer, in FIG. 5B the vertical axis is the temperature, and in FIG. 5C, the vertical axis is the flow rate of the hydrocarbon fuel ( The same applies to the following figures).

  Stepwise flow rates Fk (1) and Fk (2) = FkE are determined in advance. In this case, M = 2.

  The monitoring of the reforming catalyst layer temperature and the monitoring of the anode temperature are continuously performed before the start of the stopping method (the same applies to the subsequent cases).

  As soon as the stopping method is started, the process A is performed. That is, the reforming catalyst layer temperature T is measured, and this T and TrE are compared.

  At this time, since T ≧ TrE (FIG. 2B), Step C is performed.

  Tr (1) corresponding to Fk (1) is equal to or lower than the reforming catalyst layer temperature T measured in step A (FIG. 2 (b)). Fk (1) is not less than Fk (1) and less than FkE (FIG. 2 (c)). Corresponding Tr (j) is not defined in Fk (2). Thus, Fk (1) is the only selective flow rate. Since the selective flow rate Fk (1) exists, the steps C1 to C7 are sequentially performed.

  In step C1, the smallest Fk (j) of the selective flow rates is Fk (1), and j = 1, which gives Fk (1), J = 1. Then, the flow rate of the hydrocarbon fuel is changed from Fk0 to Fk (1). When changing the reforming method before and after the start of the stop method, the flow rate of the hydrocarbon-based fuel is changed from Fk0 to Fk (1) and the reforming method is changed in step C1.

  In step C2, the reforming catalyst layer temperature T is measured, and T and TrE are compared.

  At this time, since T> TrE (FIG. 2B), T is compared with Tr (1) in step C4. At this time, since T> Tr (1) (FIG. 2B), the process returns to step C2.

  Steps C2, C4, and C5 are repeated for a while, while the reforming catalyst layer temperature decreases with time. While T ≧ TrE, a hydrocarbon-based fuel having a flow rate of Fk (1) that is a flow rate of FkE or less can be reformed. Further, while T ≧ Tr (1), the reformed gas having a flow rate of FrMin or higher is continuously supplied to the anode by supplying the hydrocarbon-based fuel having the flow rate of Fk (1) to the reformer.

  In the case shown in FIG. 2, immediately after the reforming catalyst layer temperature becomes TrE or lower, Fk is set to FkE, and the process D is started (process C3).

  In step D, the process waits for the anode temperature to fall below the oxidation deterioration point.

  If the anode temperature is lower than the oxidation deterioration point, the supply of hydrocarbon fuel to the reformer can be stopped and the stopping method can be terminated.

  In step C2, if the anode temperature falls below the oxidative deterioration point earlier than T becomes equal to or lower than TrE, step C3 may not be performed.

  By operating in this way, it is possible to supply reformed gas of a minimum necessary flow rate or more to the anode while reliably performing reforming.

[Case 2]
In the above case, since TrE> Tr (1), Fk is set to FkE when T becomes TrE or less in Step C3. In this case, Tr (1)> TrE, and when T becomes Tr (1) or less in Step C4, Fk is set to Fk (2) = FkE (Step C6). This case will be described with reference to FIG.

  The operation is the same as that in Case 1 from the start of the stop method until the time T ≦ Tr (1). That is, the process moves from the process A to the process C, and after the process C1 is performed, the processes C2, C4, and C5 are repeated until T ≦ Tr (1). While T ≧ TrE, a hydrocarbon-based fuel having a flow rate of Fk (1) that is a flow rate of FkE or less can be reformed. Further, while T ≧ Tr (1), the reformed gas having a flow rate of FrMin or higher is continuously supplied to the anode by supplying the hydrocarbon-based fuel having the flow rate of Fk (1) to the reformer.

  When T becomes Tr (1) or less in step C4, immediately, Fk is increased from Fk (1) to Fk (2) = FkE, and J is increased by 1 to 2 (step C6). In step C7, J and M are compared. Since J = M = 2, the process proceeds to step D.

