JP2000268840A - Degradation diagnostic method for fuel cell power- generation device and its reforming device and recording medium containing program for executing the diagnostic method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To judge the replacement timing of a reform catalyst by performing degradation judgement of a reforming device momentarily at the side and continuously. SOLUTION: A fuel cell power-generating device is equipped of a reforming device 8 and a cell stack 21, and a temp. sensor measurses the temp. of the catalyst filled layer of a reforming device. Upon receiving the temp. sensing signal from the temp. sensor 6, a degradation judging means 5 judges the degraded condition of the reforming device 8 by putting the given temp. of the reforming catalyst filled layer in reference to the pre-determined temp. value and the reference data concerning the methane inverting rate of the reforming device 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 for generating electricity by reacting fuel and steam in a reformer to produce hydrogen, and reacting the hydrogen with oxygen in a cell stack to deteriorate the reformer. Diagnosis of the deterioration state of the reformer instantaneously and continuously on the recording medium on which a diagnostic method and a program for executing the method are recorded without analyzing the reformed gas, and performing reforming. The present invention relates to a fuel cell power generator capable of determining a catalyst replacement time, a method for diagnosing deterioration of a reformer thereof, and a recording medium on which a program for executing the method is recorded.

[0002]

2. Description of the Related Art FIG. 2 shows a configuration of a phosphoric acid type fuel cell power generator using city gas as fuel as a conventional example of a fuel cell power generator.

That is, the main components of the fuel cell power generator according to the prior art are a desulfurizer, an ejector, a reformer, a shift converter, a cell stack, a converter, a condenser, a pump, a steam separator, an air blower. , Evaporator, exhaust heat utilization system, sensor, flow control valve, shut-off valve and piping.

In FIG. 2, 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, and 11 is a shift. Converter, 12 for combustion air, 13 for fuel electrode exhaust gas, 14 for reformer burner combustion exhaust gas, 15 for air blower, 16 for power generation air, 17 for outside air, 18 for fuel electrode, 19 for electrolyte,
20 is an oxidizer electrode, 21 is a cell stack, 22 is a voltage sensor, 23 is a current sensor, 24 is a converter, 25 is a load,
26 is battery cooling water, 27 is a steam separator, 28 is a steam separator heater, 29 is a catalyst packed bed, 30 is a flow control valve, 31
Is steam for reforming, 33 is an evaporator, 34 is steam for exhaust heat recovery, 35 is an exhaust heat utilization system, 36 is a refrigerant, 37 is an oxidant electrode exhaust gas, 38 is a condenser, 39 is an exhaust gas, and 40 is condensed water. , 41 is a temperature sensor for measuring the reformer temperature, 43 is a makeup water pump, 44 is makeup water, 45 is a flow control valve, 46 is a flow control valve, 48 is a reforming section, 49 is a pressure sensor, and 50 is a fuel cell. Output, 52 is a flow control valve, 53 is an ejector, 5
4 is a flow control valve, 55 is a liquid level sensor, 56 is a pump,
7 is a shutoff valve, 58 is condensed water, 59 is a starter burner, 60
Is a shutoff valve, 61 is a burner air for starting the reformer, 62 is a shutoff valve, 63 is a cooler, 64 is a temperature sensor, and 65 is a shutoff valve.

[0005] The operation of this conventional fuel cell power generator will be described below with reference to FIG.

First, the shut-off valve 3 is opened, and the city gas 4 is supplied with a desulfurization catalyst (a cobalt-molybdenum catalyst and a zinc oxide adsorbent).
Is supplied to the desulfurization device 7 filled with the fuel, and the desulfurization device 7 allows the reforming device 8 and the fuel electrode 1 of the cell stack 21 to be supplied.
Sulfur contained in the deodorant in the city gas 4 which causes deterioration of the catalyst 8 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 starting burner 59.

The shut-off valve 60 is also 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 starter burner 59, when the fuel cell power generator is started, the city gas 4 burns, and the temperature of the reformer 8 is raised.

The shut-off valves 57 and 60 are kept closed except during startup.

The supply amount of city gas is determined based on the fuel cell output 50 detected by the voltage sensor 22 and the current sensor 23 and the reformer temperature detected by the reformer temperature measuring temperature sensor 41 and the fuel cell output 50 set in advance. By adjusting the opening of the flow control valve 52 based on the relationship between the reformer temperature and the opening of the flow control valve 52 (that is, the supply of city gas), the city gas supply is changed to the fuel cell output 50. To a value appropriate for the quality equipment temperature.

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 reforming catalyst (usually a nickel-based catalyst) Is supplied to the reforming section 48 of the reforming apparatus 8 in which is filled.

The supply amount of the reforming steam to the ejector 53 is determined by the preset opening degree of the flow control valve 52 (that is,
By adjusting the opening of the ejector 53 based on the relationship between the amount of city gas supplied to the reformer 8 and the opening of the ejector 53 (that is, the amount of steam for reforming), a predetermined predetermined amount is set. Control is performed to obtain a steam carbon ratio.

In the reformer 8, steam reforming of the city gas 4 as a fuel gas is performed, and a hydrogen-rich reformed gas 2 is produced.

The steam reforming reaction of methane, which is a main component of city gas, is represented by the following equation.

(Steam reforming reaction of methane)

[0017]

(Equation 1)

Since the hydrogen-rich reformed gas contains carbon monoxide which causes deterioration of the catalyst of the fuel electrode 18 of the cell stack 21, the reformed gas is a shift catalyst (copper-zinc based catalyst). Is supplied to the shift converter 11 filled with the gas, and the carbon monoxide in the reformed gas is converted into carbon dioxide by a shift reaction represented by the following equation.

(Shift reaction)

[0020]

(Equation 2)

The shift converter 11 reduces the concentration of carbon monoxide in the reformed gas to 1% or less.

The reformed gas leaving the shift converter 11 is
The fuel is supplied to the fuel electrode 18 of the cell stack 21 and used for power generation of the fuel cell.

A part of the gas at the outlet of the shift converter 11 is recycled to the desulfurizer 7, and the hydrogen in the recycled gas is used for the desulfurization reaction.

The supply amount of the recycled gas is determined by the preset opening degree of the flow control valve 52 (ie, the supply amount of the city gas to the reformer 8) and the opening degree of the flow control valve 54 (ie, the supply amount of the recycled gas). ), The flow control valve 54
By controlling the degree of opening, control is performed so that a predetermined supply amount is set in advance.

On the other hand, to the oxidizer electrode 20 of the cell stack 21, the shut-off valve 65 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 generation air 16 is determined by the voltage sensor 2
2 and the fuel cell output 50 detected by the current sensor 23, the opening of the flow control valve 46 is determined based on the relationship between the preset fuel cell output 50 and the opening of the flow control valve 46 (i.e., the air supply amount for power generation). The fuel cell output is adjusted to a value corresponding to the fuel cell output 50.

At the fuel electrode 18 of the cell stack 21,
By the reaction shown in the equation (3), hydrogen in the reformed gas is converted into hydrogen ions and electrons.

(Fuel electrode reaction)

[0029]

(Equation 3)

The hydrogen ions diffuse inside the electrolyte 19,
The oxidizer electrode 20 is reached.

On the other hand, electrons flow through an external circuit and are taken out as a fuel cell output 50.

At the oxidant electrode, 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 are reacted by the reaction shown in the equation (4). Reacts at the three-phase interface to produce water.

(Oxidant electrode reaction)

[0034]

(Equation 4)

Summarizing the equations (3) and (4), the whole battery reaction in the cell stack 21 can be expressed as a simple reaction in which water is produced from hydrogen and oxygen as shown in the equation (5).

(Battery reaction)

[0037]

(Equation 5)

Fuel cell output 50 obtained by power generation
Is supplied to the load 25 after voltage conversion or DC-AC conversion is performed by the converter 24.

At 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. This is because the cell stack 21 deteriorates.

The fuel electrode exhaust gas 13 containing unreacted hydrogen is supplied to the reformer burner 9 and used as a burner twist.

Since the methane steam reforming reaction shown in the equation (1) is an endothermic reaction, it is necessary to externally supply heat of reaction 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 62, whereby the reformer 8 of the reformer 8 is burned. The temperature of 48 is increased up to about 700 ° C.

The supply amount of the combustion air 12 is determined based on the reformer temperature preset from the reformer temperature detected by the reformer temperature measuring temperature sensor 41 and the opening degree of the flow control valve 45 (that is, the combustion air temperature). The control is performed by adjusting the opening degree of the flow control valve 45 based on the relationship of the air supply amount).

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,
It is used for battery cooling water 26, reforming steam 31, steam for exhaust heat recovery 34, and the like.

Since the battery reaction shown in the equation (5) is an exothermic reaction, the temperature of the cell stack 21 increases as the power generation time elapses.

When the temperature of the cell stack 21 rises,
Although the resistance is reduced and the output characteristics are temporarily improved due to an increase in the hydrogen ion conductivity of the electrolyte, the deterioration is apt to occur and the life is shortened.

Then, the battery cooling water 2 is supplied from the steam-water separator 27.
6 is supplied to the cooler 63 to cool the cell stack 21.

The operating temperature of the 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 depends on the temperature sensor 6
4 so that the outlet temperature of the battery cooling water cell stack detected in Step 4 falls within a predetermined temperature range set in advance.
Is controlled by adjusting the degree of opening.

The battery cooling water 26 exiting the cell stack 21
Is returned to the steam separator 27 in the form of a mixture of water and steam.

At the time of start-up and when the pressure sensor 49 detects that the pressure of the steam / water separator has dropped below a predetermined pressure, the preset predetermined power is applied to the steam / water separator by the pressure sensor 49. The water is supplied to the steam separator heater 28 until it detects that the pressure exceeds a predetermined pressure, and generates steam.

