JP2015140284A - Method for starting operation of hydrogen-containing gas generation apparatus, and hydrogen-containing gas generation apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for starting operation of a hydrogen-containing gas generation apparatus, in which damage of a CO conversion catalyst due to condensation of steam in a converter can be suppressed.SOLUTION: When a hydrogen-containing gas generation part P, which is stopped in such a state that each of a reforming treatment chamber 11 and a converter 3 is filled with raw fuel, is started, such combustion start treatment for starting combustion of a reforming burner 1 is conducted. Then, when the temperature is raised to steam supply start temperature, such steam replacement treatment where the steam from a steam generation part S is supplied to the reforming treatment chamber 11 is conducted . Afterward, when the temperature of the reforming treatment chamber 11 is raised to reforming treatment start temperature, such raw fuel supply treatment where the raw fuel of a steam-mixed state is supplied to the reforming treatment chamber 11 is conducted. When the temperature of the combustion exhaust gas after passed through the steam generation part S is equal to or lower than the dew point of the steam filled in the converter 3 by the steam replacement treatment, a cancellation means K for cancelling such a flow that the combustion exhaust gas passes through a conversion catalyst cooler 4 at the temperature equal to or lower than the dew point of steam is switched over to an operated state.

Description

The present invention provides a reforming treatment chamber for producing a reforming treatment gas mainly containing hydrogen gas by reforming a hydrocarbon-based raw fuel supplied in a mixed state of steam in a heating state by a reforming burner, A steam generation unit that generates steam mixed with raw fuel supplied to the reforming treatment chamber by heating water with combustion exhaust gas of the reforming burner, and carbon monoxide contained in the reforming treatment gas from the reforming treatment chamber And a hydrogen-containing gas generation unit comprising a conversion catalyst cooler that cools the CO conversion catalyst by the flow of combustion exhaust gas after flowing through the water vapor generation unit. Is provided,
When starting the hydrogen-containing gas generation unit that is stopped in a state in which the reforming chamber and the transformer are filled with raw fuel, a combustion start process for starting combustion of the reforming burner is performed, Thereafter, when the temperature of the reforming chamber is raised to a steam supply start temperature that can prevent thermal decomposition of the raw fuel and condensation of water vapor, the steam from the steam generator is supplied to the reforming chamber. Then, a steam replacement process is performed to replace the raw fuel charged in the reforming process chamber and the transformer with steam, and then the temperature of the reforming process chamber rises to a reforming process start temperature. Furthermore, the present invention relates to a start-up operation method for a hydrogen-containing gas generation device that performs raw fuel supply processing for supplying raw fuel to the reforming chamber in a mixed state of steam, and a hydrogen-containing gas generation device.

  The hydrogen-containing gas generation device generates a reformed gas (hydrogen-containing gas) in a hydrogen-containing gas generation unit, and uses the generated reformed gas (hydrogen-containing gas) as a fuel gas for power generation, for example, in a fuel cell. Will be supplied.

The combustion exhaust gas of the reforming burner that heats the reforming treatment chamber of the hydrogen-containing gas generation section flows to the steam generation section and is used for generation of steam, and then flows through the shift catalyst cooler to form the CO of the shift converter. Used to cool the shift catalyst.
That is, since the shift treatment by the shift converter performs a shift reaction that is an exothermic reaction, the shift of the combustion exhaust gas after flowing through the steam generation section flows through the shift catalyst cooler, for example, The CO shift catalyst is cooled so as to be in the range of 200 to 400 ° C. (see, for example, Patent Document 1).

When stopping the operation of the hydrogen-containing gas generator, the reforming chamber or shifter of the hydrogen-containing gas generator is filled with raw fuel, and the reforming catalyst or shifter charged in the reforming chamber is charged. This suppresses a decrease in the activity of the CO conversion catalyst inserted.
For this reason, when starting the hydrogen-containing gas generation unit, first, after starting the combustion process, when the temperature of the reforming process chamber rises to the steam supply start temperature, the reforming process chamber and the transformer are filled. When the temperature of the reforming chamber is raised to the reforming start temperature, the raw fuel is modified in a steam mixed state. Start-up operation to start up the normal operation state of generating reformed gas (hydrogen-containing gas) while avoiding the inconvenience of thermal decomposition of the filled raw fuel by performing the raw fuel supply process to be supplied to the quality treatment chamber (For example, refer to Patent Document 2).

  Incidentally, although Patent Document 2 does not describe the shift catalyst cooler, when the start-up operation method described in Patent Document 2 is applied to the hydrogen gas generation device described in Patent Document 1, a hydrogen-containing gas is used. In the normal operation state of the generation unit, the conversion catalyst cooler that exhibits the action of cooling the CO conversion catalyst exhibits the heating action of raising the temperature of the CO conversion catalyst when starting the hydrogen-containing gas generation part. Become.

Japanese Patent No. 4063430 Japanese Patent No. 3995503

  The temperature of the combustion exhaust gas of the reforming burner exceeds 100 ° C. in a normal operation state such as a steady operation state in which the hydrogen-containing gas generation unit is in a steady operation even after flowing through the steam generation unit. However, immediately after starting the water vapor replacement process when starting the hydrogen-containing gas generation unit, in order to start generation of water vapor in the water vapor generation unit, supply of raw material water to the water vapor generation unit is started. Due to the fact that it is immediately after, a large amount of heat tends to be taken away in the steam generating section, and the temperature of the combustion exhaust gas after flowing through the steam generating section is the dew point of steam charged in the transformer ( 100 ° C.) or less.