  The process D and subsequent steps are the same as the case 1.

  If the anode temperature falls below the oxidative deterioration point sooner than T becomes Tr (1) or less, step C6 may not be performed.

  By operating in this way, it is possible to supply reformed gas of a minimum necessary flow rate or more to the anode while reliably performing reforming.

[Case 3]
The case where M = 3 will be described with reference to FIG. Here, Tr (1)> Tr (2)> TrE. Also, both Tr (1) and Tr (2) are below the temperature T measured in step A, and both Fk (1) and Fk (2) are greater than or equal to Fk (1) and less than FkE. There are two Fk (j) as the target flow rate, that is, Fk (1) and Fk (2).

  The operation is the same as that in Case 1 from the start of the stop method until the time T ≦ Tr (1). That is, the process moves from the process A to the process C, and after the process C1 is performed, the processes C2, C4, and C5 are repeated until T ≦ Tr (1). While T ≧ TrE, it is possible to reform the hydrocarbon-based fuel having the flow rates of Fk (1) and Fk (2) that are lower than or equal to FkE. Further, while T ≧ Tr (1), the reformed gas having a flow rate of FrMin or higher is continuously supplied to the anode by supplying the hydrocarbon-based fuel having the flow rate of Fk (1) to the reformer.

  When T becomes Tr (1) or less in Step C4, Fk is immediately increased from Fk (1) to Fk (2), and J is increased by 1 to 2 (Step C6). In step C7, J and M are compared. Since J ≠ M = 3, the process returns to step C2, and steps C2, C4 and C5 are repeated for a while. While T ≧ Tr (2), the reformed gas having a flow rate of FrMin or higher is continuously supplied to the anode by supplying the hydrocarbon-based fuel having a flow rate of Fk (2) to the reformer.

  As soon as the reforming catalyst layer temperature decreases and T becomes Tr (2) or lower in Step C4, Fk is increased from Fk (2) to Fk (3) = FkE, and J is increased by 1. 3 (step C6). In step C7, J and M are compared. Since J = M = 3, the process proceeds to step D.

  The processes after the process D are the same as those in the case 1.

  Of course, even in this case, if the anode temperature falls below the oxidative deterioration point, the supply of hydrocarbon fuel to the reformer can be stopped at that time, and the stopping method can be terminated.

  Case 3 can reduce the amount of hydrocarbon fuel to be supplied before the reforming stop and can shorten the stop time (the time from the start of the stop method until the anode temperature falls below the oxidation deterioration point), compared to Case 2. it can.

[Case 4]
The case where T <TrE in step A, that is, the case where step B is performed will be described with reference to FIG.

  Immediately after the start of the stopping method, step A is performed to measure the reforming catalyst layer temperature T and compare T and TrE. Since T <TrE (FIG. 5B), the process C is not performed and the process B is performed.

  In this case, as shown in FIG. 5, an appropriate heat source such as a burner or a heater attached to the reformer is used until the reforming catalyst layer temperature becomes equal to or higher than TrE so that the hydrocarbon-based fuel having a flow rate FkE can be reformed. The temperature of the reforming catalyst layer is raised. That is, steps T1 to B3 are repeated while T (reforming catalyst layer temperature measured in step B2) <TrE.

  When T ≧ TrE in step B2, the flow rate Fk of the hydrocarbon-based fuel supplied to the reformer is changed from Fk0 to FkE (step B4). When changing the reforming method before and after the start of the stop method, the fuel flow is changed from Fk0 to FkE and the reforming method is changed. Then, the process proceeds to process D (process B4).

  The processes after the process D are the same as those in the case 1.

[About “reformable”]
In the present specification, the fact that a certain amount of hydrocarbon-based fuel can be reformed in the reforming catalyst layer means that when the hydrocarbon-based fuel of that flow rate is supplied to the reforming catalyst layer, the reforming catalyst layer This means that the composition of the gas discharged from the gas becomes a composition suitable for supplying to the anode of the SOFC.