When the liquid level sensor 55 detects that the water level of the steam-water separator 27 has dropped below a predetermined water level, the liquid level sensor 55 changes the water level of the steam-water separator 27 to a predetermined level. The makeup water pump 43 is operated to operate the steam-water separator 27 until it detects that a predetermined water level has been reached.
Is supplied with makeup water 44.

Of the steam supplied from the cell stack 21 to the steam separator 27 or the steam generated by the steam separator 27, steam other than the steam used for the reforming steam 31 is the steam 34 for exhaust heat recovery. Is supplied to the evaporator 33 and used for evaporating the refrigerant 35 of the exhaust heat utilization system 35.

Exhaust heat recovery steam 3 condensed in evaporator 33
4 condensed water 58 is returned to the steam separator 27.

[0058]

Next, problems of the fuel cell power generator according to the prior art as described above will be described.

That is, in the fuel cell power generator according to the prior art, in order to diagnose the deterioration state of the reformer,
An expensive gas analyzer such as a gas chromatograph is connected to the outlet of the reformer to continuously sample the reformed gas for gas analysis, or to periodically place the reformed gas at the outlet of the reformer in a container. By sampling and bringing the gas analyzer to a certain place and performing gas analysis, the methane conversion rate of the reformer 8 is obtained from the amount of methane (methane slip amount) in the reformed gas, and the deterioration of the reformer 8 is determined. In addition to diagnosing the condition, the time for replacing the reforming catalyst was determined.

FIG. 10 shows, for reference, the methane conversion rate and the methane conversion rate of the reformer 8 when a 200 kW phosphoric acid fuel cell power generator was used to generate power at a rated output of 200 kW using city gas as fuel. 4 shows the relationship between the amount of deterioration of the reforming catalyst of the reforming device 8.

By detecting the amount of methane in the reformed gas at the outlet of the reformer and calculating the methane conversion of the reformer 8, the methane conversion or the reforming catalyst converted from the methane conversion using FIG. The deterioration of the reforming unit 48 of the reforming device 8 can be diagnosed based on the decrease in the methane conversion rate or the increase in the deterioration amount of the reforming catalyst. The lowering rate of the methane conversion rate or the deterioration rate of the reforming catalyst is determined from the relationship between the amount of catalyst deterioration and the power generation time, and the lower limit value of the methane conversion rate that does not adversely affect the power generation of the cell stack 21 or the reforming of the reforming catalyst The replacement time of the reforming catalyst can be determined by calculating the period up to the upper limit of the catalyst deterioration amount.

However, in these methods, it takes a long time for gas analysis, and it is impossible to diagnose the deterioration state of the reformer instantly on the spot. In order to continuously diagnose the deterioration state of the reformer on the spot, a dedicated gas analyzer is required for the fuel cell power generator, or a gas analyzer is required. Since the sampling gas must be taken to a certain point, there is a problem that it takes a long time for deterioration diagnosis.

The present invention has been made in view of the above circumstances, and it is an object of the present invention to take a long time for sampling and analysis of reformed gas and to instantly diagnose deterioration of a reformer. It is impossible, and an expensive gas analyzer is required for the deterioration diagnosis of the reformer. Further, if the deterioration diagnosis of the reformer is to be continuously performed on the spot, the fuel cell power generator is not suitable. A special gas analyzer is required,
Alternatively, the problem of the fuel cell power generator according to the conventional technology, such as deterioration diagnosis taking time because the sampling gas must be taken to a certain place of the gas analyzer, is solved instantaneously and continuously on the spot. Provided is a fuel cell power generator capable of performing a deterioration diagnosis of a reformer to determine a time for replacing a reforming catalyst, a method of diagnosing deterioration of the reformer, and a recording medium on which a program for executing the method is recorded. It is in.

[0064]

In the fuel cell power generator according to the present invention, in order to solve the above problems, the temperature of the packed bed of the reformer catalyst, the temperature of the outer wall of the reformer reforming tube, and the temperature of the combustion exhaust gas of the reformer burner. Detects one or more of the reformer burner combustion exhaust gas reformer outlet temperature, reformed gas temperature, and reformed gas reformer outlet temperature, and diagnoses and modifies the deterioration state of the reformer. The most important feature is to determine the replacement time of the high quality catalyst.

The fuel cell power generator according to the present invention is different from the fuel cell power generator according to the prior art in that a temperature sensor for measuring the temperature of the catalyst packed bed of the reformer, a temperature sensor for measuring the outer wall temperature of the reformer reforming tube, A temperature sensor for measuring the temperature of the reformer burner flue gas, a temperature sensor for measuring the outlet temperature of the reformer burner flue gas reformer, a temperature sensor for measuring the temperature of the reformed gas, and a temperature sensor for measuring the outlet temperature of the reformer gas. 1
And the deterioration diagnosis means, the life diagnosis means and the verification data selection means are installed.The detected temperature is converted into a signal and transmitted to the deterioration diagnosis means, and the detected temperature is revised by the verification data selection means. The reformer temperature detected by the temperature sensor for measuring the reformer temperature is converted into a signal, and is transmitted to the deterioration diagnostic means. Temperature of reformer tube outer wall, reformer burner flue gas temperature, reformer burner flue gas reformer outlet temperature, reformed gas temperature, reformed gas reformer outlet temperature The above is compared with the comparison data of the relationship between the methane conversion rate of the reformer and the deterioration diagnosis means to obtain the methane conversion rate of the reformer or the deterioration amount of the reforming catalyst converted from the methane conversion rate, and In order to reduce the conversion rate or increase the amount of deterioration of the reforming catalyst, without using an expensive gas analyzer such as a gas chromatograph, it is necessary to analyze the reformed gas at the outlet of the reformer, which requires a long time. The deterioration condition of the reformer is diagnosed instantaneously at the site, and the life diagnosing means includes a temperature sensor for measuring the temperature of the packed bed of the reformer catalyst, a temperature sensor for measuring the outer wall temperature of the reformer reforming pipe, and the combustion of the reformer burner. One of a temperature sensor for measuring exhaust gas temperature, a temperature sensor for measuring outlet temperature of reformer burner combustion exhaust gas reformer, a temperature sensor for measuring temperature of reformed gas, and a temperature sensor for measuring outlet temperature of reformed gas reformer; Alternatively, the reformer catalyst packed bed temperature, the reformer reformer outer tube temperature, the reformer burner combustion exhaust gas temperature, the reformer burner combustion exhaust gas reformer outlet temperature, the reformer gas Any one or more of the temperature and the outlet temperature of the reformed gas reformer are detected by a deterioration diagnosis means in advance at a detected temperature (reformer catalyst packed bed temperature, reformer reformer outer wall temperature, Any one or more of reformer burner flue gas temperature, reformer burner flue gas reformer outlet temperature, reformed gas temperature, reformed gas reformer outlet temperature) and methane of reformer The rate of decrease in the methane conversion rate or the rate of degradation of the reforming catalyst from the relationship between the methane conversion rate or the conversion amount of the reforming catalyst converted from the methane conversion rate and the power generation time obtained by collation with the conversion rate relation matching data In the period up to the lower limit of methane conversion that does not adversely affect power generation,
Another difference is that it is possible to determine the time to replace the reforming catalyst by calculating the period up to the upper limit of the amount of deterioration of the reforming catalyst.

Specifically, according to one aspect of the present invention, as means for solving the above problems, there is provided a reforming tube filled with a reforming catalyst for reacting fuel with steam to produce hydrogen. A fuel cell power generator having a reformer and a cell stack in which cells composed of a fuel electrode sandwiched with an electrolyte and an oxidizer electrode for generating power by reacting hydrogen produced by the reformer with oxygen are stacked. In the reformer catalyst packed bed temperature measurement temperature sensor for measuring the temperature of the reforming catalyst packed bed of the reformer, receiving a temperature detection signal from this reformer catalyst packed bed temperature measurement temperature sensor, Comparison data of the relationship between the reformer catalyst packed bed temperature determined by the reformer catalyst packed bed temperature measuring temperature sensor and the predetermined reformer catalyst packed bed temperature and the methane conversion rate of the reformer. The fuel cell power plant for the deterioration diagnosis means for diagnosing a deterioration state of the reformer, characterized by having a is provided by matching.

According to another aspect of the present invention, there is provided a reforming apparatus having a reforming pipe filled with a reforming catalyst for reacting fuel with steam to produce hydrogen. , A reformer for a fuel cell power generator having a fuel cell sandwiched with an electrolyte for generating power by reacting hydrogen produced by the reformer with oxygen and a cell stack in which cells composed of oxidizer electrodes are stacked Detecting the temperature of the catalyst-packed bed of the reformer, and detecting the detected reformer catalyst-packed bed temperature with a predetermined reformer catalyst-packed bed temperature and methane of the reformer. Diagnosing a deterioration state of the reformer by collating with conversion data of a conversion rate relationship. .