  And, when the temperature of the combustion exhaust gas after flowing through the steam generating section becomes equal to or lower than the dew point (100 ° C.) of the steam charged in the transformer, the steam supplied into the transformer by the steam replacement process is condensed, If the condensed water is absorbed by the CO conversion catalyst and the condensed water absorbed by the CO conversion catalyst evaporates inside the CO conversion catalyst due to subsequent temperature rise, the CO conversion catalyst may be damaged, and an improvement is desired. It was a thing.

The present invention has been made in view of the above circumstances, and its purpose is to start up a hydrogen-containing gas generation device that can suppress damage to the CO shift catalyst caused by condensation of water vapor in the shift converter. Is to provide
Another object of the present invention is to provide a hydrogen-containing gas generation device that can suppress the breakage of the CO shift catalyst caused by condensation of water vapor in the shift converter.

The start-up operation method of the hydrogen-containing gas generation apparatus of the present invention is a reforming process in which a hydrocarbon-based raw fuel supplied in a mixed state of steam is reformed in a heated state by a reforming burner and mainly contains hydrogen gas. A reforming chamber for generating a processing gas, a steam generating unit for generating steam mixed with the raw fuel supplied to the reforming chamber by heating water with combustion exhaust gas of the reforming burner, from the reforming chamber A converter that converts carbon monoxide contained in the reformed gas into carbon dioxide using a CO conversion catalyst, and a conversion that cools the CO conversion catalyst by the flow of combustion exhaust gas after flowing through the steam generation unit A hydrogen-containing gas generation unit including a catalyst cooler is provided;
When starting the hydrogen-containing gas generation unit that is stopped in a state in which the reforming chamber and the transformer are filled with raw fuel, a combustion start process for starting combustion of the reforming burner is performed, Thereafter, when the temperature of the reforming chamber is raised to a steam supply start temperature that can prevent thermal decomposition of the raw fuel and condensation of water vapor, the steam from the steam generator is supplied to the reforming chamber. Then, a steam replacement process is performed to replace the raw fuel charged in the reforming process chamber and the transformer with steam, and then the temperature of the reforming process chamber rises to a reforming process start temperature. , A start-up operation method of a hydrogen-containing gas generation device that performs raw fuel supply processing for supplying raw fuel to the reforming treatment chamber in a mixed state of steam, the first characteristic configuration thereof is:
When the temperature of the combustion exhaust gas after flowing through the steam generation unit is equal to or lower than the dew point of the steam charged in the transformer in the steam replacement treatment, the combustion exhaust gas is cooled at a temperature equal to or lower than the dew point of the steam. A canceling means that operates to cancel the flow of the vessel is provided to be switchable between an operating state and a stopped state,
When the temperature of the combustion exhaust gas after flowing through the water vapor generating part is equal to or lower than the dew point of the water vapor charged in the transformer, the canceling means is switched to an operating state, and after flowing through the water vapor generating part When the temperature of the combustion exhaust gas is higher than the dew point of the water vapor charged in the transformer, the canceling means is switched to a stop state.

  That is, when the temperature of the combustion exhaust gas after flowing through the steam generation unit is equal to or lower than the dew point of the steam charged in the transformer by the steam replacement process, the canceling means is switched to the operating state, and the combustion exhaust gas is Flowing through the shift catalyst cooler at a temperature below the dew point is eliminated.

  In addition, when the temperature of the combustion exhaust gas after flowing through the steam generating unit is higher than the dew point of the steam charged in the transformer by the steam replacement process, the canceling means is switched to the stop state, and the steam generating unit passes through the steam generating unit. The flue gas after flowing flows through the shift catalyst cooler and exhibits an effect of raising the temperature of the CO shift catalyst of the shift converter.

  In this way, the combustion exhaust gas after flowing through the steam generating section is eliminated from flowing through the shift catalyst cooler at a temperature equal to or lower than the dew point of the steam charged in the shift converter by the steam replacement process. Since it is possible to avoid the condensation of water vapor in the reactor, it is possible to suppress the breakage of the CO shift catalyst caused by the condensation of water vapor in the transformer.

  In short, according to the first characteristic configuration of the start-up operation method of the hydrogen-containing gas generation device of the present invention, it is possible to suppress damage to the CO shift catalyst due to condensation of water vapor in the shift converter.

In addition to the first feature configuration described above, the second feature configuration of the start-up operation method of the hydrogen-containing gas generation device of the present invention includes:
The canceling means includes, as the working state, a bypass flow state in which the flue gas after flowing through the steam generation part bypassing the shift catalyst cooler is passed, and the shift catalyst cooler as the stop state. The flow path switching unit is switchable to a cooling fluid state in which the combustion exhaust gas after flowing through the water vapor generating unit is passed through.

  That is, when the temperature of the combustion exhaust gas after flowing through the steam generating section is equal to or lower than the dew point of the steam charged in the transformer by the steam replacement process, the flow path switching section constituting the eliminating means is The combustion exhaust gas flows through the shift catalyst cooler at a temperature lower than the dew point of the water vapor, instead of the bypass flow state in which the combustion exhaust gas after flowing through the steam generation section is bypassed. Will be.