For example, being able to be reformed in the reforming catalyst layer means that the supplied hydrocarbon fuel can be decomposed to a C1 compound (a 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. It means a case where quality can progress. The concentration of the C2 + component at this time is preferably 50 ppb or less as a mass fraction in the reformed gas. At this time, 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 if 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.

Regarding the reducing property of the reforming catalyst layer outlet gas, even if this gas is supplied to the anode, it only needs to be capable of suppressing oxidative deterioration of the anode. For this purpose, for example, 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. For example, when the anode electrode material is Ni and the anode temperature is 800 ° C., 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.

[Measurement point of reforming catalyst layer temperature]
Hereinafter, measurement points of the reforming catalyst layer temperature will be described in detail. The measurement point is, when knowing TrE and Tr (j), and T _R a (j) in advance, and, when measuring the temperature of the reforming catalyst layer in the step A through C, can be employed.

<When there is one temperature measurement point>
-Temperature measurement location When the temperature measurement point of the reforming catalyst layer is one point, the temperature measurement location is preferably a location where the temperature is relatively low in the reforming catalyst layer from the viewpoint of safety-side control, More preferably, it is preferable to employ a portion having the lowest temperature in the reforming catalyst layer. When the heat of reaction in the reforming catalyst layer is endothermic, the vicinity of the center of the catalyst layer can be selected as the temperature measurement location. When the heat of reaction in the reforming catalyst layer is exothermic, and the end portion becomes cooler than the center portion due to heat dissipation, the end portion of the catalyst layer can be selected as the temperature measurement location. The position where the temperature is lowered can be known by preliminary experiments and simulations.

<When there are multiple temperature measurement points>
The temperature measurement point need not be a single point. From the viewpoint of more accurate control, it is preferable that there are two or more temperature measurement points. For example, the inlet temperature and outlet temperature of the reforming catalyst layer are measured, and the average of these can be used as the aforementioned reforming catalyst layer temperature T. However, the reaction rate other than the reaction accompanied by a decrease in the hydrocarbon fuel (raw fuel) supplied to the reforming catalyst layer is much faster than the reaction accompanied by the decrease in the raw fuel, and components other than the raw fuel instantaneously have an equilibrium composition. When it can be assumed that the temperature reaches a point, even if there are a plurality of temperature measurement points of the reforming catalyst layer, the temperature compared with Tr (j) in Step C is the reforming catalyst layer of the temperatures measured at the plurality of points. It is preferred to use the temperature closest to the outlet. In the case where there are a plurality of temperatures closest to the reforming catalyst layer outlet, appropriately calculated values such as the lowest value and the average value thereof can be used as representative values.

Or, for example, consider a region Z _i (N is an integer greater than or equal to 2 and i is an integer greater than or equal to 1 and less than N) by dividing the reforming catalyst layer into N, knowing the temperature T _i of each of the divided regions Z _i , TrE (j) (= {TrE ₁ , TrE ₂ ,..., TrE _N }) and Tr (j) (= {Tr (j) ₁ , Tr (j) ₂ ,..., Tr (j) _N }) can be known in advance. At this time, if any of T _i becomes TrE _i or less, the flow rate of the hydrocarbon-based fuel can be set to FkE. At this time, if any of T _i becomes equal to or smaller than Tr (j) _i , Fk (j) can be increased to Fk (j + 1). Alternatively, the reaction rate other than the reaction accompanied by a decrease in the hydrocarbon-based fuel (raw fuel) supplied to the reforming catalyst layer is much faster than the reaction accompanied by the decrease in the raw fuel, and components other than the raw fuel instantaneously have an equilibrium composition. When it can be assumed that the temperature reaches the reforming catalyst layer outlet of T _{i that} is equal to or lower than Tr (j), Fk (j) can be increased to Fk (j + 1).