According to another aspect of the present invention, there is provided a reforming apparatus having a reforming tube filled with a reforming catalyst for reacting fuel with steam to produce hydrogen. , A reformer for a fuel cell power generator having a fuel cell sandwiched with an electrolyte for generating power by reacting hydrogen produced by the reformer with oxygen and a cell stack in which cells composed of oxidizer electrodes are stacked In the method for diagnosing deterioration of a reformer, at least one temperature sensor for measuring the temperature of the packed bed of the reformer, the temperature sensor for measuring the temperature of the outer wall of the reformer reforming tube, and the burner for the reformer provided in the reformer of the reformer Combustion exhaust gas temperature measurement temperature sensor, reformer burner combustion exhaust gas reformer outlet temperature measurement temperature sensor, reformed gas temperature measurement temperature sensor, reformed gas reformer exit temperature measurement temperature sensor, reformer Touch Any one of packed bed temperature, reformer reformer tube outer wall temperature, reformer burner combustion exhaust gas temperature, reformer burner combustion exhaust gas reformer outlet temperature, reformed gas temperature, reformed gas reformer outlet temperature Detecting one or more than one, transmitting a temperature detection signal from each of the temperature sensors to a deterioration diagnosis unit, and receiving a temperature detection signal from each of the temperature sensors. The reformer temperature detected by the temperature sensor for measuring the device temperature is converted into a signal, and the predetermined detected temperature selected and transmitted by the collation data selection means in correspondence with the transmitted reformer temperature and the reformer temperature. As reference data of the relationship between the methane conversion rate of the apparatus, reference data of the relation between the catalyst packed bed temperature of the reformer and the methane conversion rate of the reformer, the outer wall temperature of the reformer reforming pipe, and the methane conversion of the reformer. Rate relation Collation data of the relationship between the reformer burner combustion exhaust gas temperature and the methane conversion rate of the reformer, and the collation of the relationship between the reformer burner combustion exhaust gas reformer outlet temperature and the methane conversion rate of the reformer. Data, collation data of the relationship between the reformed gas temperature and the methane conversion rate of the reformer, one of the collation data of the relationship between the reformed gas reformer outlet temperature and the methane conversion rate of the reformer, Or matching one or more,
Based on these collation results, the methane conversion rate of the reformer or the deterioration amount of the reforming catalyst converted from the methane conversion rate is obtained, and the reduction of the methane conversion rate of the reformer or the deterioration amount of the reforming catalyst is calculated. Diagnosing a deterioration state of the reforming unit of the reformer from the increase. A method of diagnosing deterioration of the reformer of the fuel lightning pond power generator is provided.

According to another aspect of the present invention, there is provided a reforming apparatus having a reforming tube filled with a reforming catalyst for reacting fuel with steam to produce hydrogen. , A reformer for a fuel cell power generator having a fuel cell sandwiched with an electrolyte for generating power by reacting hydrogen produced by the reformer with oxygen and a cell stack in which cells composed of oxidizer electrodes are stacked A storage medium storing a program for executing a method for diagnosing deterioration of a reformer, comprising: a temperature sensor for measuring a temperature of a catalyst-packed bed of at least one reformer provided in a reformer of the reformer; Temperature sensor for measuring the temperature of the outer wall of the reforming tube, temperature sensor for measuring the temperature of the combustion exhaust gas of the reformer burner, temperature sensor for measuring the outlet temperature of the reformer burner combustion exhaust gas, temperature sensor for measuring the temperature of the reformed gas, reformed gas Temperature sensor for measuring the outlet temperature of the reformer, the temperature of the packed bed of the reformer, the temperature of the outer wall of the reformer reforming pipe, the temperature of the combustion exhaust gas of the reformer burner, the temperature of the outlet of the reformer burner exhaust gas, the temperature of the reformed gas Temperature, any one of the reformed gas reformer outlet temperature, or detecting one or more, and transmitting a temperature detection signal from each of the temperature sensors to the deterioration diagnosis unit, and from each of the temperature sensors Deterioration diagnosis unit that receives the temperature detection signal of the above, the reformer temperature detected by the temperature sensor for measuring the temperature of the reformer is converted into a signal and selected by the collation data selector in accordance with the transmitted reformer temperature The collation data of the relationship between the predetermined detected temperature transmitted and the methane conversion rate of the reformer, the collation data of the relationship between the reformer catalyst packed bed temperature and the methane conversion rate of the reformer, apparatus Data of the relationship between the outer wall temperature of the gas pipe and the methane conversion rate of the reformer, the verification data of the relationship between the temperature of the flue gas of the reformer burner and the conversion rate of methane of the reformer, the reformer burner flue gas reformer Matching data of the relationship between the outlet temperature and the methane conversion rate of the reformer, matching data of the relationship between the reformed gas temperature and the methane conversion rate of the reformer, the outlet temperature of the reformed gas reformer and the temperature of the reformer. Collating with any one or more of collation data of the relationship of methane conversion,
Based on these collation results, the methane conversion rate of the reformer or the deterioration amount of the reforming catalyst converted from the methane conversion rate is obtained, and the reduction of the methane conversion rate of the reformer or the deterioration amount of the reforming catalyst is calculated. Diagnosing a deterioration state of the reforming unit of the reformer from the increase. A recording medium on which a program for executing a method of diagnosing deterioration of the reformer of the fuel thunder pond power generator is recorded. Is provided.

[0070]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS An embodiment of a fuel cell power generator according to the present invention will be described below with reference to the drawings.

FIG. 1 is a block diagram showing an embodiment of a fuel cell power generator according to the present invention.

In FIG. 1, the same components as those in FIG. 2 described above are denoted by the same reference numerals, and description thereof will be omitted.

FIG. 3 is an enlarged view of a reformer for explaining details of the fuel cell power generator according to the present invention.

An embodiment of the fuel cell power generator according to the present invention will be described with reference to FIGS. 1 and 3.

The fuel cell power generator according to the present embodiment
The conventional fuel cell power generator shown in FIG.
As shown in FIGS. 1 and 3, the reformer 8 has a temperature sensor 6 for measuring the temperature of the catalyst packed bed of the reformer, a temperature sensor 32 for measuring the outer wall temperature of the reformer pipe, and the temperature of the combustion exhaust gas of the reformer burner. At least one temperature sensor for measurement 10, a temperature sensor 47 for measuring the outlet temperature of the reformer burner flue gas reformer, a temperature sensor 66 for measuring the temperature of the reformed gas, and a temperature sensor 51 for measuring the outlet temperature of the reformed gas reformer. The newly provided point and the reformer temperature detected by the reformer temperature measuring temperature sensor 41 are converted to a signal and transmitted, and the reformer catalyst packed bed temperature is determined in advance corresponding to the reformer temperature. And the relationship between the methane conversion rate of the reformer 8, the relationship between the outer wall temperature of the reformer reforming tube and the methane conversion rate of the reformer 8, and the relationship between the combustion exhaust gas temperature of the reformer burner and the methane conversion rate of the reformer 8. , Reformer burner flue gas reformer The relationship between the outlet temperature and the methane conversion rate of the reformer 8, the relationship between the reformed gas temperature and the methane conversion rate of the reformer 8, and the relationship between the reformed gas reformer outlet temperature and the methane conversion rate of the reformer 8. Check data selecting means 67 for selecting any one or more than one as check data, the temperature of the reformer catalyst packed bed detected by each of the temperature sensors 6, 32, 10, 47, 66, 51, Signal of one or more of the temperature of the outer wall of the heat pipe, the temperature of the reformer burner flue gas, the temperature of the reformer burner flue gas reformer outlet, the temperature of the reformed gas, and the temperature of the reformed gas reformer outlet In response, the collation data selection means 67 selects and transmits the collation data of the relationship between the predetermined reformer catalyst packed bed temperature and the methane conversion rate of the reformer 8 which are selected and transmitted, and the outer wall temperature of the reformer reforming pipe. Relationship between methane conversion rate of reformer 8 Verification data, verification data of the relationship between the reformer burner combustion exhaust gas temperature and the methane conversion rate of the reformer 8, and verification data of the relation between the reformer burner combustion exhaust gas reformer outlet temperature and the methane conversion rate of the reformer 8 One of verification data of a relationship between a reformed gas temperature and a methane conversion rate of the reformer 8; and verification data of a relation between a reformed gas reformer outlet temperature and a methane conversion rate of the reformer 8.
Alternatively, the methane conversion rate of the reformer 8 or the deterioration amount of the reforming catalyst converted from the methane conversion rate is determined by comparing with one or more, and the reforming is performed based on the decrease in the methane conversion rate or the increase in the deterioration amount of the reforming catalyst. A deterioration diagnosing means 5 for diagnosing a deterioration state of the reforming section 48 of the apparatus 8, a reformer catalyst packed bed temperature detected by each temperature sensor, a reformer reforming tube outer wall temperature, a reformer burner combustion exhaust gas temperature, One or more of the reformer burner flue gas reformer outlet temperature, reformed gas temperature, and reformed gas reformer outlet temperature are selected and transmitted by the collation data selection means 67 in the deterioration diagnosis means 5. Predetermined detected temperatures (reformer catalyst packed bed temperature, reformer reformer outer wall temperature, reformer burner combustion exhaust gas temperature, reformer burner combustion exhaust gas reformer outlet temperature, reformed gas temperature , One or more of the outlet temperatures of the reformer 8) and the methane conversion rate or methane conversion rate obtained and transmitted by collation with the collation data of the relationship between the methane conversion rate and the methane conversion rate of the reformer 8. From the relationship between the amount of deterioration of the reforming catalyst converted from and the power generation time, the rate of decrease in the methane conversion rate or the rate of deterioration of the reforming catalyst is obtained, and the period up to the lower limit of the methane conversion rate that does not adversely affect power generation, or The difference is that a lifetime diagnosis unit 68 for determining the time to replace the reforming catalyst is newly provided by calculating the period up to the upper limit of the amount of deterioration of the reforming catalyst.

Here, the collation data selecting means 67 stores predetermined detection temperatures (reformer catalyst packed bed temperature, reformer reformer outer tube temperature, reformer burner combustion exhaust gas temperature,
Verification data of the relationship between the reformer burner flue gas reformer outlet temperature, reformed gas temperature, reformed gas reformer outlet temperature, or more) and the methane conversion rate of the reformer 8 Is created and stored in advance based on FIG. 4 to FIG.

The reason why the life diagnosing means 68 can determine the time for replacing the reforming catalyst is as described below.
The deterioration amount of the reforming catalyst obtained in FIG. 10 is plotted with time, and the time for replacing the reforming catalyst can be estimated from the time trend of the deterioration. It is assumed that the life diagnosing means 68 has a function of plotting the deterioration amount of the quality catalyst over time.

The deterioration diagnosing means 5, the collation data selecting means 67, and the life diagnosing means 68 are specifically based on a deterioration diagnosing program previously recorded on a predetermined recording medium by a personal computer (PC) or the like. Shall be executed.

Next, the operation of the fuel cell power generator according to the present embodiment will be described with reference to the flowchart shown in FIG.