  In addition, when the temperature of the combustion exhaust gas after flowing through the steam generating section is higher than the dew point of the steam charged in the transformer by the steam replacement process, the flow path switching section constituting the elimination means is the shift catalyst cooler. The combustion exhaust gas after flowing through the steam generating section is switched to the cooling flow state in which the combustion exhaust gas after flowing through the steam generating section is passed through The effect of raising the temperature of the CO conversion catalyst is exhibited.

  Thus, as a means for eliminating, a simple structure of providing a flow path switching unit that can be switched between a bypass flow state and a cooling flow state, avoiding the condensation of water vapor in the transformer, Damage to the CO conversion catalyst due to the condensation of water vapor can be suppressed.

  In short, according to the second characteristic configuration of the start-up operation method of the hydrogen-containing gas generation device of the present invention, in addition to the operational effects of the first characteristic configuration, the water vapor in the transformer is condensed with a simple configuration. The resulting damage to the CO shift catalyst can be suppressed.

In addition to the first feature configuration, the third feature configuration of the start-up operation method of the hydrogen-containing gas generation device of the present invention,
As the working state, the canceling means heats the combustion exhaust gas after flowing through the water vapor generating section to a temperature higher than the dew point of the water vapor charged in the transformer, and the stop state includes the water vapor. It is characterized in that it is a combustion exhaust gas heating means switchable to a heating stop state in which heating to the combustion exhaust gas after flowing through the generating section is stopped.

  That is, when the temperature of the combustion exhaust gas after flowing through the steam generation unit is equal to or lower than the dew point of the steam charged in the transformer by the steam replacement process, the combustion exhaust gas heating means constituting the elimination means The combustion exhaust gas after passing through may be changed to a heating state in which the combustion exhaust gas is heated to a temperature higher than the dew point of water vapor charged in the transformer, and the combustion exhaust gas may flow through the shift catalyst cooler at a temperature lower than the dew point of water vapor. Will be resolved.

  Further, when the temperature of the combustion exhaust gas after flowing through the steam generation unit is higher than the dew point of the steam charged in the transformer by the steam replacement process, the combustion exhaust gas heating means constituting the elimination means It is switched to a heating stop state in which heating to the combustion exhaust gas after flowing is stopped.

  That is, when the temperature of the combustion exhaust gas after flowing through the steam generating section is lower than or equal to the dew point of the steam filled in the transformer by the steam replacement process, and when it is higher than the dew point of the steam, the steam is generated. Steam in which the temperature of the combustion exhaust gas after flowing through the steam generation section is filled in the transformer by the steam replacement process while continuing the state in which the combustion exhaust gas after flowing through the section passes through the shift catalyst cooler When the temperature is below the dew point, the combustion exhaust gas heating means constituting the elimination means is changed to a heated state, thereby eliminating the fact that the combustion exhaust gas flows through the shift catalyst cooler at a temperature below the dew point of water vapor.

  Thus, when the temperature of the flue gas after flowing through the water vapor generating part is equal to or lower than the dew point of the water vapor filled in the transformer by the water vapor replacement process, the flue gas after flowing through the water vapor generating part is transformed. It is heated by the combustion exhaust gas heating means so that the temperature becomes higher than the dew point of the water vapor charged in the vessel and flows through the shift catalyst cooler. Even when the temperature is equal to or lower than the dew point of the water vapor filled in the transformer by the steam substitution treatment, the combustion exhaust gas after flowing through the steam generating section exerts the effect of raising the temperature of the CO conversion catalyst of the transformer. As a result, the CO conversion catalyst of the converter can be appropriately heated.

  In short, according to the third characteristic configuration of the start-up operation method of the hydrogen-containing gas generation apparatus of the present invention, in addition to the operational effect of the first characteristic configuration, in the form of appropriately raising the temperature of the CO shift catalyst of the shifter, Damage to the CO shift catalyst due to the condensation of water vapor in the shift converter can be suppressed.

In addition to any of the first to third characteristic configurations described above, the fourth characteristic configuration of the start-up operation method for the hydrogen-containing gas generation device of the present invention is as follows.
Combustion exhaust gas temperature measuring means for measuring the temperature of the combustion exhaust gas after flowing through the steam generation unit is provided,
Based on the measurement result of the combustion exhaust gas temperature measuring means, it is determined whether or not the temperature of the combustion exhaust gas after flowing through the steam generation unit is equal to or lower than the dew point of the steam charged in the transformer. And

  That is, based on the measurement result of the flue gas temperature measuring means for measuring the temperature of the flue gas after flowing through the water vapor generating part, the temperature of the flue gas after flowing through the water vapor generating part was filled in the transformer Since it is to determine whether the dew point is lower than the steam dew point, the temperature of the combustion exhaust gas after flowing through the steam generating section is lower than the dew point of the water vapor charged in the transformer, or the transformer is filled. It is possible to accurately determine whether the dew point of the water vapor is higher.

  Therefore, when the temperature of the combustion exhaust gas after flowing through the water vapor generating unit is below the dew point of the water vapor charged in the transformer, the canceling means is accurately switched to the operating state, and after the flow through the water vapor generating unit When the temperature of the combustion exhaust gas is higher than the dew point of the water vapor filled in the transformer, the elimination means can be switched to the stopped state accurately, and the temperature below the dew point of the water vapor filled in the transformer of the combustion exhaust gas. Thus, it is possible to accurately eliminate the flow of the shift catalyst cooler.