When N divided regions Z _i are considered, the temperature of all the divided regions may be set as the temperature condition, or the temperature of a part of the N divided regions may be set as the temperature condition. Depending on the amount of hydrocarbon-based fuel supplied, the catalyst layer region used as the temperature condition can be appropriately changed.

The temperature of the divided region Z _i, can be used as they are actually measured temperature may be used such as the average value of the inlet temperature and the outlet temperature of the divided region, the appropriate calculated value as a representative value.

Further, it is not necessary to measure the temperature for all the divided regions Z _i . Further, the catalyst layer division number N and the number of temperature measurement points can be set independently.

  It is also possible to know the temperature by measuring the temperature of a part of the N divided regions and supplementing the remaining divided regions as appropriate from the measured temperatures.

  For example, as the temperature of the divided area where the temperature sensor is not installed, the temperature of the divided area closest to the divided area can be used. When there are two closest divided regions, the temperature of one of the two divided regions can be used, or the average value of the temperatures of the two divided regions can be used.

  Regardless of the divided region, the temperature of a plurality of points (at different positions in the gas flow direction) of the reforming catalyst layer can be measured, and the temperature of each divided region can be known from the measured temperatures of the plurality of points. For example, the temperature at the inlet and outlet of the reforming catalyst layer is measured (and the temperature at an arbitrary position in the middle portion may be measured), and the reforming catalyst layer is measured from these measured temperatures by an approximation method such as the least square method. It is possible to interpolate the temperature and know the temperature of the divided area from the interpolation curve.

(Example of temperature measurement location)
In order to know the temperature of all the divided areas, the temperature of the following points can be measured.
-Entrance and exit of each divided area.
-Inside each divided area (inside from the entrance and exit) (one or more points).
-Entrance, exit and inside of each divided area (one or more points for one divided area).

In order to know the temperature of some of the divided regions, the temperature at the following locations can be measured.
-Entrance and exit of some divided areas.
-Inside of some divided areas (inside from the inlet and outlet) (one or more points).
-Entrances, exits, and interiors of some divided areas (one or more points for one divided area).

[Others]
When the flow rate Fk of hydrocarbon-based fuel is set to FkE, the flow rate of water for steam reforming or autothermal reforming (including steam) supplied to the reformer according to the flow rate, if necessary, self-thermal reforming Or the fluid supplied to the indirect internal reforming SOFC, such as the air flow rate for partial oxidation reforming, the cathode air flow rate, the fuel and air flow rate supplied to the burner, the flow rate of fluid such as water or air supplied to the heat exchanger Indirect internal reforming SOFC, such as the flow rate of air, the reformer and the electric heater output to heat the water and liquid fuel evaporator, cell stack, fluid supply piping, etc., the thermoelectric conversion module etc. The input / output of electricity to the operation condition is set in a predetermined reforming stoppable state. That is, the operation condition of the indirect internal reforming SOFC in a predetermined reforming stoppable state is set.

  When changing the flow rate of the hydrocarbon-based fuel supplied to the reformer in step C1 and step C6, the flow rate of the fluid supplied to the indirect internal reforming SOFC according to the necessity as described above, indirect internal Input / output of electricity to the reforming SOFC can be set to predetermined operating conditions. For example, with respect to the flow rate of water supplied to the reformer, the water flow rate can be reduced as the fuel flow rate decreases so that the steam / carbon ratio is maintained at a predetermined value in order to suppress carbon deposition. As for the air flow rate supplied to the reformer, the air flow rate can be reduced as the fuel flow rate decreases so that the oxygen / carbon ratio maintains a predetermined value. Regarding the flow rate of the fluid supplied to the indirect internal reforming SOFC other than water and air supplied to the reformer, and the input / output of electricity to the indirect internal reforming SOFC, operating conditions in a predetermined reforming stoppable state Or predetermined operating conditions as a function of fuel flow rate.