In the fuel cell power generator according to the present embodiment, first, at least one temperature sensor 6 for measuring the temperature of the catalyst packed bed of the reformer provided in the reformer 48 of the reformer 8, the reformer reformer A temperature sensor 32 for measuring the pipe outer wall temperature, a temperature sensor 10 for measuring the temperature of the reformer burner flue gas, a temperature sensor 47 for measuring the outlet temperature of the reformer burner flue gas reformer, a temperature sensor 66 for measuring the temperature of the reformed gas, Temperature sensor 51 for measuring the outlet temperature of the reforming gas reformer, the temperature of the packed bed of the reformer catalyst, the outer wall temperature of the reformer reforming tube, the temperature of the combustion exhaust gas of the reformer burner, the temperature of the outlet of the reformer burner combustion exhaust gas. ,
One or more of the reformed gas temperature and the outlet temperature of the reformed gas reformer are detected (step S1).

Then, these temperature sensors transmit these temperature detection signals to the deterioration diagnosis means 5 (step S).
2).

Next, the deterioration diagnosing unit 5 receiving these temperature detection signals converts the reformer temperature detected by the reformer temperature measuring temperature sensor 41 into a signal and converts it into a transmitted reformer temperature. Corresponding collation data of the relationship between the predetermined detected temperature and the methane conversion rate of the reformer 8 correspondingly selected and transmitted by the collation data selector 67, that is, the temperature of the reformer catalyst packed bed temperature and the reformer 8 Reference data on the relationship between the methane conversion rates, reference data on the relationship between the outer wall temperature of the reformer reforming pipe and the methane conversion rate of the reformer 8, and the relationship between the combustion exhaust gas temperature of the reformer burner and the methane conversion rate of the reformer 8 Collation data, reformer burner combustion exhaust gas reformer outlet temperature and reformer 8
Of the relationship between the methane conversion rate of the reformer, the comparison data of the relationship between the reformed gas temperature and the methane conversion rate of the reformer 8, and the comparison of the relationship between the outlet temperature of the reformed gas reformer and the methane conversion rate of the reformer 8 It is checked against any one or more of the data (step S3).

In this way, the methane conversion rate of the reformer 8 or the amount of deterioration of the reforming catalyst converted from the methane conversion rate is obtained. The state of deterioration of the reforming section 48 is diagnosed (step S4).

That is, the life diagnosis means 68 detects the reformer catalyst packed bed temperature, the reformer reformer tube outer wall temperature, the reformer burner combustion exhaust gas temperature, and the reformer burner combustion exhaust gas reforming detected by each temperature sensor. Equipment outlet temperature, reformed gas temperature,
Any one or more of the outlet temperatures of the reformed gas reformer are determined by the deterioration diagnostic means 5 at a predetermined detection temperature (reformer catalyst packed bed temperature selected and transmitted by the collation data selecting means 67). , Reformer reformer tube outer wall temperature, reformer burner combustion exhaust gas temperature, reformer burner combustion exhaust gas reformer outlet temperature, reformed gas temperature, reformed gas reformer outlet temperature, or One or more) and the conversion data of the methane conversion rate of the reformer 8 and the methane conversion rate obtained by checking the data, or the methane conversion rate based on the relationship between the power generation time and the amount of deterioration of the reforming catalyst converted from the methane conversion rate. Calculate the period of time until the lower limit of the methane conversion rate that does not adversely affect power generation or the period of time until the upper limit of the amount of deterioration of the reforming catalyst is obtained, by determining the rate of reduction of the conversion rate or the rate of deterioration of the reforming catalyst. 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).

Thus, the fuel cell power generator according to the present embodiment differs from the fuel cell power generator according to the prior art in determining the time for replacing the reforming catalyst.

FIG. 4 shows a catalyst packed bed (Ni-A1203 catalyst and Ni-A1203 catalyst) of the reformer 8 when a 200 kW phosphoric acid fuel cell power generator is used to generate power at a rated output of 200 kW using city gas as fuel. A two-layer catalyst packed bed of RU-Al203 catalyst, the same applies hereinafter) raw fuel gas inlet,
20% of the total length of the catalyst packed bed (converted from the raw fuel gas inlet, the same applies hereinafter), 40% of the total length of the catalyst packed bed,
Reformer catalyst packed bed temperature and methane conversion of reformer 8 at 60% of the full length of the catalyst packed bed, at 80% of the full length of the catalyst packed bed, and at six reformed gas outlets of the catalyst packed bed. The relationship between the rates is shown.

From FIG. 4, it can be seen that with the decrease in the methane conversion,
It can be seen that the reformer catalyst packed bed temperature changes.

Accordingly, the temperature of the reformer catalyst packed bed temperature is detected by the temperature sensor 6 for measuring the temperature of the reformer catalyst packed bed, and the temperature of the reformer catalyst packed bed and the methane conversion rate of the reformer 8 shown in FIG. Is obtained as collation data to determine the methane conversion rate of the reformer 8 or the amount of deterioration of the reforming catalyst converted from the methane conversion rate using FIG. It is possible to diagnose the state of deterioration of the reforming section 48 of the reformer 8 from the increase in the amount of deterioration, and the obtained methane conversion rate or the reforming converted from the methane conversion rate using the relationship shown in FIG. From the relationship between the amount of catalyst deterioration and the power generation time, the rate of decrease in the methane conversion rate or the rate of deterioration of the reforming catalyst is determined, and the period up to the lower limit of the methane conversion rate that does not adversely affect the power generation of the fuel cell,
Alternatively, the replacement time of the reforming catalyst can be determined by calculating the period until the deterioration amount of the reforming catalyst reaches the upper limit value.

It is to be noted that two or more temperature sensors 6 for measuring the temperature of the catalyst packed bed of the reformer may be provided, and the average value of the detected temperatures may be used as the temperature of the catalyst packed bed of the reformer.

When two or more reforming tubes are installed in the reformer and there are two or more catalyst packed beds, a temperature sensor 6 for measuring the temperature of the reformed catalyst packed bed is provided for each catalyst packed bed. Is installed to detect the temperature of the packed bed of the reformer, and the relationship between the temperature of the packed bed of the reformer and the conversion rate of methane of the reformer shown in FIG. When the amount of deterioration of the reforming catalyst calculated from the methane conversion rate or the methane conversion rate using FIG. 10 is obtained, the reforming catalyst for each reforming pipe is determined from the decrease in the methane conversion rate or the increase in the deterioration amount of the reforming catalyst. It is possible to diagnose the deterioration state of the methane conversion rate, and the rate of decrease of the methane conversion rate from the relationship between the obtained methane conversion rate or the conversion amount of the reforming catalyst converted from the methane conversion rate using the relationship shown in FIG. 10 and the power generation time. Alternatively, the deterioration rate of the reforming catalyst For each reforming tube, by calculating the period up to the lower limit of the methane conversion rate that does not adversely affect the power generation of the fuel cell, or the period up to the upper limit of the amount of deterioration of the reforming catalyst, The timing for replacing the reforming catalyst for each reforming tube can be determined.

FIG. 5 similarly shows a 200 kW phosphoric acid fuel cell power generator using city gas as fuel.
When power is generated at the W rated output, the raw fuel gas inlet of the catalyst packed bed of the reformer 8, the position of 20% of the total length of the catalyst packed bed (converted from the raw fuel gas inlet, the same applies hereinafter), the catalyst filling 40% of the total length of the bed, 60% of the full length of the catalyst packed bed, 80% of the full length of the packed catalyst bed, and 6 reformer reforming tubes at the reformed gas outlet of the packed catalyst bed The relationship between the outer wall temperature and the amount of deterioration of the reforming catalyst of the reformer is shown.

From FIG. 5, it can be seen that the methane conversion rate decreases and
It can be seen that the outer wall temperature of the reformer reforming tube changes.

Therefore, the temperature sensor 32 for measuring the temperature of the outer wall of the reformer reforming tube is used to detect the temperature of the outer wall of the reformer reforming tube.
The conversion between the methane conversion rate of the reformer 8 or the methane conversion rate using FIG. 10 was performed by collating the relationship between the outer wall temperature of the reformer reformer tube and the methane conversion rate of the reformer 8 shown in FIG. When the deterioration amount of the reforming catalyst is obtained, it is possible to diagnose the deterioration state of the reforming unit 48 of the reformer 8 from the decrease in the methane conversion rate or the increase in the deterioration amount of the reforming catalyst. Alternatively, the rate of decrease in the methane conversion rate or the rate of deterioration of the reforming catalyst is determined from the relationship between the amount of deterioration of the reforming catalyst and the power generation time converted from the methane conversion rate using the relationship shown in FIG. The replacement time of the reforming catalyst can be determined by calculating the period up to the lower limit of the methane conversion rate, which does not affect the above, or the period up to the upper limit of the deterioration amount of the reforming catalyst.

It is to be noted that two or more temperature sensors 32 for measuring the temperature of the outer wall of the reformer reforming pipe may be provided, and the average value of the detected temperatures may be used as the outer wall temperature of the reformer reforming pipe.

When two or more reforming tubes are installed in the reformer, the temperature is improved by installing a temperature sensor 32 for measuring the outer wall temperature of the reformer reforming tube for each catalyst packed bed. The reformer tube outer wall temperature is detected, and the relationship between the reformer reformer tube outer wall temperature and the methane conversion rate of the reformer 8 shown in FIG. When the amount of deterioration of the reforming catalyst converted from the methane conversion rate using the conversion rate or FIG. 10 is obtained, the deterioration of the reforming catalyst in each reforming pipe is determined from the decrease in the methane conversion rate or the increase in the deterioration amount of the reforming catalyst. Diagnosis of the state is possible, and from the relationship between the obtained methane conversion rate or the deterioration amount of the reforming catalyst converted from the methane conversion rate using the relationship shown in FIG. The degradation rate of the quality catalyst, and By calculating the period up to the lower limit of the methane conversion rate that does not adversely affect the power generation of the fuel cell or the period up to the upper limit of the amount of deterioration of the reforming catalyst, the reforming of each reforming tube is performed. The catalyst replacement time can be determined.