  In short, according to the fourth characteristic configuration of the start-up operation method of the hydrogen-containing gas generation device of the present invention, in addition to the operational effects of any of the first to third characteristic configurations, the dew point of the water vapor charged in the transformer It is possible to accurately eliminate the combustion exhaust gas having the following temperature flowing through the shift catalyst cooler.

In addition to any of the first to third characteristic configurations described above, the fifth characteristic configuration of the start-up operation method for the hydrogen-containing gas generation device of the present invention is as follows:
Temperature rise until the temperature of the flue gas after flowing through the water vapor generating part becomes higher than the dew point of the water vapor charged in the transformer in the water vapor replacement process after the combustion start process is executed Predetermined elapsed time for use,
Based on whether or not the elapsed time since the start of the combustion process exceeds the elapsed time for temperature increase, the temperature of the combustion exhaust gas after flowing through the water vapor generating part is charged into the transformer. It is characterized in that it is determined whether or not the dew point is lower than the water vapor.

That is, by conducting an experiment or the like in advance, the temperature of the combustion exhaust gas after flowing through the steam generation unit is higher than the dew point of the steam filled in the transformer in the steam replacement process after performing the combustion start process. The elapsed time for temperature rise until becomes is determined in advance.
Then, based on whether or not the elapsed time since the start of combustion processing exceeds the elapsed time for temperature increase, the temperature of the combustion exhaust gas after flowing through the water vapor generation unit is filled in the transformer. It is determined whether or not the dew point is lower than the water vapor.

  As described above, the steam generation unit is set based on whether or not the elapsed time for temperature increase is determined in advance by experiments or the like, and the elapsed time after the combustion start processing exceeds the elapsed time for temperature increase. Combustion that measures the temperature of the flue gas after flowing through the water vapor generating part because it determines whether the temperature of the flue gas after flowing is below the dew point of the water vapor filled in the transformer. Without installing the exhaust gas temperature measuring means, the elimination means can be switched between the operating state and the stopped state with a simple configuration.

  In short, according to the fifth characteristic configuration of the start-up operation method of the hydrogen-containing gas generation device of the present invention, in addition to the operational effects of any of the first to third characteristic configurations, the elimination means is operated with a simple configuration. It is possible to switch between a state and a stopped state.

The hydrogen-containing gas generation apparatus of the present invention generates a reformed gas containing hydrogen gas as a main component by reforming a hydrocarbon-based raw fuel supplied in a steam-mixed state while being heated by a reforming burner. A reforming process chamber, a steam generating unit that generates steam mixed with raw fuel supplied to the reforming process chamber by heating water with combustion exhaust gas of the reforming burner, and a reforming process gas from the reforming process chamber A conversion device that converts carbon monoxide contained in the carbon dioxide into carbon dioxide by a CO conversion catalyst, and a conversion catalyst cooler that cools the CO conversion catalyst by the flow of combustion exhaust gas after flowing through the water vapor generation section A hydrogen-containing gas generator is provided,
When starting the hydrogen-containing gas generation unit that is stopped in a state in which the reforming chamber and the transformer are filled with raw fuel, a combustion start process for starting combustion of the reforming burner is performed, Thereafter, when the temperature of the reforming chamber is raised to a steam supply start temperature that can prevent thermal decomposition of the raw fuel and condensation of water vapor, the steam from the steam generator is supplied to the reforming chamber. Then, a steam replacement process is performed to replace the raw fuel charged in the reforming process chamber and the transformer with steam, and then the temperature of the reforming process chamber rises to a reforming process start temperature. , A raw fuel supply process for supplying raw fuel to the reforming process chamber in a mixed state of steam,
Reforming temperature measuring means for measuring the temperature of the reforming treatment chamber is provided,
The operation control means for controlling the operation of the hydrogen-containing gas generating section executes the combustion start processing when an activation command is issued, and then, based on the measurement result of the reforming temperature measuring means, the steam replacement Configured to perform a process and the raw fuel supply process,
When the temperature of the combustion exhaust gas after flowing through the steam generation unit is equal to or lower than the dew point of the steam charged in the transformer in the steam replacement treatment, the combustion exhaust gas is cooled at a temperature equal to or lower than the dew point of the steam. The canceling means that operates to cancel the flow of the vessel is provided to be switchable between an operating state and a stopped state,
When the operation control means has a temperature of the combustion exhaust gas after flowing through the water vapor generating section is equal to or lower than a dew point of water vapor charged in the transformer, the canceling means is switched to an operating state, and the water vapor generation is performed. When the temperature of the combustion exhaust gas after flowing through the section is higher than the dew point of the water vapor charged in the transformer, the elimination means is configured to be switched to a stopped state.

  That is, the characteristic configuration of the hydrogen-containing gas generation device of the present invention includes the configuration for implementing the first characteristic configuration of the startup operation method of the hydrogen-containing gas generation device described above. The operation and effect similar to those described in the column of the first characteristic configuration of the apparatus start-up operation method will be exhibited, and in addition, the start-up operation of the hydrogen-containing gas generation unit is automatically performed by the control operation of the operation control means. Can be done.