  When changing the reforming method, if necessary, the flow rate of the fluid supplied to the indirect internal reforming SOFC and the input / output of electricity to the indirect internal reforming SOFC are determined according to the necessity as described above. Can be a condition. For example, the flow rate of water supplied to the reformer can be changed to a flow rate with a predetermined steam / carbon ratio in order to suppress carbon deposition. The air flow rate supplied to the reformer can be changed to a flow rate that provides a predetermined oxygen / carbon ratio. Regarding the flow rate of the fluid supplied to the indirect internal reforming SOFC other than water and air supplied to the reformer, and the input / output of electricity to the indirect internal reforming SOFC, operating conditions in a predetermined reforming stoppable state Or predetermined operating conditions as a function of fuel flow rate.

  When a steam reforming reaction is performed, that is, when steam reforming or autothermal reforming is performed, steam is supplied to the reforming catalyst layer. When performing a partial oxidation reforming reaction, that is, when performing partial oxidation reforming or autothermal reforming, an oxygen-containing gas is supplied to the reforming catalyst layer. As the oxygen-containing gas, a gas containing oxygen can be used as appropriate, but air is preferable because it is easily available.

  The present invention is particularly effective when the hydrocarbon fuel has 2 or more carbon atoms. This is because such fuel is particularly required to be reformed.

[Hydrocarbon fuel]
As the hydrocarbon-based fuel, as a reformed gas raw material, a compound known from the field of SOFC, containing carbon and hydrogen (may contain other elements such as oxygen) or a mixture thereof, or a mixture thereof may be used as appropriate. And compounds having carbon and hydrogen in the molecule such as hydrocarbons and alcohols can be used. For example, 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. is there.

  Of these, 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, SOFC power generators using kerosene or LPG are useful as emergency power supplies. In particular, kerosene is preferable because it is easy to handle.

[Reformer]
The reformer produces a reformed gas containing hydrogen from a hydrocarbon fuel.

  In the reformer, any of steam reforming, partial oxidation reforming, and autothermal reforming accompanied by a partial oxidation reaction in the steam reforming reaction can 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.

  As the structure of the reformer, a structure known as a reformer can be appropriately adopted. For example, it is possible to have 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.

  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.

  Supply hydrocarbon-based fuel (pre-vaporized if necessary), water vapor, and oxygen-containing gas such as air, if necessary, individually or appropriately mixed to the reformer (reforming catalyst layer) can do. The reformed gas is supplied to the anode of the SOFC.

[SOFC]
The reformed gas obtained from the reformer is supplied to the anode of the SOFC. On the other hand, an oxygen-containing gas such as air is supplied to the cathode of the SOFC. During power generation, the SOFC generates heat with power generation, and the heat is transmitted from the SOFC to the reformer by radiant heat transfer or the like. Thus, the SOFC exhaust heat is used to heat the reformer. Gas exchange and the like are appropriately performed using piping or the like.

  As the SOFC, a known SOFC can be appropriately selected and employed. In the SOFC, oxygen ion conductive ceramics or proton ion conductive ceramics are generally used as an electrolyte.

  The SOFC 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, sometimes referred to as a bundle, but the stack in this specification includes a bundle) is preferable. Used. In this case, one or more stacks may be used.

  The shape of the SOFC is not limited to the cubic stack, and an appropriate shape can be adopted.

  For example, oxidation deterioration of the anode may occur at about 400 ° C.

[Case]
As the casing (module container), an appropriate container capable of accommodating the SOFC, the reformer, and the combustion region can be used. As 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 is preferably airtight so that the interior of the module container does not communicate with the outside (atmosphere).

(Combustion area)
The combustion region is a region where the anode off gas discharged from the anode of the SOFC can be combusted. For example, 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. For this purpose, 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.

[Reforming catalyst]
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 steam reforming catalyst include ruthenium-based and nickel-based catalysts, examples of the partial oxidation reforming catalyst include platinum-based catalysts, and examples of the autothermal reforming catalyst include rhodium-based catalysts. When steam reforming is performed, a self-thermal reforming catalyst having a steam reforming function can also be used.

