JP2000188121A - Fuel cell generator, diagnosing method for deterioration of reformer, and computer-readable recording media with deterioration diagnosing program recorded therein - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fuel cell generator capable of judging replacement timing of reforming catalyst by instantaneously and continuously diagnose deterioration of a reformer, a deterioration diagnosing method and computer-readable recording media with a deterioration diagnosing program recorded therein. SOLUTION: This fuel cell generator has a means 6 of measuring an inlet temperature of crude fuel gas reformer to measure the inlet temperature of the reformer for crude fuel gas 1 containing city gas 4 and vapor for reforming 31 and a means 5 of diagnosing deterioration to diagnose the deteriorated condition of the reformer by referring the inlet temperature of the reformer for crude fuel gas detected by the means 6 of measuring the inlet temperature of the crude fuel gas by receiving a temperature detecting signal from the means 6 of measuring the inlet temperature of the reformer for crude fuel gas to a relation between a predetermined inlet temperature of the reformer for crude fuel gas and an amount of deteriorated reforming catalyst of the reformer 8.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fuel cell power generator and a fuel cell generator for generating electricity by reacting fuel and reforming steam in a reformer to produce hydrogen, and reacting the hydrogen with oxygen in a fuel cell stack. In the computer-readable recording medium on which the deterioration diagnosis method and the deterioration diagnosis program of the reforming device are recorded, the reforming device is instantaneously and continuously instantaneously and continuously analyzed without analyzing the reformed gas at the outlet of the reforming device. The present invention relates to a fuel cell power generator, a method of diagnosing deterioration of a reformer, and a computer-readable recording medium storing a deterioration diagnosis program capable of diagnosing a deterioration state and determining a time for replacing a reforming catalyst. .

[0002]

2. Description of the Related Art FIG. 4 shows a configuration of a conventional phosphoric acid fuel cell power generator using city gas as fuel, as a conventional example of a fuel cell power generator. In the figure, 1 is a raw fuel gas, 2 is a reformed gas, 3 is a shutoff valve, 4 is a city gas, 7 is a desulfurizer, 8 is a reformer, 9 is a reformer burner, 10 is a shutoff valve, and 11 is a shutoff valve. Shift converter, 12 is combustion air, 13 is fuel electrode exhaust gas, 14 is reformer burner combustion exhaust gas, 15 is air blower, 16 is power generation air, 17 is outside air, 18 is fuel electrode, 1
9 is an electrolyte, 20 is an oxidizer electrode, 21 is a fuel cell stack, 22 is a voltage measuring means, 23 is a current measuring means, 24
Is a converter, 25 is a load, 26 is battery cooling water, 27 is a steam separator, 28 is a steam separator heater, 30 is a flow control valve, 31 is reforming steam, 33 is an evaporator, and 34 is a drain. Steam for heat recovery, 35 is a waste heat utilization system, 36 is a refrigerant, 3
7 is an oxidant electrode exhaust gas, 38 is a condenser, 39 is an exhaust gas, 4
0 is condensed water, 41 is reformer temperature measuring means, 42 is battery cooling water temperature measuring means, 43 is makeup water pump, 44 is makeup water, 45 is a flow control valve, 46 is a flow control valve, and 47 is heat exchange. , 48 is a reforming section, 49 is a pressure measuring means, 50 is a fuel cell output, 51 is a heat exchanger, 52 is a flow control valve, 53 is an ejector, 54 is a flow control valve, 55 is a liquid level measuring means,
56 is a pump, 57 is a shutoff valve, 58 is condensed water, 59 is a starter burner, 60 is a shutoff valve, 61 is a reformer starter burner air, 62 is a shutoff valve, 63 is a cooler, and 64 is a recycle gas. is there.

The operation of this conventional fuel cell power generator will be described below with reference to FIG. The desulfurization apparatus 7 in which the shut-off valve 3 is opened and the city gas 4 is heated by exchanging heat with the reformed gas 2 in the heat exchanger 47 and then filled with a desulfurization catalyst (a cobalt-molybdenum catalyst and a zinc oxide adsorbent). And the sulfur content contained in the deodorant in the city gas 4 that causes deterioration of the catalyst of the reformer 8 and the fuel electrode 18 of the fuel cell stack 21 by the desulfurizer 7 is adsorbed and removed. The shut-off valve 57 is opened only when the fuel cell power generator is started, and the city gas 4 is supplied to the starter burner 59. Also, the shut-off valve 60
The fuel cell power generator is opened only when the fuel cell power generator is started, and the starter burner air 61 is supplied to the starter burner 59 by the air blower 15. In the start-up burner 59, when the fuel cell power generator is started, the city gas 4 burns, and the temperature of the reformer 8 is raised. Except during startup, the shutoff valves 57 and 60 are kept closed. The city gas supply amount is determined in advance from the fuel cell output 50 detected by the voltage measuring means 22 and the current measuring means 23 and the fuel cell output 50 determined from the reformer temperature detected by the reformer temperature measuring means 41. Temperature and flow control valve 52
The city gas supply is set to a value commensurate with the fuel cell output 50 and the reformer temperature by adjusting the degree of opening of the flow control valve 52 based on the relationship of the opening of the fuel cell (i.e., the city gas supply). I do. The city gas 4 from which the sulfur content has been adsorbed and removed by the desulfurizer 7 is mixed with the reforming steam 31 supplied from the steam separator 27 by the ejector 53, and the raw fuel gas 1 is mixed.
Is supplied to the reforming unit 48 of the reformer 8 filled with a reforming catalyst (usually a nickel-based catalyst). Reforming steam 3
1 is heated by exchanging heat with the reformed gas 2 in the heat exchanger 51 before being supplied to the ejector 53. The supply amount of the reforming steam to the ejector 53 is determined by the predetermined opening degree of the flow control valve 52 (that is, the supply amount of the city gas to the reformer 8) and the opening degree of the ejector 53 (that is, the reforming steam). By controlling the opening degree of the ejector 53 based on the relationship of (supply amount), control is performed such that a predetermined steam carbon ratio is obtained. In the reformer 8, steam reforming of the city gas 4 as the fuel gas is performed,
A hydrogen-rich reformed gas is produced. Steam reforming reaction of methane, the main component of city gas (endothermic amount 206 kJ / m
ol) is represented by the following equation.

(Steam reforming reaction of methane)

[0005]

(Equation 1)

[0006] Since the hydrogen-rich reformed gas contains carbon monoxide which causes deterioration of the catalyst of the fuel electrode 18 of the fuel cell stack 21, the reformed gas contains a shift catalyst (copper-zinc). Converter 1 filled with a system catalyst)
1 and the shift reaction (heat generation 41.2 k
J / mol), carbon monoxide in the reformed gas is converted to carbon dioxide. The reformed gas is suitable for the shift reaction.
Since the temperature is higher than 0 to 300 ° C., the city gas 4 and the reforming steam 31 are supplied to the heat exchanger 47 and the heat exchanger 51 as described above before being supplied to the shift converter 11.
The temperature is lowered by exchanging heat with the temperature.

(Shift reaction)

[0008]

(Equation 2)

In the shift converter 11, the concentration of carbon monoxide in the reformed gas is reduced to 1% or less. The reformed gas exiting the shift converter 11 is supplied to the fuel electrode 18 of the fuel cell stack 21 and used for power generation of the fuel cell. A part of the outlet gas of the shift converter 11 is recycled to the desulfurization device 7, and the hydrogen in the recycled gas 64 is used for the desulfurization reaction. The supply amount of the recycle gas 64 depends on the predetermined opening degree of the flow control valve 52 (that is, the supply amount of the city gas to the reformer 8) and the flow control valve 54
By adjusting the opening degree of the flow control valve 54 based on the relationship of the opening degree (that is, the recycle gas supply amount),
Control is performed so that a predetermined supply amount is determined in advance.

On the other hand, to the oxidizer electrode 20 of the fuel cell stack 21, the shut-off valve 62 is opened and the outside air 17 taken in by using the air blower 15 is supplied as power generation air 16.
The supply amount of the power generating air 16 is determined from the fuel cell output 50 detected by the voltage measuring means 22 and the current measuring means 23 and the fuel cell output 50 and the opening of the flow control valve 46 (that is, the power supply amount of the power generating air). The opening degree of the flow control valve 46 is adjusted based on the relationship of (2), and the flow control valve 46 is controlled to a value corresponding to the fuel cell output 50. At the fuel electrode 18 of the fuel cell stack 21, the hydrogen in the reformed gas is converted into hydrogen ions and electrons by the reaction shown in the equation (3).

(Fuel Electrode Reaction) H ₂ → 2H ⁺ + 2e ⁻ (3) Hydrogen ions diffuse inside the electrolyte 19, and
To reach. On the other hand, electrons flow through an external circuit and are taken out as a fuel cell output 50. In the oxidant electrode 20, (4)
By the reaction shown in the formula, hydrogen ions diffused from the fuel electrode 18 into the electrolyte 19, electrons transferred from the fuel electrode 18 through an external circuit, and oxygen in the air react at the three-phase interface to generate water. .

(Oxidant electrode reaction) 2H ⁺ + 1 / 2O ₂ + 2e ⁻ → H ₂ O (4) When the equations (3) and (4) are put together, the total cell reaction in the fuel cell stack 21 is expressed by the following equation. 5) It can be expressed as a simple reaction in which water is produced from hydrogen and oxygen shown in the formula.