In other words, when the start command is instructed, the operation control means executes the combustion start process, and then executes the steam replacement process and the raw fuel supply process based on the measurement result of the reforming temperature measuring means. .
In addition, when the operation control means has the temperature of the combustion exhaust gas after flowing through the steam generating section is equal to or lower than the dew point of the steam charged in the transformer, the canceling means is switched to the operating state and the steam generating section is passed through. When the temperature of the flue gas after flowing is higher than the dew point of the water vapor charged in the transformer, the canceling means is switched to the stop state.

  In this way, the combustion exhaust gas after flowing through the steam generating section is eliminated from flowing through the shift catalyst cooler at a temperature equal to or lower than the dew point of the steam charged in the shift converter by the steam replacement process. Since it is possible to avoid the condensation of water vapor in the reactor, it is possible to suppress the breakage of the CO shift catalyst caused by the condensation of water vapor in the transformer.

  In short, according to the characteristic configuration of the hydrogen-containing gas generation device of the present invention, the start-up operation of the hydrogen-containing gas generation unit is automatically performed while suppressing the breakage of the CO conversion catalyst due to the condensation of water vapor in the converter. Can be done.

Block diagram of hydrogen-containing gas generator Longitudinal front view of the hydrogen-containing gas generator Perspective view of twin chamber container Perspective view of single chamber container The figure which shows the flowchart of control action The figure which shows the flowchart of control action The figure which shows the flowchart of control action Diagram showing the relationship between target output and target raw fuel flow rate Diagram showing the relationship between target output and target combustion chamber temperature The figure which shows the relationship between the target output and the target rotational speed of the raw material water pump A diagram showing the relationship between the target output and the target rotational speed of the combustion fan The figure which shows the relationship between target output and target rotational speed of the fan for selective oxidation The figure which shows the flowchart of the control action of 1st another embodiment. Block diagram of a hydrogen-containing gas generator of a second alternative embodiment

Embodiment
Hereinafter, an embodiment in which the present invention is applied to a hydrogen-containing gas generating device for a fuel cell will be described.
(overall structure)
As shown in FIG. 1, the hydrogen-containing gas generation device operates a hydrogen-containing gas generation unit P that generates a reformed gas (hydrogen-containing gas) mainly composed of hydrogen gas, and the operation of the hydrogen-containing gas generation unit P. A control unit C as an operation control unit to be controlled is provided, and the reformed gas (hydrogen-containing gas) generated by the hydrogen-containing gas generation unit P is supplied to the fuel cell G as a fuel gas. Has been.

  The hydrogen-containing gas generation unit P reforms the raw fuel that has been desulfurized by the water vapor generation unit S that generates water vapor, the desulfurization unit D that desulfurizes sulfur contained in the raw fuel, and the desulfurization unit D. In the reforming section R, the CO shift section T that converts carbon monoxide contained in the reforming process gas reformed in the reforming section R into carbon dioxide, and the reformed reformed process gas A selective oxidation part U that selectively oxidizes the remaining carbon monoxide is configured as a main part.

  That is, the hydrogen-containing gas generation unit P desulfurizes the raw fuel supplied to the reforming unit R in the desulfurization unit D, mixes the desulfurized raw fuel with the steam generated in the steam generation unit S, The mixed raw fuel is reformed in the reforming section R to generate a reforming process gas, and the reforming process gas generated in the reforming section R is supplied to the CO shift section T for reforming. The carbon monoxide gas in the process gas is converted to carbon dioxide, and the reformed gas that has been converted in the CO shift unit T is supplied to the selective oxidation unit U, so that the monoxide remaining in the reformed gas By selectively oxidizing the carbon gas, a reformed gas (hydrogen-containing gas) having a low carbon monoxide content is generated.

  In the hydrogen-containing gas generation part P of the present embodiment, the reforming part R and the reforming part heating flow part 6 provided so as to be able to transfer heat, and the raw fuel supplied to the desulfurization part D are heated for the raw fuel before desulfurization. A heat exchange unit Eb and a heat exchange unit Ea for heating the raw fuel after desulfurization for heating the raw fuel after being desulfurized in the desulfurization unit D are provided.

  Then, the reformed gas discharged from the reforming section R sequentially flows through the reforming section heating flow section 6, the heat exchange section Ea for heating the raw fuel after desulfurization, and the heat exchange section Eb for heating the raw fuel before desulfurization. After that, the raw fuel is configured to flow to the CO conversion section T, and the raw fuel is sequentially passed through the heat exchange section Eb for heating the raw fuel before desulfurization, the desulfurization section D, and the heat exchange section Ea for heating the raw fuel after desulfurization. , And is configured to flow to the reforming section R.

  That is, when the reforming process gas discharged from the reforming section R flows through the reforming section heating flow section 6, the reforming section R is heated and the raw fuel heating heat exchange section Ea after desulfurization. When flowing through, the raw fuel mixed with the steam supplied to the reforming section R is heated, and the raw fuel supplied to the desulfurizer 5 when flowing through the heat exchange section Eb for heating the raw fuel before desulfurization. It is configured to heat the fuel.