  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 or autothermal reforming reaction can proceed is, for example, 400 ° C. or more.

[Operation conditions of reformer]
Hereinafter, the conditions at the time of stop operation in the reformer will be described for each of steam reforming, autothermal reforming, and partial oxidation reforming.

In 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 1.5-7, more preferably 2-5. When the hydrocarbon fuel is liquid, 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 , and still more preferably 0.2 to 5 h ⁻¹ .

In autothermal reforming, 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. Equilibrium calculations can be performed and an oxygen-containing gas can be added so that the overall reaction heat is exothermic. 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, for example, in the range of 400 ° C to 1000 ° C, preferably 450 ° C to 850 ° C, more preferably 500 ° C to 800 ° C. When the hydrocarbon fuel is a liquid, the space velocity (LHSV) at this time is preferably 0.05 to 20 ⁻¹ , more preferably 0.1 to 10 ⁻¹ , and still more preferably 0.2 to 5 ^−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.

In partial oxidation reforming, 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. In order to secure a temperature for proceeding the reaction, 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, and more preferably 550 ° C to 800 ° C. When the hydrocarbon-based fuel is liquid, the space velocity (LHSV) is preferably selected in the range of 0.1 to 30 ^-1. Steam can be introduced to suppress the generation of soot in the reaction system, and the amount thereof is preferably 0.1 to 5, more preferably 0.1 to 3, more preferably 1 to 1, as a steam / carbon ratio. 2.

[Other equipment]
Known components of the indirect internal reforming SOFC can be appropriately provided as necessary. Specific examples include a vaporizer for vaporizing liquid, a pump for pressurizing various fluids, a pressure increasing means such as a compressor and a blower, a valve for adjusting the flow rate of the fluid, or for blocking / switching the flow of the fluid. Such as flow rate control means, flow path blocking / switching means, heat exchanger for heat exchange / recovery, condenser for condensing gas, heating / heat-retaining means for externally heating various devices with steam, etc., hydrocarbon system Fuel (reforming raw materials) and combustion fuel storage means, instrumentation air and electrical systems, control signal systems, control devices, output and power electrical systems, desulfurization to reduce the concentration of sulfur in the fuel Such as a vessel.

  The present invention can be applied to, for example, an indirect internal reforming SOFC used in a stationary or moving power generator or a cogeneration system.

DESCRIPTION OF SYMBOLS 1 Water vaporizer 2 Electric heater attached to water vaporizer 3 Reformer 4 Reforming catalyst layer 5 Combustion zone 6 SOFC
7 Igniter 8 Case (module container)
9 Electric heater attached to the reformer

Claims (3)