FIG. 6 shows a 200 kW phosphoric acid type fuel cell power generator using city gas as fuel.
When power is generated at the rated output, the raw fuel gas inlet of the catalyst packed bed of the reformer 8, the position of 20% of the total length of the catalyst packed bed (converted from the raw fuel gas inlet, the same applies hereinafter), the catalyst packed bed 40% of the total length of the catalyst packed bed, 60% of the total length of the catalyst packed bed, 80% of the total length of the catalyst packed bed, and the reformer burner flue gas at 6 places at the reformed gas outlet of the catalyst packed bed The relationship between the temperature and the methane conversion rate of the reformer 8 is shown.

FIG. 6 shows that the methane conversion rate decreased and
It can be seen that the reformer burner flue gas temperature changes.

Accordingly, the temperature of the reformer burner flue gas is detected by the reformer burner flue gas temperature measurement temperature sensor 10, and the reformer burner flue gas temperature and the methane conversion rate of the reformer 8 shown in FIG. Is obtained as collation data to determine the methane conversion rate of the reformer 8 or the amount of deterioration of the reforming catalyst converted from the methane conversion rate using FIG. The deterioration state of the reforming section 48 of the reformer 8 can be diagnosed from the increase in the deterioration amount, and the obtained methane conversion rate or the conversion rate of the reforming catalyst converted from the methane conversion rate using the relationship shown in FIG. From the relationship between the amount of deterioration and the power generation time, the rate of decrease in the methane conversion rate or the rate of deterioration of the reforming catalyst is determined, and there is a period until the lower limit of the methane conversion rate does not adversely affect the power generation of the fuel cell It can determine the replacement timing of the reforming catalyst by calculating the period up to the upper limit of the amount of degradation of the reforming catalyst.

Incidentally, two or more temperature sensors 10 for measuring the temperature of the combustion exhaust gas of the reformer burner may be provided, and the average value of the detected temperatures may be used as the temperature of the combustion exhaust gas of the reformer burner.

FIG. 7 further shows a 200 kW phosphoric acid type fuel cell power generator using city gas as fuel.
4 shows the relationship between the reformer burner flue gas reformer outlet temperature and the methane conversion rate of the reformer 8 when power is generated at the W rated output.

From FIG. 7, it can be seen that as the methane conversion rate decreases,
It can be seen that the outlet temperature of the reformer burner flue gas reformer rises.

Therefore, by installing the temperature sensor 47 for measuring the outlet temperature of the reformer burner flue gas reformer, the outlet temperature of the reformer burner flue gas reformer is detected, and the reformer burner shown in FIG. 7 is detected. The methane conversion rate of the reforming apparatus 8 or the conversion rate of the reforming catalyst converted from the methane conversion rate using FIG. 10 by collating the relationship between the exhaust gas reformer outlet temperature and the methane conversion rate of the reforming apparatus 8 as collation data. When the deterioration amount is obtained, it is possible to diagnose the deterioration state of the reforming unit 48 of the reformer 8 from the decrease in the methane conversion rate or the increase in the deterioration amount of the reforming catalyst, and obtain the obtained methane conversion rate or methane conversion rate. From the relationship between the amount of deterioration of the reforming catalyst and the power generation time converted using the relationship shown in FIG. 10, the rate of decrease in the methane conversion rate or the rate of deterioration of the reforming catalyst is determined, which has a negative effect on the power generation of the fuel cell. Can determine the replacement timing of the reforming catalyst by calculating the time to reach the lower limit value of the methane conversion rate that does not adversely or period up to the upper limit of the amount of degradation of the reforming catalyst.

Incidentally, two or more temperature sensors 47 for measuring the outlet temperature of the reformer burner flue gas reformer outlet temperature may be provided, and the average value of the detected temperatures may be used as the outlet temperature of the reformer burner flue gas reformer.

FIG. 8 shows a raw fuel gas inlet of the catalyst packed bed of the reformer 8 when a 200 kW phosphoric acid type fuel cell power generator is used to generate power at a rated output of 200 kW using city gas as fuel. 20% of the total length of the catalyst packed bed (converted from the raw fuel gas inlet, the same applies hereinafter), 40% of the total length of the catalyst packed bed, 60% of the total length of the catalyst packed bed, The relationship between the methane conversion rate of the reformer 8 and the temperature of the reformed gas at the 80% position and at the six reformed gas outlets of the catalyst packed bed is shown.

FIG. 8 shows that the methane conversion rate decreased and
It can be seen that the reformed gas temperature changes.

Therefore, the temperature sensor 6 for measuring the reformed gas temperature
The temperature of the reformed gas is detected at 6 and the relationship between the reformed gas temperature and the methane conversion rate of the reformer 8 shown in FIG. When the amount of deterioration of the reforming catalyst converted from the methane conversion rate is obtained, the deterioration state of the reforming unit 48 of the reforming device 8 can be diagnosed from the decrease in the methane conversion rate or the increase in the deterioration amount of the reforming catalyst. Based on the obtained methane conversion rate or the conversion rate of methane converted from the methane conversion rate using the relationship shown in FIG. 10 and the power generation time, the rate of decrease in the methane conversion rate or the rate of deterioration of the reforming catalyst is determined. And calculate the period up to the lower limit of the methane conversion rate, which does not adversely affect the power generation of the fuel cell, or the period up to the upper limit of the amount of deterioration of the reforming catalyst. Determining replacement time It can be.

The temperature sensor 66 for measuring the temperature of the reformed gas.
May be installed, and the average value of the detected temperatures may be used as the reformed gas temperature.

When two or more reforming tubes are provided in the reformer and there are two or more catalyst packed beds, a temperature sensor 66 for measuring the temperature of the reformed gas is provided for each catalyst packed bed. Thus, the temperature of the reformed gas is detected, and the relationship between the reformed gas temperature and the methane conversion rate of the reformer 8 shown in FIG. When the amount of deterioration of the reforming catalyst converted from the methane conversion rate is calculated using, the deterioration state of the reforming catalyst for each reforming pipe can be diagnosed from the decrease in the methane conversion rate or the increase in the deterioration amount of the reforming catalyst. From the relationship between the obtained methane conversion rate or the conversion amount of the methane converted from the methane conversion rate using the relationship shown in FIG. 10 and the power generation time, the reduction rate of the methane conversion rate or the degradation rate of the reforming catalyst For each reforming tube By calculating the period up to the lower limit of the methane conversion rate that does not adversely affect power generation or the period up to the upper limit of the amount of deterioration of the reforming catalyst, the amount of the reforming catalyst in each reforming tube can be calculated. The replacement time can be determined.

FIG. 9 shows a 200 kW phosphoric acid-type fuel cell power generator using city gas as fuel.
4 shows the relationship between the outlet temperature of the reformed gas reformer and the methane conversion rate of the reformer 8 when power is generated at the W rated output.

FIG. 9 shows that the methane conversion rate decreased and
It can be seen that the outlet temperature of the reformed gas reformer rises.

Therefore, the outlet temperature of the reformed gas reformer is detected by the temperature sensor 51 for measuring the outlet temperature of the reformed gas reformer,
The relationship between the reformed gas reformer outlet temperature and the methane conversion rate of the reformer 8 shown in FIG. 9 is collated as collation data to obtain the methane conversion rate of the reformer 8 or the methane conversion rate using FIG. By obtaining the converted amount of the deterioration of the reforming catalyst, it is possible to diagnose the deterioration state of the reforming section 48 of the reformer 8 from the decrease in the methane conversion rate or the increase in the amount of deterioration of the reforming catalyst. The rate of decrease in the methane conversion rate or the rate of deterioration of the reforming catalyst is obtained from the relationship between the amount of power generation and the amount of deterioration of the reforming catalyst converted from the conversion rate or methane conversion rate using the relationship shown in FIG. The period up to the lower limit of methane conversion that does not adversely affect
Alternatively, the replacement time of the reforming catalyst can be determined by calculating the period until the deterioration amount of the reforming catalyst reaches the upper limit value.

It is to be noted that two or more temperature sensors 51 for measuring the outlet temperature of the reformed gas reformer may be provided, and the average value of the detected temperatures may be used as the outlet temperature of the reformed gas reformer.