As shown in FIG. 2, the hydrogen-containing gas generation unit P of the present embodiment is configured such that a plurality of flat rectangular plate-like containers B (9 in this embodiment) are arranged in the thickness direction of the containers B. It is configured.
Then, in nine juxtaposed containers B, the steam generation part S, the reforming part R, the reforming part heating flow part 6, the heat exchange part Eb for heating the raw fuel before desulfurization, the desulfurization part D, the raw material after desulfurization The fuel heating heat exchange section Ea, the CO conversion section T, and the selective oxidation section U are configured, and details thereof will be described later.
In FIG. 2, from the left end to the right end side, the steam generation section S, the reforming section R, the reforming section heating flow section 6, the heat exchange section Ea for heating the raw fuel after desulfurization, the desulfurization section D, The heat exchange part Eb for heating raw fuel before desulfurization, the CO conversion part T, and the selective oxidation part U are provided in a state of being arranged in the order of description.

As shown in FIG. 1, the reformed gas (hydrogen-containing gas) generated in the hydrogen-containing gas generation unit P is supplied to the fuel cell G as the fuel gas as described above, and the selective oxidation unit U A fuel gas passage 9 is provided for guiding the reformed gas (hydrogen-containing gas) discharged from the fuel cell G to the fuel cell G.
Although detailed description is omitted, the fuel cell G of the present embodiment is of a solid polymer type using a polymer membrane as an electrolyte, hydrogen in the fuel gas supplied from the hydrogen-containing gas generation unit P, and power generation Electricity is generated by an electrochemical reaction with oxygen in the reaction air supplied from the fan 13.

Hereinafter, the configuration of each part of the hydrogen-containing gas generation part P will be described.
(Configuration of desulfurization section)
The desulfurization part D includes a desulfurizer 5 in which a desulfurization catalyst is charged, and is configured to flow raw fuel through the desulfurizer 5.
As the desulfurization catalyst, an adsorptive desulfurization agent such as a copper-zinc-based desulfurization agent is used. For example, at a desulfurization treatment temperature in the range of 150 to 300 ° C., the sulfur compound in the raw fuel is hydrogenated with the desulfurization catalyst. The hydride is adsorbed on zinc oxide and desulfurized.

  Incidentally, as the desulfurization catalyst, a hydrogenated desulfurization agent may be used. In this case, for example, after being discharged from the CO conversion part T, a reformed treatment gas from which moisture has been removed as described below is used. It will be supplied to the desulfurizer 5 as recycle gas.

(Configuration of reformer)
The reforming section R reforms the hydrocarbon-based raw fuel supplied in a mixed state of steam in a heated state by the reforming burner 1 so as to generate a reforming gas mainly composed of hydrogen gas. It is configured.
Specifically, the reforming section R is provided with a reforming treatment chamber 11 in which a large number of ceramic porous granular materials holding a reforming catalyst such as ruthenium, nickel, platinum, etc. are introduced in a state where they can be vented. The combustion chamber 12 provided with the reforming burner 1 is provided so as to be able to transfer heat with the reforming processing chamber 11.
In the combustion chamber 12, gas fuel is combusted by the reforming burner 1 and the reforming processing chamber 11 is heated.

In the reforming section R, when the raw fuel is city gas (13A) mainly composed of methane gas, under the reforming treatment temperature in the range of 600 to 700 ° C., for example, due to the catalytic action of the reforming catalyst, Methane gas and water vapor are reformed by the following reaction formula (1) to generate a reformed gas containing hydrogen gas and carbon monoxide gas.
Incidentally, since the reforming reaction in the reforming section R is an endothermic reaction, the reforming catalyst charged in the reforming process chamber 11 is heated in the combustion chamber 12 and the reforming section heating flow section 6. become.
CH ₄ + H ₂ O → CO + 3H ₂ O -------- (1)

(Configuration of water vapor generation unit)
The steam generation unit S is configured to generate steam mixed with the raw fuel supplied to the reforming treatment chamber 11 by heating water with combustion exhaust gas from the reformer burner 1.
Specifically, a steam generation chamber 2A to which raw water for steam generation is supplied and a heating exhaust gas flow chamber 2B through which the combustion exhaust gas of the reforming burner 1 is passed are arranged side by side so that heat can be transferred. The generation chamber 2A is heated by heat transfer from the heating exhaust gas flow chamber 2B so that steam is generated inside the water vapor generation chamber 2A.

  Incidentally, although detailed explanation is omitted, the heat transfer promoting material made of stainless wool or the like is filled in the water vapor generating chamber 2A and the heating exhaust gas flow chamber 2B in a state where it can be ventilated.

(Configuration of CO Transformer)
The CO conversion unit T is configured to convert carbon monoxide contained in the reforming process gas from the reforming processing chamber 11 into carbon dioxide using a CO conversion catalyst.
Specifically, in this embodiment, a transformer 3 is provided in which a large number of ceramic porous particles holding an iron oxide-based or copper-zinc-based CO conversion catalyst are charged. The reforming process gas supplied from the reforming section R is configured to flow.

The CO shift section T is provided with a shift catalyst cooler 4 through which the combustion exhaust gas after passing through the heating exhaust gas flow chamber 2B of the steam generation section S flows so as to be able to transfer heat to the shift converter 3. The CO shift catalyst charged in the converter 3 is cooled.
Incidentally, in FIG. 1, only one transformer 3 is shown to simplify the drawing. However, as shown in FIG. 2, in this embodiment, the transformer 3 is a transformation catalyst cooler. Four are provided in a state where two are located on both sides of the four.