(Cell Reaction) H ₂ + 1 / 2O ₂ → H ₂ O (5) The fuel cell output 50 obtained by the power generation is
After voltage conversion or DC-AC conversion is performed in 4,
The load 25 is supplied. In the fuel electrode 18, not all of the hydrogen in the reformed gas is consumed by the electrode reaction shown in the equation (3), but only about 80% of the total hydrogen is used. About 20% of the remaining hydrogen remains in the anode exhaust gas as unreacted hydrogen. This is because, when all of the hydrogen in the reformed gas is consumed by the electrode reaction at the fuel electrode 18, the hydrogen is locally insufficient near the gas outlet, and the carbon on the fuel electrode substrate reacts instead of hydrogen, and the fuel cell This is because the stack 21 is deteriorated. Fuel electrode exhaust gas 1 containing unreacted hydrogen
3 is supplied to the reformer burner 9 and used as burner fuel. Since the steam reforming reaction of methane shown in the equation (1) is an endothermic reaction, it is necessary to externally provide heat corresponding to the reaction heat to the reforming section 48 of the reformer 8. For this reason,
The reformer burner 9 burns hydrogen in the fuel electrode exhaust gas 13 together with the combustion air 12 supplied by the air blower 15 by opening the shut-off valve 10 to raise the temperature of the reformer 48 of the reformer 8 up to 700. Raise the temperature to about ° C. The supply amount of the combustion air 12 is determined based on the reformer temperature predetermined from the reformer temperature detected by the reformer temperature measuring means 41 and the opening degree of the flow control valve 45 (that is, the combustion air supply amount). The control is performed by adjusting the opening of the flow control valve 45 based on the relationship.

Further, the reformer burner combustion exhaust gas 14 containing unreacted steam and steam generated by the combustion reaction of unreacted hydrogen in the fuel electrode exhaust gas 13 and steam generated by the cell reaction shown in equation (5). The oxidant electrode exhaust gas 37 is sent to a condenser 38, where water vapor is removed as condensed water 40, and then released to the atmosphere as exhaust gas 39. The condensed water 40 is returned to the steam separator 27, and is used as the battery cooling water 26, the reforming steam 31, and the exhaust heat recovery steam 34.

Since the battery reaction shown in the equation (5) is an exothermic reaction, the temperature of the fuel cell stack 21 rises as the power generation time elapses. When the temperature of the fuel cell stack 21 increases, the hydrogen ion conductivity of the electrolyte increases, so that the resistance decreases and the output characteristics temporarily improve.
Deterioration is likely to occur, and the life is shortened. Therefore, the battery cooling water 26 is supplied from the steam separator 27 to the cooler 63,
The fuel cell stack 21 is cooled. The operating temperature of the fuel cell stack 21 is generally set at around 190 ° C. in consideration of both the life and the performance. The supply amount of the battery cooling water 26 is adjusted so that the battery cooling water fuel cell stack outlet temperature detected by the battery cooling water temperature measuring means 42 falls within a predetermined temperature range.
It is controlled by adjusting the opening of 0. The battery cooling water 26 exiting the fuel cell stack 21 is returned to the steam separator 27 in the form of a mixture of water and steam. At startup and when the pressure measuring means 49 detects that the steam-water separator pressure has dropped below a predetermined pressure, the pressure measuring means 49 applies a predetermined power to the steam-water separator pressure. Is supplied to the steam / water separator heater 28 until it detects that the pressure exceeds a predetermined pressure. When the liquid level measuring means 55 detects that the water level of the steam-water separator 27 has dropped below a predetermined water level, the liquid level measuring means 55 sets the water level of the steam-water separator 27 in advance. The makeup water pump 43 is operated to supply the makeup water 44 to the steam separator 27 until it is detected that the water level has reached the predetermined level. Steam supplied from the fuel cell stack 21 to the steam separator 27 or steam separator 2
7 are supplied to the evaporator 33 as steam 34 for exhaust heat recovery, and are supplied to the evaporator 33 as the steam 34 for exhaust heat recovery.
Used for evaporation. The condensed water 58 of the exhaust heat recovery steam 34 condensed in the evaporator 33 is returned to the steam separator 27.

[0016]

Next, problems of the conventional fuel cell power generator will be described. In the conventional fuel cell power generator, an expensive gas analyzer such as a gas chromatograph is connected to the outlet of the reformer 8 to continuously diagnose the deterioration state of the reformer 8 in order to diagnose the deterioration state. In the reformed gas obtained by sampling the gas and performing gas analysis, or by periodically sampling the reformed gas at the outlet of the reformer in a container and bringing it to the gas analyzer to perform gas analysis. The deterioration state of the reformer 8 is diagnosed from the decrease in the methane conversion rate calculated from the methane amount (methane slip amount), and the rate of decrease in the methane conversion rate is determined from the relationship between the methane conversion rate and the power generation time to generate the fuel cell. The replacement time of the reforming catalyst has been determined by calculating a period until the lower limit of the methane conversion rate has no adverse effect. However, in this method, it takes a long time for gas analysis, and it is not possible to diagnose the deterioration state of the reformer 8 instantly on the spot, and an expensive gas analyzer is required for the deterioration diagnosis of the reformer 8. In order to continuously diagnose the deterioration state of the reformer 8 in the field, a dedicated gas analyzer is required for the fuel cell power generator, and the sampling gas must be taken to the place where the gas analyzer is located. There was a problem that it took time.

An object of the present invention is to provide an expensive gas analyzer for the deterioration diagnosis of the reformer, which requires a long time for the sampling and analysis of the reformed gas and cannot perform the deterioration diagnosis of the reformer instantaneously. It is necessary to solve the problems such as the need for a dedicated gas analyzer for the fuel cell power generator when trying to continuously perform the deterioration diagnosis of the reformer on the spot.
A fuel cell power generator, a method for diagnosing deterioration of the reformer, and a deterioration diagnosing program capable of performing the deterioration diagnosis of the reformer instantly and continuously on the spot and determining the replacement timing of the reforming catalyst are recorded. It is to provide a computer-readable recording medium.

[0018]

SUMMARY OF THE INVENTION In order to achieve the above object, the present invention provides a reforming apparatus filled with a reforming catalyst for producing hydrogen by reacting a fuel gas with reforming steam, and the reforming apparatus. In a fuel cell power generation device having a fuel cell stack in which fuel cells comprising an electrolyte sandwiched between an electrolyte and an oxidant electrode for generating electricity by reacting hydrogen produced with oxygen with oxygen, the fuel gas and A raw fuel gas reformer inlet temperature measuring means for measuring a reformer inlet temperature of the raw fuel gas containing the reforming steam; and receiving a temperature detection signal from the raw fuel gas reformer inlet temperature measuring means. The raw fuel gas reformer inlet temperature detected by the raw fuel gas reformer inlet temperature measuring means is used to determine the relationship between the predetermined raw fuel gas reformer inlet temperature and the deterioration amount of the reforming catalyst of the reformer. Teru It is characterized in that it has a deterioration diagnosis means for diagnosing a deterioration state of the reformer by.

The present invention also provides a reforming apparatus filled with a reforming catalyst for producing hydrogen by reacting fuel gas with reforming steam, and generating electricity by reacting the hydrogen produced by the reforming apparatus with oxygen. In a fuel cell power generator having a fuel cell stack in which fuel cells each comprising an electrolyte sandwiched between an electrolyte and an oxidizer electrode are stacked, the fuel gas and the raw fuel gas containing the reforming steam are reformed. Raw material gas reformer inlet temperature measuring means for measuring the inlet temperature of the reformer, and a temperature detection signal from the raw fuel gas reformer inlet temperature measuring means for detecting the temperature by the raw fuel gas reformer inlet temperature measuring means. The deteriorated state of the reformer is checked by comparing the determined inlet temperature of the reformer with the relationship between the inlet temperature of the reformer and the methane conversion rate of the reformer. It is characterized in that it has a deterioration diagnosis means diagnose.

Further, the present invention provides an ejector for mixing and supplying reforming steam with a fuel gas, and a reformer filled with a reforming catalyst for reacting the fuel gas with the reforming steam to produce hydrogen. Fuel cell having a fuel cell stack comprising a fuel cell and an oxidizer electrode sandwiching an electrolyte for generating electricity by reacting hydrogen produced by the reformer with oxygen to generate electricity. In the power generator, the reforming steam ejector inlet temperature measuring means for measuring an ejector inlet temperature of the reforming steam, and the reforming steam ejector receiving a temperature detection signal from the reforming steam ejector inlet temperature measuring means. The reforming steam ejector inlet temperature detected by the inlet temperature measuring means is changed to a predetermined reforming steam ejector inlet temperature and the reformer reforming device. It is characterized in that it has a deterioration diagnosis means for diagnosing a deterioration state of the reformer by matching the amount of degradation relationships catalyst.

The present invention also provides an ejector for mixing and supplying reforming steam with a fuel gas, and a reformer filled with a reforming catalyst for reacting the fuel gas with the reforming steam to produce hydrogen. Fuel cell having a fuel cell stack comprising a fuel cell and an oxidizer electrode sandwiching an electrolyte for generating electricity by reacting hydrogen produced by the reformer with oxygen to generate electricity. In the power generator, the reforming steam ejector inlet temperature measuring means for measuring an ejector inlet temperature of the reforming steam, and the reforming steam ejector receiving a temperature detection signal from the reforming steam ejector inlet temperature measuring means. The reforming steam ejector inlet temperature detected by the inlet temperature measuring means is changed to a predetermined reforming steam ejector inlet temperature and the It is characterized in that it has a deterioration diagnosis means for diagnosing a deterioration state of the reformer by matching the a down conversion relationship.

The present invention also provides a desulfurization apparatus for removing sulfur from fuel gas, a reforming apparatus filled with a reforming catalyst for reacting the fuel gas with reforming steam to produce hydrogen, and In a fuel cell power generation apparatus having a fuel cell stack in which fuel cells comprising an electrolyte sandwiched between an electrolyte and an oxidant electrode for generating power by reacting hydrogen produced by the apparatus with oxygen are used as the fuel gas, A fuel gas desulfurization device inlet temperature measuring means for measuring the temperature of the desulfurization device inlet temperature, and a fuel gas desulfurization detected by the fuel gas desulfurization device inlet temperature measuring device receiving a temperature detection signal from the fuel gas desulfurization device inlet temperature measuring device. By comparing the inlet temperature of the reformer with the predetermined relationship between the fuel gas desulfurizer inlet temperature and the amount of deterioration of the reforming catalyst of the reformer, the deterioration state of the reformer is determined. It is characterized in that it has a deterioration diagnosis means for diagnosing.