As described above, according to the fuel cell power generator of the present invention, the temperature sensor for measuring the temperature of the catalyst packed bed of the reformer, the temperature sensor for measuring the outer wall temperature of the reformer reforming pipe, and the burner of the reformer burner. Temperature sensor for measuring exhaust gas temperature, temperature sensor for measuring outlet temperature of reformer burner combustion exhaust gas reformer,
At least one temperature sensor for measuring the temperature of the reformed gas and one or more temperature sensors for measuring the temperature at the outlet of the reformed gas reformer, and deterioration diagnosis means, life diagnosis means, and verification data selection means are installed. Temperature of the catalyst packed bed of reformer, temperature of outer wall of reformer reformer tube, temperature of flue gas of reformer burner, temperature of reformer burner flue gas reformer outlet, temperature of reformer gas,
One of the reformed gas reformer outlet temperatures, or one or more of them, is converted to a signal and transmitted to the deterioration diagnostic means, and the detected temperature is compared with the reforming device temperature measuring temperature sensor by the collation data selecting means. Predetermined reformer catalyst packed bed temperature, reformer reformer tube outer wall temperature, and reformer which are selected with respect to the reformer temperature which is detected and converted into a signal and transmitted to the deterioration diagnosis means. Relationship between any one or more of burner combustion exhaust gas temperature, reformer burner combustion exhaust gas reformer outlet temperature, reformed gas temperature, reformed gas reformer outlet temperature, and methane conversion rate of reformer The methane conversion rate of the reformer or the deterioration amount of the reforming catalyst converted from the methane conversion rate is obtained by comparing the comparison data with the comparison data of the deterioration diagnosis means, and from the decrease in the methane conversion rate or the increase in the deterioration amount of the reforming catalyst, Reform With diagnosing the state of deterioration of the location,
In the life diagnosing means, a temperature sensor for measuring the temperature of the reformer catalyst packed bed temperature, a temperature sensor for measuring the outer wall temperature of the reformer reforming pipe, a temperature sensor for measuring the temperature of the combustion exhaust gas of the reformer burner,
Detected by one or more of the temperature sensor for measuring the outlet temperature of the reformer burner flue gas reformer, the temperature sensor for measuring the temperature of the reformed gas, and the temperature sensor for measuring the outlet temperature of the reformed gas reformer Reformer catalyst packed bed temperature, reformer reformer tube outer wall temperature, reformer burner combustion exhaust gas temperature, reformer burner combustion exhaust gas reformer outlet temperature, reformed gas temperature, reformed gas reformer outlet temperature One or more than one of the detected temperatures (reformer catalyst packed bed temperature, reformer reformer outer tube temperature,
Any one or more of reformer burner flue gas temperature, reformer burner flue gas reformer outlet temperature, reformed gas temperature, reformed gas reformer outlet temperature) and methane of reformer The rate of decrease in the methane conversion rate or the rate of degradation of the reforming catalyst is determined from the relationship between the conversion rate of the methane converted from the methane conversion rate or the methane conversion rate and the power generation time. (1) Replacement of the reforming catalyst by calculating the period up to the lower limit of the methane conversion rate that does not adversely affect the power generation or the period up to the upper limit of the amount of deterioration of the reforming catalyst Since the timing is determined, it is not necessary to perform a time-consuming analysis operation of the reformed gas using an expensive gas analyzer such as a gas chromatograph for diagnosing the deterioration state of the reformer, and (2)
Diagnosis of the deterioration state of the reformer can be performed instantaneously and continuously on the spot. (3) Since the deterioration state of the reforming catalyst can be always grasped and the time for replacing the reforming catalyst can be known in advance, the reforming can be performed. There is an effect that the reforming catalyst can be replaced before the performance of the apparatus deteriorates.

[0115]

Therefore, as described above, according to the present invention, it takes a long time to sample and analyze the reformed gas, and it is impossible to diagnose deterioration of the reformer instantaneously.
In addition, an expensive gas analyzer is required for the deterioration diagnosis of the reformer, and if the deterioration diagnosis of the reformer is to be continuously performed on the spot, a dedicated gas analyzer is required for the fuel cell power generator. It is necessary, or it is necessary to take the sampling gas to the place where the gas analyzer is located. A fuel cell power generator capable of continuously performing deterioration diagnosis of a reformer and determining a time for replacing a reforming catalyst, a deterioration diagnosis method for the reformer, and a program for executing the method are recorded. A recording medium can be provided.

[Brief description of the drawings]

FIG. 1 is a connection diagram showing a configuration of a fuel cell power generator according to one embodiment of the present invention.

FIG. 2 is a connection diagram showing a configuration of a conventional fuel cell power generator.

FIG. 3 is an enlarged view of a reformer illustrating details of a fuel cell power generator according to the present invention.

FIG. 4 is a diagram showing reforming at each position in the catalyst packed bed of the reformer 8 when a 200 kW phosphoric acid fuel cell power generator is used to generate power at a rated output of 200 kW using city gas as fuel. FIG. 4 is a diagram showing a relationship between a temperature of a catalyst packed bed of a reformer and a methane conversion rate of a reformer.

FIG. 5 is a diagram showing reforming at each position in a catalyst packed bed of a reformer 8 when a 200 kW phosphoric acid-type fuel cell power generator is used to generate power at a rated output of 200 kW using city gas as fuel. FIG. 3 is a diagram showing a relationship between the outer wall temperature of the reformer and the methane conversion rate of the reformer.

FIG. 6 is a diagram showing a modification at each position in the catalyst packed bed of the reformer 8 when a 200 kW phosphoric acid type fuel cell power generator is used to generate power at a rated output of 200 kW using city gas as fuel. Reformer 8
It is a figure which shows the relationship of the methane conversion of this.

FIG. 7 is a diagram showing a reformer burner combustion exhaust gas reformer outlet temperature and reformer when a 200 kW phosphoric acid fuel cell power generator is used to generate power at a rated output of 200 kW using city gas as fuel. FIG. 4 is a diagram showing a relationship between methane conversion rates of a device 8;

FIG. 8 is a diagram showing a reform at each position in the catalyst packed bed of the reformer 8 when a 200 kW phosphoric acid fuel cell power generator is used to generate power at a rated output of 200 kW using city gas as fuel. FIG. 3 is a diagram showing a relationship between a raw gas temperature and a methane conversion rate of a reformer 8.

FIG. 9 is a graph showing the outlet temperature of the reformed gas reformer and the temperature of the reformer 8 when the 200 kW phosphoric acid fuel cell power generator is used to generate power at a rated output of 200 kW using city gas as fuel. It is a figure which shows the relationship of a methane conversion.

FIG. 10 is a diagram showing the methane conversion rate of the reformer 8 and the methane conversion rate of the reformer 8 when a 200 kW phosphoric acid fuel cell power generator is used to generate power at a rated output of 200 kW using city gas as fuel. It is a figure which shows the relationship of the deterioration amount of a reforming catalyst.

FIG. 11 is a flowchart illustrating a deterioration diagnosis method for explaining the operation of the fuel cell power generator according to the present embodiment, and a program recorded on a recording medium for executing the method.

[Explanation of symbols]

1. Raw fuel gas 2. 2. Reformed gas Shut-off valve 4. City gas 5. 5. Deterioration diagnosis means 6. Temperature sensor for measuring the temperature of the packed bed of the reformer catalyst 7. Desulfurization device Reformer 9. Reformer burner 10. 10. Temperature sensor for measuring combustion exhaust gas temperature of reformer burner Shift converter 12. Combustion air 13. Fuel electrode exhaust gas 14. 14. Reactor burner combustion exhaust gas Air blower 16. Air for power generation 17. Outside air 18. Fuel electrode 19. Electrolyte 20. Oxidizer electrode 21. Cell stack 22. Voltage sensor 23. Current sensor 24. Conversion device 25. Load 26. Battery cooling water 27. Steam separator 28. Steam-water separator heater 29. Catalyst packed layer 30. Flow control valve 31. Steam for reforming 32. Temperature sensor for measuring outer wall temperature of reformer reformer tube 33. Evaporator 34. Steam for exhaust heat recovery 35. Waste heat utilization system 36. Refrigerant 37. Oxidizer exhaust gas 38. Condenser 39. Exhaust gas 40. Condensed water 41. Temperature sensor for measuring reformer temperature 42. Reforming tube 43. Makeup water pump 44. Makeup water 45. Flow control valve 46. Flow control valve 47. Temperature sensor for measuring outlet temperature of reformer burner flue gas reformer outlet 48. Reforming unit 49. Pressure sensor 50. Fuel cell output 51. Temperature sensor for measuring outlet temperature of reformed gas reformer 52. Flow control valve 53. Ejector 54. Flow control valve 55. Liquid level sensor 56. Pump 57. Shut-off valve 58. Condensed water 59. Start-up burner 60. Shut-off valve 61. Burner air for starting reformer 62. Shut-off valve 63. Cooler 64. Temperature sensor 65. Shut-off valve 66. Temperature sensor for measuring reformed gas temperature 67. Verification data selection means 68. Lifetime diagnosis means

Claims (30)