A reformer having a reforming catalyst layer for reforming hydrocarbon fuel to produce reformed gas;
A solid oxide fuel cell that generates electric power using the reformed gas; and
A combustion region for burning anode off-gas discharged from the solid oxide fuel cell;
A method for stopping an indirect internal reforming solid oxide fuel cell comprising: a reformer, a solid oxide fuel cell, and a housing that houses a combustion region;
The following conditions i to iv,
i) The anode temperature of the solid oxide fuel cell is steady,
ii) the anode temperature is below the oxidative degradation point;
iii) In the reformer, the hydrocarbon-based fuel is reformed, and a reformed gas having a composition suitable for supplying to the anode is generated,
iv) The amount of the reformed gas generated is equal to or higher than the minimum flow rate FrMin necessary for preventing the oxidative deterioration of the anode when the anode temperature of the solid oxide fuel cell is equal to or higher than the oxidative deterioration point.
The flow rate of the hydrocarbon-based fuel supplied to the reformer in a state where all of the above are satisfied is represented as FkE, and the temperature condition of the reforming catalyst layer in the state is represented as TrE,
A stepwise hydrocarbon-based fuel flow rate Fk (j) is determined in advance (where j is an integer of 1 to M, and M is an integer of 2 or more), where Fk (j) is The largest Fk (M) among Fk (j) s is equal to FkE, and Fk (j) is not changed in the reaction temperature range of the reforming method of the kind performed after the start of the stopping method. It is above the minimum value of the hydrocarbon fuel flow rate that can obtain the reformed gas with a flow rate of FrMin or higher by the quality method,
The flow rate of the hydrocarbon-based fuel that has been supplied to the reformer at the start of the stop method is expressed as Fk0,
The temperature of the reforming catalyst layer at which the flow rate of the reformed gas obtained when the hydrocarbon-based fuel at the flow rate Fk (j) is reformed in the reforming catalyst layer by the kind of reforming method performed after the start of the stopping method is FrMin. Knowing the condition Tr (j) in advance (where j is an integer greater than or equal to 1 and less than or equal to M−1)
When the anode temperature falls below the oxidative degradation point, the supply of hydrocarbon fuel to the reformer is stopped and the stopping method is terminated.
While the anode temperature is not below the oxidation degradation point,
A) a step of measuring the reforming catalyst layer temperature T and comparing the measured temperature T with TrE;
B) A step of sequentially performing the following steps B1 to B4 when T <TrE in step A,
B1) Step of heating the reforming catalyst layer
B2) a step of measuring the reforming catalyst layer temperature and comparing the measured temperature T with TrE;
B3) A process of returning to the process B1 when T <TrE in the process B2,
B4) When T ≧ TrE in step B2, the flow rate of the hydrocarbon-based fuel supplied to the reformer is changed from Fk0 to FkE, and the process proceeds to step D.
C) In the case of T ≧ TrE in step A,
Of the predetermined hydrocarbon fuel flow rate Fk (j), the corresponding temperature condition Tr (j) is equal to or lower than the reforming catalyst layer temperature T measured in step A and is equal to or higher than Fk (1) and smaller than FkE. If Fk (j) does not exist, the flow rate of the hydrocarbon-based fuel supplied to the reformer is changed from Fk0 to FkE, and the process proceeds to step D.
Of the predetermined hydrocarbon fuel flow rate Fk (j), the corresponding temperature condition Tr (j) is equal to or lower than the reforming catalyst layer temperature T measured in step A and is equal to or higher than Fk (1) and smaller than FkE. If Fk (j) is present, the following steps C1 to C7 are sequentially performed,
C1) The smallest Fk (j) out of the flow rates Fk (j) where the corresponding temperature condition Tr (j) is equal to or lower than the reforming catalyst layer temperature T measured in step A and is equal to or higher than Fk (1) and smaller than FkE. J is given as J,
Changing the flow rate of the hydrocarbon-based fuel supplied to the reformer from Fk0 to Fk (J);
C2) a step of measuring the reforming catalyst layer temperature and comparing the measured temperature T with TrE;
C3) Step T2, when T ≦ TrE, the flow rate of the hydrocarbon-based fuel supplied to the reformer is set to FkE, and the flow proceeds to Step D.
C4) a step of comparing T with Tr (J) when T> TrE in Step C2,
C5) If T> Tr (J) in step C4, returning to step C2,
C6) A step of increasing the flow rate of the hydrocarbon-based fuel supplied to the reformer from Fk (J) to Fk (J + 1) and increasing J by 1 when T ≦ Tr (J) in step C4.
C7) After step C6, J and M are compared. If J ≠ M, the process returns to step C2, and if J = M, the process moves to step D.
and,
D) A method for stopping an indirect internal reforming solid oxide fuel cell, which includes a step of waiting for the anode temperature to fall below the oxidation deterioration point.   The method according to claim 1, wherein the hydrocarbon fuel includes a hydrocarbon fuel having 2 or more carbon atoms.   The method according to claim 2, wherein the concentration of the compound having 2 or more carbon atoms in the reformed gas is 50 ppb or less on a mass basis.

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