The present invention also provides a desulfurization apparatus for removing sulfur in fuel gas, a reforming apparatus filled with a reforming catalyst for producing hydrogen by reacting the fuel gas with reforming steam, In a fuel cell power generation apparatus having a fuel cell stack in which fuel cells comprising an electrolyte sandwiched between an electrolyte and an oxidant electrode for generating power by reacting hydrogen produced by the apparatus with oxygen are used as the fuel gas, A fuel gas desulfurization device inlet temperature measuring means for measuring the temperature of the desulfurization device inlet temperature, and a fuel gas desulfurization detected by the fuel gas desulfurization device inlet temperature measuring device receiving a temperature detection signal from the fuel gas desulfurization device inlet temperature measuring device. The deterioration state of the reformer is determined by comparing the inlet temperature of the reformer with a predetermined relationship between the fuel gas desulfurizer inlet temperature and the methane conversion rate of the reformer. It is characterized in that it has a deterioration diagnosis means for disconnection.

The present invention also provides a reforming apparatus filled with a reforming catalyst for producing hydrogen by reacting a fuel gas with reforming steam, and generating electricity by reacting the hydrogen produced by the reforming apparatus with oxygen. A method for diagnosing deterioration of a reformer of a fuel cell power generator having a fuel cell stack comprising a fuel cell comprising an electrolyte sandwiched between an electrolyte and an oxidizer electrode for performing the fuel gas and the reforming Detecting the reformer inlet temperature of the raw fuel gas containing steam, and detecting the raw fuel gas reformer inlet temperature detected in this step with a predetermined raw fuel gas reformer inlet temperature and the reformer inlet temperature. A step of diagnosing the deterioration state of the reformer by collating with the relationship of the amount of deterioration of the reforming catalyst.

The present invention also provides a reforming apparatus filled with a reforming catalyst for producing hydrogen by reacting fuel gas and reforming steam, and generating electricity by reacting the hydrogen produced by the reforming apparatus with oxygen. A method for diagnosing deterioration of a reformer of a fuel cell power generator having a fuel cell stack comprising a fuel cell comprising an electrolyte sandwiched between an electrolyte and an oxidizer electrode for performing the fuel gas and the reforming Detecting the reformer inlet temperature of the raw fuel gas containing steam, and detecting the raw fuel gas reformer inlet temperature detected in this step with a predetermined raw fuel gas reformer inlet temperature and the reformer inlet temperature. A step of diagnosing a deterioration state of the reformer by collating with a relationship of a methane conversion rate is provided.

The present invention also provides an ejector for supplying reforming steam mixed with a fuel gas, and a reforming apparatus filled with a reforming catalyst for producing hydrogen by reacting the fuel gas with the reforming steam. And a fuel cell power generation device having a fuel cell stack in which fuel cells each comprising an anode and an oxidant electrode sandwiching an electrolyte for generating power by reacting hydrogen produced by the reformer with oxygen are stacked. Detecting the ejector inlet temperature of the reforming steam, the reforming steam ejector inlet temperature detected in this step, the reforming steam ejector inlet temperature and the predetermined reforming steam ejector inlet temperature A step of diagnosing the deterioration state of the reformer by collating with the relationship of the amount of deterioration of the reforming catalyst of the reformer.

Also, the present invention provides an ejector for supplying a reforming steam mixed with a fuel gas, and a reforming apparatus filled with a reforming catalyst for reacting the fuel gas with the reforming steam to produce hydrogen. And a fuel cell power generation device having a fuel cell stack in which fuel cells each comprising an anode and an oxidant electrode sandwiching an electrolyte for generating power by reacting hydrogen produced by the reformer with oxygen are stacked. Detecting the ejector inlet temperature of the reforming steam, the reforming steam ejector inlet temperature detected in this step, the reforming steam ejector inlet temperature and the predetermined reforming steam ejector inlet temperature A step of diagnosing a deterioration state of the reformer by collating with a relationship of a methane conversion rate of the reformer.

The present invention also provides a desulfurization apparatus for removing sulfur in fuel gas, a reforming apparatus filled with a reforming catalyst for producing hydrogen by reacting the fuel gas with reforming steam, Reforming of a fuel cell power generator with a fuel cell stack consisting of stacked fuel cells consisting of a fuel electrode and an oxidizer electrode sandwiching an electrolyte for generating power by reacting hydrogen produced by the reformer with oxygen In the method for diagnosing deterioration of a device, a step of detecting a fuel gas desulfurization unit inlet temperature of the fuel gas, and a step of detecting the fuel gas desulfurization unit inlet temperature detected in this step and a predetermined fuel gas desulfurization unit inlet temperature and a modification of the reformer. A step of diagnosing the deterioration state of the reformer by checking the relationship with the relationship of the amount of deterioration of the quality catalyst.

The present invention also provides a desulfurization device for removing sulfur in fuel gas, a reforming device filled with a reforming catalyst for producing hydrogen by reacting the fuel gas with reforming steam, Reforming of a fuel cell power generator with a fuel cell stack consisting of stacked fuel cells consisting of a fuel electrode and an oxidizer electrode sandwiching an electrolyte for generating power by reacting hydrogen produced by the reformer with oxygen Detecting a fuel gas desulfurization unit inlet temperature; and detecting the fuel gas desulfurization unit inlet temperature detected in this step with a predetermined fuel gas desulfurization unit inlet temperature and methane of the reformer. A step of diagnosing the deterioration state of the reformer by collating the conversion rate relationship is provided.

Further, according to the present invention, in the fuel cell power generator, the reformer temperature measuring means for detecting the temperature of the reformer, and a temperature detection signal from the reformer temperature measuring means, Deterioration diagnosis means for selecting one from a plurality of relationships between the raw fuel gas reformer inlet temperature and the amount of deterioration of the reforming catalyst of the reformer determined in advance by the reformer temperature detected by the temperature measuring means. Characterized in that it has a data selection means for transmitting the data.

Further, according to the present invention, in the fuel cell power generator, the reformer temperature measuring means for detecting the temperature of the reformer, and a temperature detection signal from the reformer temperature measuring means, One of a plurality of relations between the raw material gas reformer inlet temperature and the methane conversion rate of the reformer determined in advance by the reformer temperature detected by the temperature measuring means is selected and transmitted to the deterioration diagnostic means. It has data selection means.

Further, according to the present invention, in the fuel cell power generator, a reformer temperature measuring means for detecting a temperature of the reformer, and a temperature detection signal from the reformer temperature measuring means, One is selected from the relationship between a plurality of reformer steam ejector inlet temperatures predetermined by the reformer temperature detected by the temperature measuring means and the amount of deterioration of the reforming catalyst of the reformer, and the deterioration diagnosis means is selected. It is characterized by having data selecting means for transmission.

Further, according to the present invention, in the fuel cell power generator, a reformer temperature measuring means for detecting a temperature of the reformer, and a temperature detection signal from the reformer temperature measuring means, Data to select one from a plurality of relations between the reformer steam ejector inlet temperature and the methane conversion rate of the reformer determined in advance by the reformer temperature detected by the temperature measuring means, and to transmit to the deterioration diagnostic means. It has a selection means.

Further, according to the present invention, in the fuel cell power generator, the reformer temperature measuring means for detecting the temperature of the reformer, and a temperature detection signal from the reformer temperature measuring means, One is selected from the relationship between a plurality of fuel gas desulfurization unit inlet temperatures predetermined by the reformer temperature detected by the temperature measuring unit and the amount of deterioration of the reforming catalyst of the reformer, and transmitted to the deterioration diagnosis unit. Characterized in that it has a data selection means for performing the operation.

Further, according to the present invention, in the fuel cell power generator, the reformer temperature measuring means for detecting a temperature of the reformer, and a temperature detection signal from the reformer temperature measuring means, Data selection to select one from a plurality of relations between the fuel gas desulfurization unit inlet temperature and the methane conversion rate of the reformer determined in advance based on the reformer temperature detected by the temperature measuring unit, and to transmit to the deterioration diagnosis unit It is characterized by having means.

Further, according to the present invention, in the method for diagnosing deterioration of a reformer of a fuel cell power generator, a step of detecting a temperature of the reformer, and a plurality of reformers predetermined in accordance with the reformer temperatures detected in this step. The method includes a step of selecting one from a relationship between a raw fuel gas reformer inlet temperature and a deterioration amount of a reforming catalyst of the reformer.

Further, according to the present invention, in the method for diagnosing deterioration of a reformer of a fuel cell power generator, a step of detecting a temperature of the reformer and a plurality of reformers determined in advance in the step. The method includes a step of selecting one from a relationship between a raw fuel gas reformer inlet temperature and a methane conversion rate of the reformer.

Further, according to the present invention, in the method for diagnosing deterioration of a reformer of a fuel cell power generator, a step of detecting a temperature of the reformer and a plurality of reformers determined in advance by the reformer temperatures detected in this step. The method includes a step of selecting one from the relationship between the inlet temperature of the reforming steam ejector and the amount of deterioration of the reforming catalyst of the reformer.

Further, according to the present invention, in the method for diagnosing deterioration of a reformer of a fuel cell power generator, a step of detecting a temperature of the reformer and a plurality of reformers determined in advance by the temperature of the reformer detected in this step. The method includes a step of selecting one from a relationship between a reforming steam ejector inlet temperature and a methane conversion rate of a reformer.

Further, according to the present invention, in the method for diagnosing deterioration of a reformer of a fuel cell power generator, a step of detecting a temperature of the reformer and a plurality of reformers determined in advance by the temperature of the reformer detected in this step. The method includes a step of selecting one from a relationship between a fuel gas desulfurization unit inlet temperature and a deterioration amount of a reforming catalyst of a reformer.

Further, according to the present invention, in the method for diagnosing deterioration of a reformer of a fuel cell power generator, a step of detecting a temperature of the reformer and a plurality of reformers determined in advance by the reformer temperatures detected in this step. The method includes a step of selecting one from a relationship between a fuel gas desulfurization unit inlet temperature and a methane conversion rate of a reformer.

Further, according to the present invention, in the fuel cell power generator, the deterioration amount of the reforming catalyst of the reforming device is transmitted from the deterioration diagnosing means, and the relationship between the deterioration amount of the reforming catalyst and the power generation time is used. It is necessary to have a life diagnosing means for determining a deterioration rate, calculating a period until reaching an upper limit value of the amount of deterioration of the reforming catalyst which does not adversely affect the power generation of the fuel cell, and determining a replacement time of the reforming catalyst. It is a feature.