[Claims] 1. A reformer having a reforming tube filled with a reforming catalyst for producing hydrogen by reacting fuel and steam, and generating hydrogen by reacting the hydrogen produced by the reformer with oxygen. A fuel cell power generator having a fuel electrode sandwiching an electrolyte for sandwiching and a cell stack in which cells composed of an oxidizer electrode are stacked, wherein a reformer catalyst-packed layer for measuring the temperature of the reformer catalyst-packed layer of the reformer is provided. A temperature sensor for measuring temperature, a temperature detection signal from the temperature sensor for measuring the temperature of the packed bed of the reformer catalyst, and the temperature of the packed bed of the reformer catalyst detected by the temperature sensor for measuring the packed bed temperature of the reformer. Degradation diagnosis means for diagnosing the degradation state of the reformer by collating the predetermined value with collation data of the relationship between the reformer catalyst packed bed temperature and the methane conversion rate of the reformer. Fuel cell power generation apparatus characterized by. 2. A reforming device temperature measuring temperature sensor for measuring the temperature of the reforming device, and a temperature detecting signal from the reforming device temperature measuring temperature sensor, the reforming device temperature measuring temperature sensor receiving the temperature detection signal from the reforming device temperature measuring temperature sensor. And selecting one of the collation data of the relationship between the methane conversion rate of the reformer and a plurality of reformer catalyst packed bed temperatures predetermined by the reformer temperature detected by the The fuel cell power generator according to claim 1, further comprising: verification data selecting means for transmitting. 3. A reforming apparatus having a reforming tube filled with a reforming catalyst for producing hydrogen by reacting fuel with steam and generating hydrogen by reacting the hydrogen produced by the reforming apparatus with oxygen. Fuel cell power generator having a fuel cell and a cell stack in which cells composed of an oxidant electrode are stacked with an electrolyte sandwiched therebetween for reforming, wherein a temperature of a reforming tube outer wall of the reformer is measured. A temperature sensor for measuring temperature, and a temperature detection signal from the temperature sensor for measuring outer wall temperature of the reformer reforming tube, and the reformer reforming tube detected by the temperature sensor for measuring outer wall temperature of the reforming device reforming tube. Degradation diagnosis means for diagnosing the degradation state of the reformer by comparing the outer wall temperature with a predetermined comparison data of the relationship between the outer wall temperature of the reformer reforming tube and the methane conversion rate of the reformer. Having Fuel cell power generation system according to claim. 4. A reformer temperature measuring temperature sensor for measuring the temperature of the reformer, and a temperature sensor for receiving a temperature detection signal from the reformer temperature measuring temperature sensor. The degradation diagnostic means by selecting one of a plurality of collation data of the relationship between the outer wall temperature of the reformer reforming pipe and the methane conversion rate of the reformer determined in advance by the reformer temperature detected by 4. The fuel cell power generator according to claim 3, further comprising: verification data selecting means for transmitting the data to the power generation apparatus. 5. A reformer having a reforming tube filled with a reforming catalyst for producing hydrogen by reacting fuel and steam, and generating electricity by reacting the hydrogen produced by the reformer with oxygen. Cell fuel cell power generator having a fuel electrode sandwiched with electrolytes and a cell stack formed by laminating cells composed of oxidizer electrodes, wherein the temperature of the burner combustion exhaust gas of the reformer is measured. A temperature sensor for detecting the temperature of the reformer burner flue gas temperature measurement temperature sensor, and predetermining the reformer burner flue gas temperature detected by the reformer burner flue gas temperature measurement temperature sensor. The deterioration state of the reformer is diagnosed by comparing the temperature of the reformer burner flue gas with the comparison data of the relationship between the methane conversion rate of the reformer and the reference data. A fuel cell power generator, comprising: 6. A reformer temperature measuring temperature sensor for measuring the temperature of the reformer, and a temperature sensor for receiving a temperature detection signal from the reformer temperature measuring temperature sensor. A plurality of reformer burner combustion exhaust gas temperatures determined in advance by the reformer temperature detected by the method and one of collation data of the relationship between the methane conversion rate of the reformer is selected, and the deterioration diagnostic means is selected. The fuel cell power generator according to claim 5, further comprising: verification data selecting means for transmitting. 7. A reformer having a reforming tube filled with a reforming catalyst for reacting fuel with steam to produce hydrogen, and generating hydrogen by reacting the hydrogen produced by the reformer with oxygen. Fuel cell power generator having a fuel electrode sandwiched with electrolytes and a cell stack in which cells composed of oxidizer electrodes are stacked, wherein a reformer burner for measuring a reformer outlet temperature of a burner combustion exhaust gas of the reformer is provided. A temperature sensor for measuring the outlet temperature of the flue gas reformer; and a temperature detection signal from the temperature sensor for measuring the outlet temperature of the flue gas reformer of the reformer. The reformer burner flue gas reformer outlet temperature detected by the temperature sensor for the reformer burner flue gas reformer outlet temperature and the metamer of the reformer are determined in advance. And a deterioration diagnosing means for diagnosing the deterioration state of the reformer by comparing the data with the comparison data of the conversion ratio. 8. A reformer temperature measuring temperature sensor for measuring the temperature of the reformer, and a temperature sensor for receiving the temperature detection signal from the reformer temperature measuring temperature sensor. A plurality of reformer burner combustion exhaust gas reformer exit temperatures determined in advance by the reformer temperature detected by the reformer temperature and methane conversion rate of the reformer. The fuel cell power generator according to claim 7, further comprising: verification data selection means for transmitting to the diagnosis means. 9. A reformer having a reforming tube filled with a reforming catalyst for producing hydrogen by reacting fuel with steam and generating hydrogen by reacting the hydrogen produced by the reformer with oxygen. A fuel cell power generator having a fuel electrode having an electrolyte sandwiched between the fuel electrode and a cell stack having a stack of oxidizer electrodes, a temperature sensor for measuring the temperature of the reformed gas, A relationship between a predetermined reformed gas temperature and a methane conversion rate of the reformer, wherein the temperature of the reformed gas detected by the temperature sensor for measuring reformed gas temperature is received from the temperature sensor for measuring gas temperature. And a deterioration diagnosing means for diagnosing the deterioration state of the reformer by comparing with the comparison data of (1). 10. A reformer temperature measuring temperature sensor for measuring the temperature of the reformer, and a temperature sensor for receiving a temperature detection signal from the reformer temperature measuring temperature sensor. A collation for selecting one of collation data of a relationship between a plurality of reformed gas temperatures determined in advance by the reformer temperature detected and a methane conversion rate of the reformer and transmitting the selected data to the deterioration diagnosis means. 10. The fuel cell power generator according to claim 9, comprising: data selection means. 11. A reformer having a reforming tube filled with a reforming catalyst for producing hydrogen by reacting fuel and steam, and generating hydrogen by reacting the hydrogen produced by the reformer with oxygen. Fuel cell power generator having a fuel electrode sandwiched with an electrolyte and a cell stack in which cells composed of an oxidant electrode are stacked for measuring the outlet temperature of the reformed gas reformer for measuring the outlet temperature of the reformed gas reformer A temperature sensor, receives a temperature detection signal from the reformed gas reformer outlet temperature measuring temperature sensor, and detects the reformed gas reformer outlet temperature detected by the reformed gas reformer outlet temperature measuring temperature sensor. Degradation diagnosis means for diagnosing a degradation state of the reformer by collating with predetermined collation data of a relationship between a reformed gas reformer outlet temperature and a methane conversion rate of the reformer. Fuel cell power generation apparatus characterized by. 12. A temperature sensor for measuring the temperature of the reforming device for measuring the temperature of the reforming device, and a temperature sensor for measuring the temperature of the reforming device which receives a temperature detection signal from the temperature sensor for measuring the temperature of the reforming device. The degradation diagnostic means by selecting one of a plurality of collation data of the relationship between the reformer outlet temperature and the methane conversion rate of the reformer determined in advance by the reformer temperature detected by 12. The fuel cell power generator according to claim 11, further comprising: a collation data selecting unit that transmits the data to the power generation device. 13. A methane conversion rate or a deterioration amount of the reforming catalyst converted from the methane conversion rate is transmitted from the deterioration diagnosis means, and the methane conversion rate or the deterioration amount of the reforming catalyst converted from the methane conversion rate and the power generation time The rate of decrease in the methane conversion rate or the rate of deterioration of the reforming catalyst is calculated from the relationship, and the period until the lower limit of the methane conversion rate does not adversely affect the power generation of the fuel cell, or the deterioration of the reforming catalyst of the reforming catalyst The fuel cell power generator according to any one of claims 1 to 12, further comprising a life diagnosis unit that determines a replacement time of the reforming catalyst by calculating a period until the amount reaches the upper limit value. 14. A reforming apparatus having a reforming tube filled with a reforming catalyst for producing hydrogen by reacting fuel with steam and generating hydrogen 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 electrode sandwiched with an electrolyte and a cell stack formed by laminating cells composed of oxidizer electrodes for detecting a temperature of a catalyst packed layer of the reformer Step, the state of deterioration of the reformer by comparing the detected reformer catalyst packed bed temperature with collation data of a predetermined relationship between the reformer catalyst packed bed temperature and the methane conversion rate of the reformer. Diagnosing the deterioration of the reformer of the fuel cell power generator, comprising the steps of: 15. A step of detecting the temperature of the reformer, and collating a relationship between a plurality of reformer catalyst packed bed temperatures determined in advance by the detected reformer temperature 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 14, comprising: selecting one of the data. 16. A reformer having a reforming tube filled with a reforming catalyst for reacting fuel with steam to produce hydrogen, 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 generator having a fuel electrode sandwiched with an electrolyte and a cell stack formed by stacking cells composed of oxidizer electrodes for detecting a temperature of an outer wall of a reformer tube of the reformer. Step, by comparing the detected reformer reforming tube outer wall temperature with predetermined collation data of the relationship between the reformer reforming tube outer wall temperature and the methane conversion rate of the reformer, Diagnosing a deterioration state of the fuel cell power generator. 17. A step of detecting a temperature of the reformer, and a relation between a plurality of reformer reformer outer wall temperatures predetermined by the detected reformer temperature 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 16, comprising: selecting one of the collation data. 18. A reformer having a reformer tube filled with a reforming catalyst for producing hydrogen by reacting fuel and 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 electrode sandwiched with an electrolyte and a cell stack in which cells composed of oxidizer electrodes are stacked for detecting a burner combustion exhaust gas temperature of the reformer By comparing the detected reformer burner flue gas temperature with predetermined collation data of the relationship between the reformer burner flue gas temperature and the methane conversion rate of the reformer, the deterioration state of the reformer is determined. Diagnosing a deterioration of the reformer of the fuel cell power generator, comprising the steps of: 19. A step of detecting a temperature of the reformer, and collating a relationship between a plurality of reformer burner combustion exhaust gas temperatures determined in advance by the detected reformer temperature and a methane conversion rate of the reformer. 