In the CO shift section T, carbon monoxide gas and water vapor in the reforming process gas are converted into the following reaction formula under the shift processing temperature in the range of 150 to 310 ° C., for example, by the catalytic action of the CO shift catalyst. In step (2), the carbon monoxide gas is converted into carbon dioxide gas through a conversion reaction.
Incidentally, since the shift reaction in the CO shift section T is an exothermic reaction, the CO shift catalyst charged in the shift converter 3 is cooled by the shift catalyst cooler 4.
CO + H ₂ O → CO ₂ + H ₂ -------- (2)

  The shift catalyst cooler 4 exhibits an effect of heating and raising the temperature of the CO shift catalyst charged in the shift converter 3 when starting the hydrogen-containing gas generator P. During operation, the CO conversion catalyst is cooled.

(Configuration of selective oxidation unit)
The selective oxidation unit U is configured to selectively oxidize the carbon monoxide gas remaining in the reforming process gas after the shift treatment by the catalytic action of the selective oxidation catalyst.
Specifically, there is provided a selective oxidation reactor 15 in which a large number of ceramic porous particles holding a noble metal-based selective oxidation catalyst such as platinum, ruthenium, and rhodium are charged. The reforming process gas supplied from the CO shift section T is configured to flow in a state in which the oxidizing air is mixed.

  In other words, a selective oxidation fan 52 that supplies oxidation air to the selective oxidation reactor 15 of the selective oxidation unit U is supplied from the shift converter 3 to the selective oxidation reactor 15 through the oxidation air supply path 37. The reforming gas is provided in a state in which oxidizing air is supplied to the reforming treatment gas after the shift treatment, and the reforming processing gas mixed with the oxidizing air is configured to flow to the selective oxidation reactor 15.

In the selective oxidation unit U, the carbon monoxide gas remaining in the reformed treatment gas after the shift treatment, for example, under a selective oxidation treatment temperature in the range of 80 to 100 ° C. by the catalytic action of the selective oxidation catalyst. Is selectively oxidized to produce a reformed gas having a low carbon monoxide gas concentration, for example, a reformed gas (hydrogen-containing gas) having a carbon monoxide gas concentration of 10 ppm or less.
Since the selective oxidation reaction in the selective oxidation unit U is an exothermic reaction, a cooling fan 8 for blowing cooling air to the selective oxidation unit U is provided so that the selective oxidation unit U is cooled. .

The selective oxidation unit U is provided with an oxidation unit cooling air flow unit 7 through which combustion air supplied to the reforming burner 1 flows so as to be able to transfer heat with the selective oxidation reactor 15. The oxidation reactor 15 is configured to be cooled.
That is, in the summer season when the outside air temperature is high, in addition to cooling the selective oxidation unit U by blowing cooling air with the cooling fan 8, it is supplied to the reforming burner 1 through the oxidation unit cooling air flow unit 7. The selective oxidation unit U is cooled by flowing the combustion air.

(Configuration of heat exchanger for heating raw fuel after desulfurization)
After the desulfurization, the raw fuel heating heat exchange section Ea has an upstream heat exchange flow section 16 through which the reforming gas discharged from the reforming section heating flow section 6 flows and a desulfurizer 5 discharge. The desulfurized raw fuel flow-through portion 17 through which the raw fuel mixed with water vapor is passed is provided so as to be capable of exchanging heat so that the raw fuel mixed with water vapor is heated with the reforming gas. It is configured.

(Configuration of heat exchanger for heating raw fuel before desulfurization)
The heat exchange section Eb for heating the raw fuel before desulfurization is a downstream heat exchange flow for passing the reforming gas discharged from the upstream heat exchange flow section 16 of the heat exchange section Ea for heating the raw fuel after desulfurization. The raw fuel supplied to the desulfurizer 5 is heated with the reforming treatment gas by providing the section 18 and the raw fuel flow passage 19 before desulfurization for allowing the raw fuel supplied to the desulfurizer 5 to flow freely. It is configured as follows.

(Container configuration)
As described above, the hydrogen-containing gas generation unit P is configured by arranging a plurality (9 in the present embodiment) of flat rectangular plate-like containers B in the container thickness direction. There is a single-chamber container Bm having one flat chamber and a twin-chamber container Bd having two flat chambers.

As shown in FIG. 3, the twin-chamber container Bd has a pair of dish-shaped container forming members 41 and a partition member 43 in a state where a flat partition member 43 is positioned between the pair of dish-shaped container forming members 41. The two peripheral chambers are partitioned and formed by welding the peripheral portions of the two.
As shown in FIG. 4, the single-chamber container Bm is configured to form a single flat chamber by welding and connecting the peripheral portions of the dish-shaped container forming member 41 and the flat container forming member 42. Yes.
And the connection nozzle 44 for fluid supply and fluid discharge | emission is attached to the internal chamber Bm and the double-chamber container Bd in the state connected to an internal chamber as needed.

(Parallel form of container)
As shown in FIG. 2, in this embodiment, eight twin-chamber equipped containers Bd and one single-chamber equipped container Bm are provided, and these nine containers B are 3 from the left end toward the right end. The single chamber-equipped container Bm is positioned in parallel with the container B in the thickness direction.
In order to clarify the distinction between the eight twin-chamber equipped containers Bd, for convenience, reference numerals 1, 2, 3,... ............ 8 is attached.