Also, according to the present invention, in the fuel cell power generator, the methane conversion of the reformer is transmitted from the deterioration diagnosing means, and the rate of decrease of the methane conversion is determined from the relationship between the methane conversion and the power generation time. It is characterized by having a life diagnosis means for judging a time to replace the reforming catalyst by calculating a period up to a lower limit value of the methane conversion rate which does not adversely affect the power generation of the battery.

Further, according to the present invention, in the method for diagnosing deterioration of a reforming device of a fuel cell power generator, the deterioration rate of the reforming catalyst is obtained from the relationship between the amount of deterioration of the reforming catalyst of the reformer and the power generation time. A step of calculating a period until reaching the upper limit value of the amount of deterioration of the reforming catalyst that does not adversely affect the power generation of the fuel cell, thereby determining a time to replace the reforming catalyst.

Further, according to the present invention, in the method for diagnosing deterioration of a reformer of a fuel cell power generator, the rate of decrease of the methane conversion is determined from the relationship between the methane conversion of the reformer and the power generation time. The method further comprises a step of determining a time to replace the reforming catalyst by calculating a period until the lower limit of the methane conversion rate has no adverse effect.

The present invention also provides a desulfurization device for removing sulfur in fuel gas, an ejector for mixing and supplying fuel gas and reforming steam, and reacting the fuel gas with reforming steam to form hydrogen. A reformer filled with a reforming catalyst for making, and a fuel cell unit comprising a fuel electrode and an oxidizer electrode sandwiching an electrolyte for generating electricity by reacting hydrogen produced by the reformer with oxygen. A computer-readable recording medium storing a deterioration diagnosis program for a reformer of a fuel cell power generator having a stacked fuel cell stack, wherein the raw fuel gas reformer inlet is provided at an inlet of the reformer. Temperature measuring means, reforming steam ejector inlet temperature measuring means installed at the inlet of the ejector, and fuel gas desulfurizing apparatus inlet temperature measuring instrument installed at the desulfurizing apparatus inlet Detecting one or more of the raw fuel gas reformer inlet temperature, reforming steam ejector inlet temperature, and fuel gas desulfurizer inlet temperature with any one or more of Transmitting the temperature detection signal from each of the temperature measuring means to the deterioration diagnosing means; and receiving the temperature detection signal from each of the temperature measuring means, and converting the converted signal into a signal detected by the reforming apparatus temperature measuring means. The predetermined raw fuel gas reformer inlet temperature, reformer steam ejector inlet temperature, and fuel gas selected by the data selecting means and transmitted to the deterioration diagnosing means in accordance with the reformer temperature transmitted as such. A procedure for collating collation data on the relationship between any one of the desulfurization unit inlet temperatures, or one or more and the amount of deterioration of the reforming catalyst of the reformer or the methane conversion rate, the result of the collation Then, the deterioration amount of the reforming catalyst or the methane conversion rate of the reforming device is obtained, and the deterioration amount of the reforming section of the reforming device is determined based on the increase in the deterioration amount of the reforming catalyst of the reforming device or the decrease in the methane conversion rate. This is for executing a procedure for diagnosing a condition.

Further, the present invention is a computer-readable recording medium recording a deterioration diagnosis program for the reformer of the fuel cell power generator, wherein the life diagnosis procedure is as follows.
Raw fuel gas reformer inlet temperature measuring means, reforming steam ejector inlet temperature measuring means, and fuel gas desulfurizing apparatus inlet temperature measuring means, or raw fuel gas reformer inlet detected by one or more of them Any one or more of the temperature, the reforming steam ejector inlet temperature, and the fuel gas desulfurizer inlet temperature, and the predetermined raw fuel gas reformer inlet temperature selected and transmitted by the data selection means. Deterioration diagnosis means for collation data on the relationship between one or more of the inlet temperature of the reforming steam ejector and the inlet temperature of the fuel gas desulfurization unit and the amount of deterioration of the reforming catalyst of the reforming unit or the methane conversion rate. The deterioration rate of the reforming catalyst or the rate of decrease in the methane conversion rate is determined from the relationship between the amount of deterioration of the reforming catalyst or the methane conversion rate and the power generation time, and the fuel Procedure for calculating the period up to the lower limit of the period or methane conversion, up to the upper limit of the amount of degradation of the reforming catalyst does not adversely affect the generation of the battery,
Based on the period up to the upper limit of the amount of deterioration of the reforming catalyst thus obtained, or the period up to the lower limit of the methane conversion rate, a procedure for determining the timing of replacing the reforming catalyst is executed. It is for.

The present invention relates to a raw fuel gas reformer inlet temperature,
Detecting one or more of the inlet temperature of the reforming steam ejector and the inlet temperature of the fuel gas desulfurization unit to diagnose the deterioration state of the reforming unit and determine the timing of replacing the reforming catalyst. Is the most important feature. With the conventional technology, the raw fuel gas reformer inlet temperature measurement means in the reformer,
Either one or more of the reforming steam ejector inlet temperature measuring means and the fuel gas desulfurization unit inlet temperature measuring means are installed, and the deterioration diagnosis means and the life diagnosis means are installed, and the detected temperature is signaled. The temperature detected by the deterioration diagnosing means is transmitted to the deterioration diagnosing means, and the relationship between the predetermined raw fuel gas reformer inlet temperature and the amount of deterioration of the reforming catalyst of the reforming apparatus or the methane conversion rate is improved. The relationship between the inlet temperature of the steam ejector for fuel and the amount of deterioration of the reforming catalyst of the reforming unit or the methane conversion ratio, and the relationship between the inlet temperature of the fuel gas desulfurization unit and the amount of deterioration of the reforming catalyst of the reforming unit or the methane conversion ratio To determine the amount of degradation of the reforming catalyst or the methane conversion rate of the reformer, and use an expensive gas analyzer such as a gas chromatograph to convert the reformed gas at the outlet of the reformer, which takes a long time. Diagnosis of the deterioration state of the reformer instantly on the spot without performing the analysis work, the raw fuel gas reformer inlet temperature measuring means, the reforming steam ejector inlet temperature measuring means, and the fuel gas desulfurizer Any one or one of the raw fuel gas reformer inlet temperature, reforming steam ejector inlet temperature, and fuel gas desulfurizer inlet temperature detected by any one or more of the inlet temperature measuring means. The above is the detection temperature (one or more of the inlet temperature of the raw fuel gas reformer, the inlet temperature of the reforming steam ejector, and the inlet temperature of the fuel gas desulfurizer) predetermined by the deterioration diagnosis means. The rate of deterioration of the reforming catalyst is determined from the relationship between the amount of deterioration of the reforming catalyst or the relationship between the methane conversion rate and the power generation time, which is obtained by collating with the relationship between the amount of deterioration of the reforming catalyst or the relationship between methane conversion rates. Alternatively, determine the rate of decrease in methane conversion, and calculate the period up to the upper limit of the amount of deterioration of the reforming catalyst that does not adversely affect the power generation of the fuel cell, or the period up to the lower limit of the methane conversion. Thus, it is possible to determine the time for replacing the reforming catalyst. In addition, a data selection means is provided as necessary, and the reformer temperature is detected by the reformer temperature measuring means and converted into a signal and transmitted. Relationship between the amount of deterioration of the reforming catalyst or the methane conversion rate, the relationship between the inlet temperature of the reforming steam ejector and the amount of deterioration of the reforming catalyst or the methane conversion rate of the reforming unit, and the temperature of the fuel gas desulfurization unit and the temperature of the reforming unit It is also different from the prior art in that one or more of the relationship between the amount of deterioration of the reforming catalyst and the methane conversion rate is selected and transmitted to the deterioration diagnosis means.

[0049]

Embodiments of the present invention will be described below in detail with reference to the drawings.

FIG. 1 is a structural explanatory view showing a first embodiment of the present invention. 4 are denoted by the same reference numerals, and description thereof will be omitted. The present invention will be described with reference to FIG. The first embodiment differs from the conventional example shown in FIG. 4 in that, as shown in FIG. 1, the raw fuel gas reformer inlet temperature measuring means 6, the reforming steam ejector inlet temperature measuring means 32, and the fuel gas Desulfurization unit inlet temperature measuring means 29
Of the reformer 8 and the ejector 5
3 and the point newly provided at the inlet of the desulfurization device 7,
A raw fuel gas reformer inlet temperature signal detected by one or more of the raw fuel gas reformer inlet temperature measuring means 6, the reforming steam ejector inlet temperature measuring means 32, and the fuel gas desulfurizer inlet temperature measuring means 29. Receiving one or more of the reforming steam ejector inlet temperature signal and the fuel gas desulfurizer inlet temperature signal, and storing the raw fuel gas reformer inlet temperature and the reforming catalyst deterioration amount stored in advance in advance. Or the relationship between the methane conversion rate, the relationship between the inlet temperature of the reforming steam ejector and the deterioration amount of the reforming catalyst of the reforming unit or the methane conversion ratio, and the relationship between the fuel gas desulfurization unit inlet temperature and the deterioration amount of the reforming catalyst or the methane conversion ratio. The difference is that a deterioration diagnosis means 5 for diagnosing the deterioration state of the reforming device 8 by collating with the relation of (1) is newly provided.

Next, the operation of the first embodiment will be described. In the first embodiment, the raw fuel gas reformer inlet temperature measuring means 6 installed at the inlet of the reformer 8, the reforming steam ejector inlet temperature measuring means 32 installed at the inlet of the ejector 53, the desulfurizer One or more of the fuel gas desulfurization unit inlet temperature measuring means 29 installed at the inlet of No. 7 detects one or more of the raw fuel gas reforming unit inlet temperature, the reforming steam ejector inlet temperature, and the fuel gas desulfurizing unit inlet temperature. Then, these temperature detection signals are transmitted to the deterioration diagnosing means 5, and the deterioration diagnosing means 5 which has received the temperature detection signals detects the stored temperature and the deterioration amount of the reforming catalyst of the reformer 8 or the methane conversion. The relationship between the rates, that is, the relationship between the raw fuel gas reformer inlet temperature and the amount of deterioration of the reforming catalyst in the reformer or the methane conversion rate, the temperature of the reforming steam ejector inlet and the amount of deterioration of the reforming catalyst in the reformer Or The amount of deterioration of the reforming catalyst, that is, the reforming of the reforming device 8, is checked by comparing the relationship between the conversion rate of the reforming device and the relationship between the inlet temperature of the fuel gas desulfurization device and the amount of deterioration of the reforming catalyst of the reforming device or the methane conversion rate. Diagnosing the deterioration state of the unit 48 differs from the prior art.