19. The method for diagnosing deterioration of a reformer of a fuel cell power generator according to claim 18, comprising: selecting one of the data. 20. A reformer having a reforming tube filled with a reforming catalyst for producing hydrogen by reacting fuel and 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 generator having a fuel electrode sandwiched with an electrolyte and a cell stack formed by laminating cells comprising oxidizer electrodes for the burner combustion exhaust gas reformer outlet temperature of the reformer Detecting the temperature of the reformer burner combustion exhaust gas reformer outlet temperature and the collation data of the relationship between the predetermined reformer burner combustion exhaust gas reformer outlet temperature and the methane conversion rate of the reformer. Diagnosing a deterioration state of the reformer by collating; a method of diagnosing deterioration of the reformer of the fuel cell power generation apparatus. 21. A step of detecting a temperature of the reformer, a plurality of reformer burner combustion exhaust gas reformer outlet temperatures predetermined by the detected reformer temperature, and a methane conversion rate of the reformer. 21. The method for diagnosing deterioration of a reformer of a fuel cell power generator according to claim 20, further comprising the step of selecting one from the collation data of the relationship of. 22. A reforming apparatus having a reforming tube filled with a reforming catalyst for producing hydrogen by reacting fuel and steam, and generating electricity by reacting the hydrogen produced by the reforming apparatus with oxygen. Detecting a reformed gas temperature in a method of diagnosing deterioration of a reformer of a fuel cell power generation device having a cell stack in which a cell composed of a fuel electrode and an oxidizer electrode sandwiched by an electrolyte is stacked, Diagnosing the deterioration state of the reformer by comparing the gas temperature with collation data of a predetermined relationship between the reformed gas temperature and the methane conversion rate of the reformer. A method for diagnosing deterioration of a reformer of a fuel cell power generator. 23. A step of detecting a temperature of the reformer; and a plurality of collation data of a relationship between a plurality of reformed gas temperatures predetermined by the detected reformer temperature 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 22, comprising the step of selecting one. 24. A reforming apparatus having a reforming tube filled with a reforming catalyst for producing hydrogen by reacting fuel and steam, and generating electricity by reacting the hydrogen produced by the reforming apparatus with oxygen. Detecting a reformed gas reformer outlet temperature in a method of diagnosing deterioration of a reformer of a fuel cell power generation device having a fuel cell sandwiching an electrolyte and a cell stack in which cells composed of an oxidizer electrode are stacked. Deterioration state of the reformer by comparing the detected reformed gas reformer outlet temperature with predetermined collation data of the relationship between the reformed gas reformer outlet temperature and the methane conversion rate of the reformer. Diagnosing the deterioration of the reformer of the fuel thunder pond power generator. 25. A step of detecting the reformer temperature, and collating a relationship between a plurality of reformed gas reformer outlet temperatures predetermined by the detected reformer temperature 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 24, comprising: selecting one from data. 26. A rate of decrease in the methane conversion rate or a rate of deterioration of the reforming catalyst is determined from the relationship between the methane conversion rate or the deterioration amount of the reforming catalyst converted from the methane conversion rate and the power generation time, and adversely affects the power generation of the fuel cell. Determining the replacement time of the reforming catalyst by calculating the period up to the lower limit value of the methane conversion rate that does not affect the amount or the period up to the upper limit value of the amount of deterioration of the reforming catalyst. Claim 1
4 to. 25. The method for diagnosing deterioration of a reformer of a fuel cell power generator according to any one of 25. 27. A reformer having a reformer tube filled with a reforming catalyst for producing hydrogen by reacting fuel with steam and generating hydrogen by reacting the hydrogen produced by the reformer with oxygen. A method for diagnosing deterioration of a reforming device of a fuel cell power generation device having a fuel electrode sandwiched with an electrolyte and a cell stack formed by laminating cells composed of oxidizer electrodes, comprising: Temperature sensor for measuring the temperature of the reformer catalyst packed bed temperature, temperature sensor for measuring the temperature of the outer wall of the reformer reforming tube, temperature sensor for measuring the temperature of the combustion exhaust gas of the reformer burner, and the outlet temperature of the reformer burner combustion exhaust gas. Temperature sensor for measurement, temperature sensor for measuring reformed gas temperature, temperature sensor for measuring outlet temperature of reformed gas reformer, temperature of packed bed of reformer catalyst, outer wall temperature of reformer reformer tube, burner of reformer burner Exhaust gas temperature Detecting any one or more of the reformer burner combustion exhaust gas reformer outlet temperature, the reformed gas temperature, and the reformed gas reformer outlet temperature; and detecting the temperature from each of the temperature sensors. Transmitting a signal to a deterioration diagnosis unit; and a deterioration diagnosis unit that receives a temperature detection signal from each of the temperature sensors, in which the reformer temperature detected by the temperature sensor for measuring reformer temperature is converted into a signal and transmitted. As the comparison data of the relationship between the predetermined detected temperature and the methane conversion rate of the reformer, which is selected and transmitted by the collation data selection means corresponding to the reformer temperature, the reformer catalyst packed bed temperature and The collation data of the relationship between the methane conversion rate of the reformer, the collation data of the relationship between the outer wall temperature of the reformer reforming pipe and the methane conversion rate of the reformer, the reformer burner combustion exhaust gas temperature and the Meta Verification data on the relationship between the conversion rates of the reformer, verification data on the relationship between the outlet temperature of the reformer burner flue gas reformer and the methane conversion rate of the reformer, and the relation between the reformed gas temperature and the methane conversion rate of the reformer. Collation data, a step of collating with one or more of collation data of a relationship between a reformed gas reformer outlet temperature and a methane conversion rate of the reformer, based on these collation results Calculating the methane conversion rate of the reformer or the amount of deterioration of the reforming catalyst converted from the methane conversion rate, and determining the deterioration rate of the reformer from the decrease in the methane conversion rate of the reformer or the increase in the deterioration amount of the reforming catalyst. Diagnosing the deterioration state of the reforming unit. 28. The life diagnosis means, wherein the reformer catalyst packed bed temperature detected by each temperature sensor, the reformer reformer tube outer wall temperature, the reformer burner combustion exhaust gas temperature, the reformer burner combustion exhaust gas reformer. Outlet temperature, reformed gas temperature, one or more of the reformed gas reformer outlet temperature,
As the predetermined detection temperatures selected and transmitted by the collation data selecting means in the deterioration diagnosis means, the reformer catalyst packed bed temperature, the reformer reforming tube outer wall temperature, the reformer burner combustion exhaust gas temperature, the reforming Apparatus burner flue gas reformer outlet temperature, reformed gas temperature, any one or more of reformed gas reformer outlet temperature and collation with collation data of the relationship of methane conversion rate of the reformer The rate of decrease in methane conversion rate or the rate of deterioration of the reforming catalyst is determined from the relationship between the methane conversion rate or the conversion amount of the reforming catalyst converted from the methane conversion rate and the power generation time, and methane that does not adversely affect power generation is determined. Calculating a period until reaching the lower limit of the conversion rate or a period until reaching the upper limit of the amount of deterioration of the reforming catalyst; 28. The fuel cell according to claim 27, further comprising: determining a replacement time of the reforming catalyst based on a period until the fuel cell reaches the upper limit of the amount of deterioration of the reforming catalyst. A method for diagnosing deterioration of a reformer of a battery power generator. 29. A reforming apparatus having a reforming tube filled with a reforming catalyst for producing hydrogen by reacting fuel with steam and generating hydrogen by reacting the hydrogen produced by the reforming apparatus with oxygen. A storage medium storing a program for executing a method for diagnosing deterioration of a reformer of a fuel cell power generation apparatus having a fuel electrode sandwiched with an electrolyte and a cell stack formed by laminating cells composed of oxidizer electrodes for the purpose of the present invention. A temperature sensor for measuring the temperature of one or more reformer catalyst packed beds provided in the reforming section of the reformer, a temperature sensor for measuring the temperature of the outer wall of the reformer reforming tube, and a temperature sensor for measuring the temperature of the combustion exhaust gas of the reformer burner. Temperature sensor, reformer burner combustion exhaust gas reformer outlet temperature measurement temperature sensor, reformed gas temperature measurement temperature sensor, reformed gas reformer outlet temperature measurement temperature sensor, reformer catalyst packed bed temperature, Reform Any one or more of the following: the outer wall temperature of the reforming pipe, the reformer burner combustion exhaust gas temperature, the reformer burner combustion exhaust gas reformer outlet temperature, the reformed gas temperature, and the reformed gas reformer outlet temperature. Detecting the temperature detection signal from each of the temperature sensors to the deterioration diagnosis unit; and receiving the temperature detection signal from each of the temperature sensors in the deterioration diagnosis unit. The predetermined detection temperature selected and transmitted by the collation data selection means corresponding to the reformer temperature transmitted by converting the reformer temperature detected in the signal and the methane conversion rate of the reformer As the collation data of the relationship, collation data of the relationship between the reformer catalyst packed bed temperature and the methane conversion rate of the reformer, collation data of the relationship between the reformer reforming tube outer wall temperature and the methane conversion rate of the reformer , Data of the relationship between the reformer burner flue gas temperature and the methane conversion rate of the reformer, verification data of the relationship between the reformer burner flue gas reformer outlet temperature and the methane conversion rate of the reformer, reformed gas Matching data of the relationship between the temperature and the methane conversion rate of the reformer, any one of the comparison data of the relationship between the reformed gas reformer outlet temperature and the methane conversion rate of the reformer, or one or more. Collating, based on these collation results, determining the methane conversion rate of the reformer or the amount of deterioration of the reforming catalyst converted from the methane conversion rate, and reducing or lowering the methane conversion rate of the reformer. Diagnosing the deterioration state of the reforming section of the reformer from the increase in the amount of catalyst deterioration. Recording medium on which beam has been recorded. 30. A life diagnosing means, wherein a reformer catalyst packed bed temperature detected by each temperature sensor, a reformer reformer tube outer wall temperature, a reformer burner combustion exhaust gas temperature, a reformer burner combustion exhaust gas reformer. Outlet temperature, reformed gas temperature, one or more of the reformed gas reformer outlet temperature,
As the predetermined detection temperatures selected and transmitted by the collation data selecting means in the deterioration diagnosis means, the reformer catalyst packed bed temperature, the reformer reforming tube outer wall temperature, the reformer burner combustion exhaust gas temperature, the reforming Apparatus burner flue gas reformer outlet temperature, reformed gas temperature, any one or more of reformed gas reformer outlet temperature and collation with collation data of the relationship of methane conversion rate of the reformer The rate of decrease in methane conversion rate or the rate of deterioration of the reforming catalyst is determined from the relationship between the methane conversion rate or the conversion amount of the reforming catalyst converted from the methane conversion rate and the power generation time, and methane that does not adversely affect power generation is determined. Calculating a period until reaching the lower limit of the conversion rate or a period until reaching the upper limit of the amount of deterioration of the reforming catalyst; 30. The fuel cell according to claim 29, further comprising: determining a time to replace the reforming catalyst based on a period until the reforming catalyst reaches an upper limit of the amount of deterioration of the reforming catalyst. A recording medium on which a program for executing a method for diagnosing deterioration of a reformer of a battery power generator is recorded.