When the reforming catalyst in the reforming section 48 of the reformer 8 deteriorates, the steam reforming reaction of methane represented by the equation (1) of the endothermic reaction hardly occurs in the reforming section 48 of the reformer 8. Thus, the methane conversion rate of the reformer 8 decreases. as a result,
The methane amount (methane slip amount) in the reformer outlet gas (reformed gas) increases. At this time, the reforming unit 4 of the reforming device 8
Since the amount of heat absorbed by the steam reforming reaction of methane at 8 decreases, when the reforming catalyst in the reforming section 48 of the reformer 8 deteriorates, the temperature of the reformer outlet gas (reformed gas) and the temperature of the burner combustion exhaust gas are reduced. Will rise. Therefore, the temperature of the city gas 4 which is heated by exchanging heat with the reformed gas 2 which is the reformer outlet gas in the heat exchanger 47 is the same as the temperature of the desulfurizer inlet gas, and the heat exchanger 51 is the reformer outlet gas. Ejector inlet temperature of the reforming steam 31 heated by heat exchange with the reformed gas 2, and raw fuel composed of the heated city gas 4, the reforming steam 31, and the recycle gas from the shift converter 11 The reformer inlet temperature of gas 1 will also increase. Therefore, by detecting the inlet temperature of the raw fuel gas reformer, the inlet temperature of the fuel gas desulfurizer, and the inlet temperature of the reforming steam ejector, it is possible to estimate the deterioration amount of the reforming catalyst or the methane conversion rate, Diagnosis of the deterioration state of the reforming section 48 of the device 8 is possible. The inlet temperature of the raw fuel gas reformer, the inlet temperature of the fuel gas desulfurizer, and the inlet temperature of the reforming steam ejector may each be detected by installing a plurality of sensors, and their average values may be taken.

FIG. 2 is a structural explanatory view showing a second embodiment of the present invention. 1 and 4 are denoted by the same reference numerals, and description thereof will be omitted. FIG.
The second embodiment will be described with reference to FIG. Second embodiment example
4 is different from the conventional example shown in FIG. 4 in that, as shown in FIG. 2, the raw fuel gas reformer inlet temperature measuring means 6, the reforming steam ejector inlet temperature measuring means 32, and the fuel gas desulfurizer inlet temperature measuring means. Any one or more of the means 29 may be connected to the inlet of the reformer 8, the inlet of the ejector 53,
And a point newly provided at the inlet of the desulfurizer 7, any one of the raw fuel gas reformer inlet temperature measuring means 6, the reforming steam ejector inlet temperature measuring means 32, and the fuel gas desulfurizing apparatus inlet temperature measuring means 29. One or more raw fuel gas reformer inlet temperature signal, reformer steam ejector inlet temperature signal, and city gas (fuel gas)
Receiving one or more signals of the desulfurizer inlet temperature, the relationship between the predetermined raw fuel gas reformer inlet temperature and the amount of deterioration of the reforming catalyst of the reformer or the methane conversion rate, the reforming steam ejector inlet temperature The deterioration state of the reformer 8 by comparing the relationship between the temperature of the reforming catalyst and the amount of methane conversion in the reformer and the relationship between the inlet temperature of the fuel gas desulfurization unit and the amount of deterioration of the reforming catalyst or the methane conversion. Of the degradation diagnostic means 5 for diagnosing the fuel gas, and any one of the raw fuel gas reformer inlet temperature measuring means 6, the reforming steam ejector inlet temperature measuring means 32, and the fuel gas desulfurizer inlet temperature measuring means 29 Or one or more raw fuel gas reformer inlet temperature detected, reformer steam ejector inlet temperature,
And one or more of the inlet temperatures of the fuel gas desulfurization unit, the detected temperature (the raw fuel gas reformer inlet temperature, the reforming steam ejector inlet temperature, and the fuel Any one or more of the gas desulfurization unit inlet temperatures) and the amount of deterioration of the reforming catalyst or the methane conversion obtained by collating with the relationship between the amount of deterioration of the reforming catalyst of the reformer 8 or the conversion rate of methane. The rate of deterioration of the reforming catalyst or the rate of reduction of the methane conversion rate is determined from the relationship between the conversion rate and the power generation time, and the period up to the upper limit of the amount of deterioration of the reforming catalyst that does not adversely affect the power generation of the fuel cell, or methane conversion The difference is that a life diagnosis means 65 for determining the time to replace the reforming catalyst is newly provided by calculating the period until the rate reaches the lower limit value.

Next, the operation of the second embodiment will be described. In the second embodiment, the raw fuel gas reformer inlet temperature measuring means 6 installed at the inlet of the reformer 8, the reforming steam ejector inlet temperature measuring means 32 installed at the inlet of the ejector 53, and desulfurization One of the fuel gas desulfurization device inlet temperature measuring means 29 installed at the inlet of the device 7,
Or at least one, the raw fuel gas reformer inlet temperature, reforming steam ejector inlet temperature, and one or more of the fuel gas desulfurizer inlet temperature is detected,
These temperature detection signals are transmitted to the deterioration diagnosing means 5, and the deterioration diagnosing means 5 which has received the temperature detection signals determines predetermined detection temperatures (the raw fuel gas reformer inlet temperature, the reforming steam ejector inlet temperature). , And any one or more of the fuel gas desulfurization unit inlet temperatures) and the relationship between the deterioration amount of the reforming catalyst of the reforming unit 8 or the methane conversion rate,
Relationship between raw fuel gas reformer inlet temperature and reforming catalyst deterioration amount or methane conversion rate of reformer 8, reforming steam ejector inlet temperature and reforming catalyst deterioration amount or methane conversion rate of reformer 8 And the relationship between the fuel gas desulfurization unit inlet temperature and the relationship between the amount of deterioration of the reforming catalyst of the reforming device 8 or the methane conversion rate, the deterioration of the reforming catalyst, Along with diagnosing the deterioration state, the life diagnosing means 65 includes a raw fuel gas reformer inlet temperature measuring means 6, a reforming steam ejector inlet temperature measuring means 32,
And any one of the raw fuel gas reformer inlet temperature, reforming steam ejector inlet temperature, and fuel gas desulfurizer inlet temperature detected by one or more of the fuel gas desulfurizer inlet temperature measuring means 29. One or more of the detected temperatures (any one of the inlet temperature of the raw fuel gas reformer, the inlet temperature of the reforming steam ejector, and the inlet temperature of the fuel gas desulfurizer) determined by the deterioration diagnosis means 5 ,
Or one or more) and the relationship between the amount of deterioration of the reforming catalyst of the reformer 8 or the relationship between the methane conversion and the methane conversion obtained from the relationship between the amount of methane conversion and the power generation time. Calculate the rate of deterioration or the rate of decrease in methane conversion, and calculate the period up to the upper limit of the amount of deterioration of the reforming catalyst that does not adversely affect the power generation of the fuel cell, or the period up to the lower limit of the methane conversion. Thus, the determination of the time for replacing the reforming catalyst is different from that of the related art.

In the life diagnosing means 65, any one of the raw fuel gas reformer inlet temperature measuring means 6, the reforming steam ejector inlet temperature measuring means 32, and the fuel gas desulfurizer inlet temperature measuring means 29 in the deterioration diagnosing means 5 is used. One or more of the raw fuel gas reformer inlet temperature, reforming steam ejector inlet temperature, and fuel gas desulfurizer inlet temperature detected by one or more fuel gas reformers The relationship between the unit inlet temperature and the amount of deterioration of the reforming catalyst or the methane conversion rate of the reformer, the relationship between the inlet temperature of the reforming steam ejector and the amount of deterioration of the reforming catalyst or the methane conversion rate of the reformer, and fuel gas desulfurization Relationship between the amount of deterioration of the reforming catalyst or the methane conversion rate and the power generation time obtained by collating with the relationship between the unit inlet temperature and the amount of deterioration of the reforming catalyst or the methane conversion rate of the reformer Calculate the deterioration rate of the reforming catalyst or the rate of decrease of the methane conversion rate from the calculated value, and calculate the period up to the upper limit of the deterioration amount of the reforming catalyst or the lower limit of the methane conversion rate that does not adversely affect the power generation of the fuel cell By doing so, it is possible to determine the time to replace the reforming catalyst. The inlet temperature of the raw fuel gas reformer, the inlet temperature of the reforming steam ejector, and the inlet temperature of the fuel gas desulfurizer may each be detected by installing a plurality of sensors, and the average value thereof may be taken.

FIG. 3 is a structural explanatory view showing a third embodiment of the present invention. 1, 2, and 4 are denoted by the same reference numerals, and description thereof will be omitted. Third Embodiment A third embodiment will be described with reference to FIG. The third embodiment differs from the second embodiment of the present invention shown in FIG. 2 in that the raw fuel temperature is detected by the reformer temperature measuring means 41, converted into a signal, and transmitted. The relationship between the gas reformer inlet temperature and the amount of deterioration of the reforming catalyst or methane conversion of the reformer, the relationship between the reforming steam ejector inlet temperature and the amount of deterioration of the reforming catalyst of the reformer or methane conversion, and A new data selection unit 66 for selecting one or more of the relationship between the fuel gas desulfurization unit inlet temperature and the deterioration amount of the reforming catalyst or the methane conversion rate of the reforming unit and transmitting it to the deterioration diagnosis unit 5 The point provided is different.

Next, the operation of the third embodiment will be described. In the third embodiment, the raw fuel gas reformer inlet temperature measuring means 6 installed at the inlet of the reformer 8, the reforming steam ejector inlet temperature measuring means 32 installed at the inlet of the ejector 53, and desulfurization One of the fuel gas desulfurization device inlet temperature measuring means 29 installed at the inlet of the device 7,
Or at least one, the raw fuel gas reformer inlet temperature, reforming steam ejector inlet temperature, and one or more of the fuel gas desulfurizer inlet temperature is detected,
These temperature detection signals are transmitted to the deterioration diagnosing means 5, and the deterioration diagnosing means 5 receiving the temperature detection signals converts the signals detected by the reformer temperature measuring means 41 in the data selecting means 66 and transmits the signals. A predetermined detection temperature selected for the reformer temperature and transmitted to the deterioration diagnosing means 5 (any one of the raw fuel gas reformer inlet temperature, the reforming steam ejector inlet temperature, and the fuel gas desulfurizer inlet temperature) One or more) and the relationship between the amount of deterioration of the reforming catalyst or the methane conversion rate of the reforming device 8, the deterioration of the reforming catalyst, that is, the deterioration of the reforming section 48 of the reforming device 8. Along with diagnosing the condition, the life diagnosing means 65 includes a raw fuel gas reformer inlet temperature measuring means 6, a reforming steam ejector inlet temperature measuring means 32, and a fuel gas desulfurizer inlet temperature measuring means 29. Deterioration diagnosis of any one or more of the raw fuel gas reformer inlet temperature, reformer steam ejector inlet temperature, and fuel gas desulfurizer inlet temperature detected by any one or more than one The detection temperature (one or more of the inlet temperature of the raw fuel gas reformer, the inlet temperature of the reforming steam ejector, and the inlet temperature of the fuel gas desulfurizer) predetermined by the means 5 and the reformer 8 From the relationship between the amount of deterioration of the reforming catalyst or the relationship between the methane conversion rate and the power generation time obtained by comparing with the relationship between the deterioration amount of the reforming catalyst or the methane conversion rate, the deterioration rate of the reforming catalyst or the rate of decrease of the methane conversion rate was determined. By calculating the period up to the upper limit of the amount of deterioration of the reforming catalyst that does not adversely affect the power generation of the fuel cell, or the period up to the lower limit of the methane conversion, Is possible to determine the replacement time of the medium is different from the prior art.

The deterioration diagnosis means 5, the life diagnosis means 65,
The data selecting means 66 is specifically executed by a personal computer (PC) or the like based on a deterioration diagnosis program recorded in a predetermined recording medium in advance.

FIG. 5 is a flowchart based on a deterioration diagnosis method and a deterioration diagnosis program for a reformer of a fuel cell power generator according to an embodiment of the present invention.

In the fuel cell power generator according to this embodiment, the raw fuel gas reformer inlet temperature measuring means 6 installed at the inlet of the reformer 8 and the reforming steam ejector installed at the inlet of the ejector 53 Either one or more of the inlet temperature measuring means 32 and the fuel gas desulfurizing apparatus inlet temperature measuring means 29 installed at the inlet of the desulfurizing apparatus 7,
One or more of the raw fuel gas reformer inlet temperature, the reforming steam ejector inlet temperature, and the fuel gas desulfurizer inlet temperature are detected (step S1).

Then, these temperature detection signals are transmitted from the temperature measuring means 6, 29, 32 to the deterioration diagnosing means 5 (step S2).

Next, the deterioration diagnosing means 5 receiving these temperature detection signals, the data selecting means 66 converts the converted signals into signals detected by the reforming apparatus temperature measuring means 41 and transmits the signals. The predetermined detection temperature (one of the inlet temperature of the raw fuel gas reformer, the inlet temperature of the reforming steam ejector, and the inlet temperature of the fuel gas desulfurizer) selected and transmitted to the deterioration diagnosis means 5 that's all)
Then, the collation data of the relationship between the deterioration amount of the reforming catalyst of the reformer 8 or the methane conversion rate is collated (step S3).

Thus, the deterioration amount of the reforming catalyst or the methane conversion rate of the reforming device 8 is obtained, and the deterioration amount of the reforming section 48 of the reforming device 8 is determined from the increase in the deterioration amount of the reforming catalyst or the decrease in the methane conversion ratio. The state is diagnosed (step S4).

That is, in the life diagnosis means 65, any one of the raw fuel gas reformer inlet temperature measuring means 6, the reforming steam ejector inlet temperature measuring means 32, and the fuel gas desulfurizer inlet temperature measuring means 29, Alternatively, one or more of the inlet temperature of the raw fuel gas reformer, the inlet temperature of the reforming steam ejector, and the inlet temperature of the fuel gas desulfurizer detected by one or more are selected by the deterioration diagnosis means 5. The predetermined detected temperature selected and transmitted by the means 66 (one or more of the raw fuel gas reformer inlet temperature, the reforming steam ejector inlet temperature, and the fuel gas desulfurizer inlet temperature) And reformer 8
The rate of decrease in the methane conversion rate or the conversion rate of the reforming catalyst from the relationship between the amount of deterioration of the reforming catalyst or the relationship between the methane conversion rate and the power generation time obtained by collation with the comparison data on the relationship between the degradation amount of the reforming catalyst or the methane conversion rate The deterioration rate is obtained, and a period until reaching the lower limit of the methane conversion rate that does not adversely affect the power generation of the fuel cell or a period until reaching the upper limit of the amount of deterioration of the reforming catalyst is calculated (step S5).

Then, the replacement time of the reforming catalyst is determined based on the period up to the lower limit of the methane conversion rate or the period up to the upper limit of the deterioration amount of the reforming catalyst. (Step S6).

As described above, in the fuel cell power generator according to the present embodiment, the time for replacing the reforming catalyst can be determined.

[0067]

As described above, according to the present invention, any one of the raw fuel gas reformer inlet temperature measuring means, the reforming steam ejector inlet temperature measuring means, and the fuel gas desulfurizer inlet temperature measuring means is used. Or one or more,
Any one or more of the detected raw fuel gas reformer inlet temperature, reforming steam ejector inlet temperature, and fuel gas desulfurizer inlet temperature is converted to a signal and transmitted to the deterioration diagnosis means to diagnose deterioration. The relationship between the raw fuel gas reformer inlet temperature and the amount of deterioration of the reforming catalyst or methane conversion of the reformer, the temperature detected by the means, and the reformer steam ejector inlet temperature and reformer reforming Diagnosis of the deterioration state of the reforming catalyst by collating with the relationship between the catalyst deterioration amount or methane conversion rate, and the relationship between the fuel gas desulfurization unit inlet temperature and the reforming catalyst deterioration amount or methane conversion rate of the reformer One of the raw fuel gas reformer inlet temperature measuring means, the reforming steam ejector inlet temperature measuring means, and the fuel gas desulfurizing apparatus inlet temperature measuring means in the life diagnostic means. Is one or more of the raw fuel gas reformer inlet temperature, the reforming steam ejector inlet temperature, and the fuel gas desulfurizer inlet temperature detected by at least one of the raw fuel gas reformer inlet temperatures. Between the temperature of the reforming catalyst and the amount of methane conversion in the reformer, the relationship between the inlet temperature of the reforming steam ejector and the amount of deterioration or the methane conversion of the reforming catalyst in the reformer, and the temperature of the fuel gas desulfurization unit Deterioration of the reforming catalyst from the relationship between the deterioration amount of the reforming catalyst or the conversion amount of methane obtained by comparing the relationship between the deterioration amount of the reforming catalyst of the reformer or the methane conversion rate with the deterioration diagnosis means, and the power generation time The rate of decrease in the methane conversion rate is calculated by calculating the rate of decrease in the methane conversion rate or the upper limit value of the amount of deterioration of the reforming catalyst that does not adversely affect the power generation of the fuel cell, or the lower limit value of the methane conversion rate. Since the time to replace the catalyst is determined, it is not necessary to use a costly gas analyzer such as a gas chromatograph for diagnosing the state of deterioration of the reformer. It is possible to diagnose the deterioration state of the reformer instantaneously and continuously on the spot.Also, the deterioration state of the reforming catalyst can be always grasped and the time for replacing the reforming catalyst can be known in advance. There is an effect that the reforming catalyst can be replaced before the power generation of the fuel cell is adversely affected by the deterioration of the quality device performance.

[Brief description of the drawings]

FIG. 1 is a configuration explanatory view showing a first embodiment of the present invention.

FIG. 2 is a configuration explanatory view showing a second embodiment of the present invention.

FIG. 3 is a configuration explanatory view showing a third embodiment of the present invention.

FIG. 4 is an explanatory diagram showing a configuration of a conventional fuel cell power generator.

FIG. 5 is a flowchart based on a deterioration diagnosis method and a deterioration diagnosis program for a reformer of a fuel cell power generator according to an embodiment of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Raw fuel gas 2 Reformed gas 3 Shut-off valve 4 City gas 5 Degradation diagnostic means 6 Raw fuel gas reformer inlet temperature measuring means 7 Desulfurizer 8 Reformer 9 Reformer burner 10 Shutoff valve 11 Shift converter 12 Combustion Air 13 fuel electrode exhaust gas 14 reformer burner combustion exhaust gas 15 air blower 16 power generation air 17 outside air 18 fuel electrode 19 electrolyte 20 oxidizer electrode 21 fuel cell cell stack 22 voltage measuring means 23 current measuring means 24 converter 25 load 26 battery Cooling water 27 Gas-water separator 28 Gas-water separator heater 29 Fuel gas desulfurization unit inlet temperature measuring means 30 Flow control valve 31 Reforming steam 32 Reforming steam ejector inlet temperature measuring means 33 Evaporator 34 Steam for exhaust heat recovery 35 Exhaust heat utilization system 36 Refrigerant 37 Oxidizer electrode exhaust gas 38 Condenser 39 Exhaust gas 40 Condensed water 41 Reformer temperature measuring means 42 Battery cooling water temperature measuring means 43 Make-up water pump 44 Make-up water 45 Flow control valve 46 Flow control valve 47 Heat exchanger 48 Reforming unit 49 Pressure measuring means 50 Fuel cell output 51 Heat exchange Device 52 Flow control valve 53 Ejector 54 Flow control valve 55 Liquid level measuring means 56 Pump 57 Shutoff valve 58 Condensed water 59 Starter burner 60 Shutoff valve 61 Reformer starter burner air 62 Shutoff valve 63 Cooler 64 Recycle gas 65 Life Diagnosis means 66 Data selection means

Claims (30)

[Claims] 1. A reformer filled with a reforming catalyst for producing hydrogen by reacting fuel gas with reforming steam, and a method for generating electricity by reacting hydrogen produced by the reformer with oxygen. A fuel cell power generator having a fuel cell stack in which fuel cells each comprising a fuel electrode sandwiching an electrolyte and an oxidizer electrode are stacked, wherein a reformer inlet for a raw fuel gas containing the fuel gas and the reforming steam is provided. A raw fuel gas reformer inlet temperature measuring means for measuring a temperature, and a temperature detected by the raw fuel gas reformer inlet temperature measuring means which receives a temperature detection signal from the raw fuel gas reformer inlet temperature measuring means. Diagnosing the deterioration state of the reformer by comparing the fuel gas reformer inlet temperature with a predetermined relationship between the raw fuel gas reformer inlet temperature and the deterioration amount of the reforming catalyst of the reformer. Fuel cell power plant characterized by having a deterioration diagnosis means. 2. A reformer filled with a reforming catalyst for producing hydrogen by reacting a fuel gas with reforming steam, and for generating power by reacting the hydrogen produced by the reformer with oxygen. A fuel cell power generator having a fuel cell stack in which fuel cells each comprising a fuel electrode sandwiching an electrolyte and an oxidizer electrode are stacked, wherein a reformer inlet for a raw fuel gas containing the fuel gas and the reforming steam is provided. A raw fuel gas reformer inlet temperature measuring means for measuring a temperature, and a temperature detected by the raw fuel gas reformer inlet temperature measuring means which receives a temperature detection signal from the raw fuel gas reformer inlet temperature measuring means. By comparing the inlet temperature of the fuel gas reformer with a predetermined relationship between the inlet temperature of the raw fuel gas reformer and the methane conversion rate of the reformer, the deterioration state of the reformer is diagnosed. Fuel cell power plant characterized by having a diagnostic means. 3. An ejector for mixing and supplying reforming steam with a fuel gas, and a reforming device filled with a reforming catalyst for reacting the fuel gas with the reforming steam to produce hydrogen. A fuel cell power generation device having a fuel cell stack in which fuel cells comprising an electrolyte sandwiched between an electrolyte and an oxidizer electrode for generating power by reacting hydrogen produced by the reformer with oxygen are used. A reforming steam ejector inlet temperature measuring means for measuring an ejector inlet temperature of the reforming steam; and a reforming steam ejector inlet temperature measurement receiving a temperature detection signal from the reforming steam ejector inlet temperature measuring means. Means for detecting the reforming steam ejector inlet temperature detected by the means and the predetermined reforming steam ejector inlet temperature and deterioration of the reforming catalyst of the reformer. Fuel cell power plant by matching the relationship characterized by having a deterioration diagnosis means for diagnosing a deterioration state of the reformer. 4. An ejector for mixing and supplying reforming steam with a fuel gas, and a reforming device filled with a reforming catalyst for reacting the fuel gas with the reforming steam to produce hydrogen. A fuel cell power generation device having a fuel cell stack in which fuel cells comprising an electrolyte sandwiched between an electrolyte and an oxidizer electrode for generating power by reacting hydrogen produced by the reformer with oxygen are used. A reforming steam ejector inlet temperature measuring means for measuring an ejector inlet temperature of the reforming steam; and a reforming steam ejector inlet temperature measurement receiving a temperature detection signal from the reforming steam ejector inlet temperature measuring means. The reformer steam ejector inlet temperature detected by the means is adjusted to a predetermined reformer steam ejector inlet temperature and the methane conversion rate of the reformer. Fuel cell power plant characterized by having a deterioration diagnosis means for diagnosing a deterioration state of the reformer by matching the engagement. 5. A desulfurizer for removing sulfur from fuel gas, a reformer filled with a reforming catalyst for reacting the fuel gas with reforming steam to produce hydrogen, and a desulfurizer formed by the reformer. A fuel cell power generator having a fuel cell stack in which fuel cells each comprising an electrolyte sandwiched between an electrolyte and an oxidizer electrode for generating power by reacting the hydrogen with oxygen to generate power, the fuel gas desulfurization device A fuel gas desulfurization apparatus inlet temperature measuring means for measuring an inlet temperature; a fuel gas desulfurization apparatus inlet temperature detected by the fuel gas desulfurization apparatus inlet temperature measuring means upon receiving a temperature detection signal from the fuel gas desulfurization apparatus inlet temperature measuring means. Is compared with a predetermined relationship between the fuel gas desulfurization unit inlet temperature and the amount of deterioration of the reforming catalyst of the reforming unit to diagnose the deterioration state of the reforming unit. Fuel cell power plant characterized by having a reduction diagnostic means. 6. A desulfurizer for removing sulfur from fuel gas, a reformer filled with a reforming catalyst for reacting the fuel gas with reforming steam to produce hydrogen, and a desulfurizer formed by the reformer. A fuel cell power generator having a fuel cell stack in which fuel cells each comprising an electrolyte sandwiched between an electrolyte and an oxidizer electrode for generating power by reacting the hydrogen with oxygen to generate power, the fuel gas desulfurization device A fuel gas desulfurization apparatus inlet temperature measuring means for measuring an inlet temperature; a fuel gas desulfurization apparatus inlet temperature detected by the fuel gas desulfurization apparatus inlet temperature measuring means upon receiving a temperature detection signal from the fuel gas desulfurization apparatus inlet temperature measuring means. To determine the deterioration state of the reformer by comparing the predetermined relationship between the fuel gas desulfurization unit inlet temperature and the methane conversion rate of the reformer. Fuel cell power generation apparatus characterized by having a cross-sectional section. 7. A reformer filled with a reforming catalyst for producing hydrogen by reacting fuel gas with reforming steam, and for generating electricity by reacting the hydrogen produced by the reformer with oxygen. A method for diagnosing deterioration of a reformer of a fuel cell power generation device having a fuel cell stack in which a fuel electrode composed of a fuel electrode and an oxidizer electrode sandwiched by an electrolyte is stacked, wherein the fuel gas and the reforming steam are included. Detecting the raw fuel gas reformer inlet temperature; and determining the raw fuel gas reformer inlet temperature detected in this step by a predetermined raw fuel gas reformer inlet temperature and the reforming catalyst of the reformer. Diagnosing a deterioration state of the reformer by comparing the deterioration state of the reformer with a relation of the deterioration amount of the reformer. 8. A reformer filled with a reforming catalyst for producing hydrogen by reacting a fuel gas with reforming steam, and generating electricity by reacting the hydrogen produced by the reformer with oxygen. A method for diagnosing deterioration of a reformer of a fuel cell power generation device having a fuel cell stack in which a fuel electrode composed of a fuel electrode and an oxidizer electrode sandwiched by an electrolyte is stacked, wherein the fuel gas and the reforming steam are included. Detecting the raw fuel gas reformer inlet temperature; and determining the raw fuel gas reformer inlet temperature detected in this step as a predetermined raw fuel gas reformer inlet temperature and methane conversion rate of the reformer. Diagnosing the deterioration state of the reformer by collating with the relationship of 9. An ejector for supplying a reforming steam mixed with a fuel gas to supply the reforming steam, a reforming device filled with a reforming catalyst for reacting the fuel gas with the reforming steam to produce hydrogen, Reforming of a fuel cell power generator with a fuel cell stack consisting of stacked fuel cells consisting of a fuel electrode and an oxidizer electrode sandwiching an electrolyte for generating power by reacting hydrogen produced by the reformer with oxygen In the method for diagnosing deterioration of a device, a step of detecting an ejector inlet temperature of the reforming steam; and a step of setting the reforming steam ejector inlet temperature detected in this step to a predetermined reforming steam ejector inlet temperature and the reforming. Diagnosing the deterioration state of the reformer by comparing the deterioration amount of the reformer with the relationship of the deterioration amount of the reformer catalyst. Deterioration diagnosis method of the device. 10. An ejector for supplying a reforming steam mixed with a fuel gas to supply the reforming steam, a reforming device filled with a reforming catalyst for reacting the fuel gas with the reforming steam to produce hydrogen, Reforming of a fuel cell power generator with a fuel cell stack consisting of stacked fuel cells consisting of a fuel electrode and an oxidizer electrode sandwiching an electrolyte for generating power by reacting hydrogen produced by the reformer with oxygen In the method for diagnosing deterioration of a device, a step of detecting an ejector inlet temperature of the reforming steam; and a step of setting the reforming steam ejector inlet temperature detected in this step to a predetermined reforming steam ejector inlet temperature and the reforming. Diagnosing a deterioration state of the reformer by collating with a relation of a methane conversion rate of the apparatus. Deterioration diagnosis method of location. 11. A desulfurizer for removing sulfur in fuel gas, a reformer filled with a reforming catalyst for reacting the fuel gas with reforming steam to produce hydrogen, and the reformer. Degradation of reformer of fuel cell power plant with fuel cell stack consisting of fuel cell with electrolyte sandwiched and oxidizer electrode for generating electricity by reacting hydrogen produced by oxygen with oxygen In the diagnostic method, a step of detecting the temperature of the fuel gas desulfurization apparatus inlet, and a step of detecting the fuel gas desulfurization apparatus inlet temperature detected in this step and the predetermined fuel gas desulfurization apparatus inlet temperature and the reforming catalyst of the reformer. A method of diagnosing deterioration of a reformer of a fuel cell power generator, comprising the step of diagnosing a deterioration state of the reformer by collating with a relationship of the amount of deterioration. 12. A desulfurizer for removing sulfur in fuel gas, a reformer filled with a reforming catalyst for reacting the fuel gas with reforming steam to produce hydrogen, and the reformer. Degradation of reformer of fuel cell power plant with fuel cell stack consisting of fuel cell with electrolyte sandwiched and oxidizer electrode for generating electricity by reacting hydrogen produced by oxygen with oxygen In the diagnosis method, a step of detecting a fuel gas desulfurization apparatus inlet temperature of the fuel gas; and a step of detecting the fuel gas desulfurization apparatus inlet temperature detected in this step as a predetermined fuel gas desulfurization apparatus inlet temperature and a methane conversion rate of the reformer. Diagnosing a deterioration state of the reformer by comparing the relationship with a relationship. 13. A reformer temperature measuring means for detecting a temperature of the reformer, and receiving a temperature detection signal from the reformer temperature measuring means,
One is selected from the relationship between a plurality of raw fuel gas reformer inlet temperatures predetermined by the reformer temperature detected by the reformer temperature measuring means and the deterioration amount of the reforming catalyst of the reformer. 2. The fuel cell power generator according to claim 1, further comprising data selection means for transmitting the data to the deterioration diagnosis means. 14. A reformer temperature measuring means for detecting the temperature of the reformer, and receiving a temperature detection signal from the reformer temperature measuring means,
Deterioration diagnosis by selecting one from a plurality of relationships between the raw fuel gas reformer inlet temperature and the methane conversion rate of the reformer determined in advance by the reformer temperature detected by the reformer temperature measuring means 3. The fuel cell power generator according to claim 2, further comprising data selection means for transmitting the data to the means. 15. A reformer temperature measuring means for detecting a temperature of the reformer, and receiving a temperature detection signal from the reformer temperature measuring means,
One is selected from the relationship between a plurality of reforming steam ejector inlet temperatures predetermined by the reformer temperature detected by the reformer temperature measuring means and the amount of deterioration of the reforming catalyst of the reformer. 4. The fuel cell power generator according to claim 3, further comprising data selection means for transmitting the data to the deterioration diagnosis means. 16. A reformer temperature measuring means for detecting the temperature of the reformer, and receiving a temperature detection signal from the reformer temperature measuring means,
Deterioration diagnosis means for selecting one from a plurality of relations between the reformer steam ejector inlet temperature and the methane conversion rate of the reformer, which is predetermined by the reformer temperature detected by the reformer temperature measuring means. 5. The fuel cell power generator according to claim 4, further comprising data selection means for transmitting the data to the fuel cell power generator. 17. A reformer temperature measuring means for detecting a temperature of the reformer, and receiving a temperature detection signal from the reformer temperature measuring means,
One of a plurality of fuel gas desulfurization unit inlet temperatures predetermined by a reformer temperature detected by the reformer temperature measuring means and a deterioration amount of a reforming catalyst of the reformer is selected and deteriorated. 6. The fuel cell power generator according to claim 5, further comprising data selection means for transmitting the data to the diagnosis means. 18. A reformer temperature measuring means for detecting the temperature of the reformer, and receiving a temperature detection signal from the reformer temperature measuring means,
One of a plurality of fuel gas desulfurization unit inlet temperatures and a relationship between the methane conversion rate of the reformer, which is determined in advance by the reformer temperature detected by the reformer temperature measuring unit, is selected as the deterioration diagnostic unit. 7. The fuel cell power generator according to claim 6, further comprising a data selection unit for transmitting. 19. A step of detecting a temperature of the reformer, a plurality of raw fuel gas reformer inlet temperatures predetermined by the reformer temperature detected in this step, and deterioration of the reformer catalyst of the reformer. 8. The method for diagnosing deterioration of a reformer of a fuel cell power generator according to claim 7, further comprising the step of selecting one of the quantities from the relationship. 20. A step of detecting a temperature of a reformer, and a relationship between a plurality of raw fuel gas reformer inlet temperatures predetermined by the reformer temperature detected in this step and a methane conversion rate of the reformer. The method for diagnosing deterioration of a reformer of a fuel cell power generator according to claim 8, further comprising the step of selecting one from the following. 21. A step of detecting a temperature of the reformer, a plurality of reformer steam ejector inlet temperatures predetermined by the reformer temperature detected in this step, and a deterioration amount of the reforming catalyst of the reformer. 10. The method for diagnosing deterioration of a reformer of a fuel cell power generator according to claim 9, further comprising the step of selecting one from the following relationships: 22. A step of detecting a temperature of the reformer, and a step of detecting a temperature of a plurality of reforming steam ejector inlets predetermined by the temperature of the reformer detected in this step and a methane conversion rate of the reformer. The method for diagnosing deterioration of a reformer of a fuel cell power generator according to claim 10, further comprising the step of selecting one. 23. A step of detecting a temperature of the reformer, a plurality of fuel gas desulfurization unit inlet temperatures predetermined by the reformer temperature detected in this step, and a deterioration amount of the reforming catalyst of the reformer. The method for diagnosing deterioration of a reformer of a fuel cell power generator according to claim 11, further comprising the step of selecting one of the relations. 24. A step of detecting a temperature of the reformer, and a step of detecting a temperature of a plurality of fuel gas desulfurization units and a methane conversion rate of the reformer determined in advance by the temperature of the reformer detected in this step. 13. The method for diagnosing deterioration of a reformer of a fuel cell power generator according to claim 12, further comprising the step of selecting one of the two. 25. A deterioration diagnostic means transmits a deterioration amount of the reforming catalyst of the reforming device, and determines a deterioration speed of the reforming catalyst from a relationship between the deterioration amount of the reforming catalyst and a power generation time, and uses the speed for power generation of the fuel cell. 6. The fuel cell system according to claim 1, further comprising: a life diagnosis unit that determines a replacement time of the reforming catalyst by calculating a period up to an upper limit value of the amount of deterioration of the reforming catalyst that does not have an adverse effect. , 13, 15 or 17. 26. The methane conversion rate of the reformer is transmitted from the deterioration diagnosis means, and from the relationship between the methane conversion rate and the power generation time,
Have a life diagnostic means for determining the rate of decrease of the methane conversion rate and calculating the period up to the lower limit value of the methane conversion rate which does not adversely affect the power generation of the fuel cell to determine the timing of replacing the reforming catalyst. Claims 2 and 4,
19. The fuel cell power generator according to 6, 14, 16 or 18. 27. A deterioration rate of a reforming catalyst is determined from a relationship between a deterioration amount of a reforming catalyst of a reformer and a power generation time, and reaches an upper limit of a deterioration amount of the reforming catalyst which does not adversely affect power generation of a fuel cell. 24. The reforming apparatus for a fuel cell power generator according to claim 7, further comprising a step of determining a time to replace the reforming catalyst by calculating a period up to Deterioration diagnosis method. 28. A rate of decrease of the methane conversion rate is determined from a relationship between the methane conversion rate of the reformer and the power generation time, and a period until reaching the lower limit value of the methane conversion rate which does not adversely affect the power generation of the fuel cell is calculated. Wherein the step of determining the time to replace the reforming catalyst is performed.
25. The method for diagnosing deterioration of a reformer of a fuel cell power generator according to 10, 12, 20, 22, or 24. 29. A desulfurization apparatus for removing sulfur in fuel gas, an ejector for mixing and supplying fuel gas and reforming steam, and an ejector for reacting fuel gas with reforming steam to produce hydrogen. A fuel in which a reforming device filled with a reforming catalyst and a fuel cell cell composed of a fuel electrode and an oxidizer electrode sandwiching an electrolyte for generating electricity by reacting hydrogen produced by the reforming device with oxygen are used. A computer-readable recording medium recording a deterioration diagnosis program for a reformer of a fuel cell power generator having a battery cell stack, wherein a raw fuel gas reformer inlet temperature measuring means installed at an inlet of the reformer Any one of a reforming steam ejector inlet temperature measuring means installed at an inlet of the ejector, and a fuel gas desulfurizing apparatus inlet temperature measuring means installed at an inlet of the desulfurizing apparatus. 1, or by one or more, the raw fuel gas reformer inlet temperature, reforming steam ejector inlet temperature,
A procedure for detecting any one or more of the inlet temperatures of the fuel gas desulfurization apparatus, a procedure for transmitting a temperature detection signal from each of the temperature measuring means to the deterioration diagnosing means, and a temperature detection from each of the temperature measuring means. In the deterioration diagnosing means which has received the signal, a predetermined signal which is selected by the data selecting means and transmitted to the deterioration diagnosing means in accordance with the reforming apparatus temperature which is detected by the reforming apparatus temperature measuring means and converted into a signal and transmitted. One or more of the raw fuel gas reformer inlet temperature, the reforming steam ejector inlet temperature, and the fuel gas desulfurizer inlet temperature, and the deterioration amount of the reforming catalyst of the reformer or the methane conversion rate A step of collating the collation data of the relationship, based on the result of the collation, determining a deterioration amount or a methane conversion rate of the reforming catalyst of the reformer, and determining a deterioration amount of the reforming catalyst of the reformer. A computer-readable recording medium degradation diagnosis program of the reformer of the fuel cell power generation system for the increase or decrease in the methane conversion execute a procedure to diagnose a degradation state of the reforming portion of the reformer. 30. A computer-readable recording medium having recorded thereon a deterioration diagnosis program for a reformer of a fuel cell power generator according to claim 29, wherein: a raw fuel gas reformer inlet temperature measuring means One of the reforming steam ejector inlet temperature measuring means, and the fuel gas desulfurizing device inlet temperature measuring means, or the raw fuel gas reforming device inlet temperature detected by one or more of the reforming steam ejector inlet temperature, And any one or more of the fuel gas desulfurization unit inlet temperatures, the predetermined raw fuel gas reformer inlet temperature selected and transmitted by the data selection means, the reforming steam ejector inlet temperature, and Poor collation data on the relationship between one or more of the fuel gas desulfurization unit inlet temperatures and the amount of degradation of the reforming catalyst in the reformer or methane conversion. The deterioration rate of the reforming catalyst or the rate of decrease in the methane conversion rate is determined from the relationship between the amount of deterioration of the reforming catalyst or the methane conversion rate obtained by collation by the diagnostic means, and the reforming catalyst that does not adversely affect the power generation of the fuel cell is obtained. The procedure to calculate the period up to the upper limit of the amount of deterioration of the methane or the period up to the lower limit of the methane conversion rate, the period up to the upper limit of the amount of deterioration of the reforming catalyst obtained by this, or A computer readable recording of a deterioration diagnosis program for a reformer of a fuel cell power generator for executing a procedure for determining a time for replacing a reforming catalyst based on a period up to a lower limit value of a methane conversion rate. recoding media.