  Further, the leftmost double chamber container Bd1 and the second double chamber container Bd2 from the left end, the single chamber container Bm and the third twin chamber container Bd3 from the left end, and 3 from the left end. A heat insulating material 22 for adjusting the amount of heat transfer is arranged between each of the second twin-chamber equipped container Bd3 and the fourth twin-chamber equipped container Bd3 from the left end.

The leftmost double chamber container Bd1 forms the heating exhaust gas flow chamber 2B and the steam generation chamber 2A of the steam generation unit S, and the second twin chamber container Bd2 from the left end is the combustion chamber of the reforming unit R. 12 and the reforming treatment chamber 11 are formed.
Unlike the shape shown in FIG. 3, the second twin-chamber equipped container Bd <b> 2 from the left end is formed in a shape in which one of the pair of dish-shaped container forming members 41 is bent in accordance with the shape of the combustion chamber 12. However, detailed description is omitted in this embodiment.

  The single-chamber equipped container Bm forms the reforming section heating flow section 6, and the third twin-chamber equipped container Bd3 from the left end is the upstream heat exchange passage for the raw fuel heating heat exchange section Ea after desulfurization. The flow portion 16 and the raw fuel flow portion 17 after desulfurization are formed.

The left chamber of the fourth double chamber equipped container Bd4 from the left end forms the desulfurizer 5 of the desulfurization section D, and the right chamber of the double chamber equipped container Bd4 is the heat exchanger Eb for heating the raw fuel before desulfurization. It is comprised so that the raw fuel flow part 19 before desulfurization may be formed.
The left chamber of the fifth double chamber container Bd5 from the left end is configured to form the downstream heat exchange flow passage 18 of the raw fuel heating heat exchange portion Eb before desulfurization.

  The right-hand chamber of the fifth double-chamber container Bd5 from the left end, the left-hand chamber of the sixth twin-chamber container Bd6 from the left end, and the left and right chambers of the seventh twin-chamber container Bd7 from the left end However, it forms the transformer 3 of the CO shift section T, and the right chamber of the sixth twin-chamber equipped container Bd6 from the left end forms four shift converters 3 in the form of the shift catalyst cooler 4. The CO transformation part T is formed.

  In other words, the reforming gas flows first through the transformer 3 formed in the right chamber of the fifth twin chamber container Bd5 from the left, and the left side of the sixth twin chamber container Bd6 from the left. The reforming process gas flows through the transformer 3 formed in the chamber No. 2 second, and the transformer 3 formed in the chamber on the left side of the seventh double chamber container Bd7 from the left is modified third. The reforming gas is passed through the reformer 3 formed in the right chamber of the seventh double-chamber container Bd7. The reforming process gas is configured to flow therethrough.

  The left chamber of the eighth chamber from the left end (in other words, the right end) of the double-chamber container Bd8 forms the oxidation portion cooling air flow section 7, and the right chamber of the twin-chamber container Bd8 is selected. An oxidation reactor 15 is configured to be formed.

  Incidentally, although detailed description is omitted, the nine containers B and the heat insulating material 22 are tightened in the container thickness direction, and the nine containers B are adjusted in the amount of heat transfer by the heat insulating material 22. Thus, by performing heat transfer between adjacent members, the temperature of each part is maintained at an appropriate temperature.

  That is, the desulfurization part D, the reforming part R, the CO conversion part T, and the selective oxidation part U among the reforming part R that needs to be maintained at the highest temperature and the selective oxidation that is required to be maintained at the lowest temperature. Adjacent to the unit U in a form in which the desulfurization unit D and the CO conversion unit T that need to be maintained at a temperature between the temperature of the reforming unit R and the temperature of the selective oxidation unit U are juxtaposed. The steam generating section S that is provided so as to be able to transfer heat between them, and that needs to be maintained at a temperature lower than that of the reforming section R, on the side opposite to the side where the desulfurizing section D is provided in the reforming section R. Is provided so as to be able to transfer heat with the reforming unit R, and the temperatures of the steam generation unit S, the desulfurization unit D, the reforming unit R, the CO conversion unit T, and the selective oxidation unit U can be maintained at appropriate temperatures. It is like that.

(Flow form of raw fuel)
1 and 2, the raw fuel supply path 23 is connected to the pre-desulfurization raw fuel flow section 19 of the pre-desulfurization raw fuel heating heat exchanging section Eb, as indicated by white lines.
Further, the raw fuel flow section 19 before desulfurization, the desulfurizer 5, the raw fuel flow section 17 after desulfurization of the heat exchange section Ea after heating for desulfurization, the reforming treatment chamber 11 of the reforming section R, and for heating the reforming section The flow section 6, the upstream heat exchange flow section 16 of the raw fuel heating heat exchange section Ea after desulfurization, the downstream heat exchange flow section 18 of the raw fuel heating heat exchange section Eb before desulfurization, the CO conversion section T The gas treatment flow path 24 connected in this order to the four-stage transformer 3 and the selective oxidation reactor 15 of the selective oxidation unit U is provided.

  Therefore, the raw material gas from the raw fuel supply passage 23 is fed into the raw fuel flow section 19 before desulfurization, the desulfurizer 5, the raw fuel flow section 17 after desulfurization of the heat exchange section Ea for heating the raw fuel after desulfurization, and the reforming section. The reforming process gas flowing in the order of the reforming process chamber 11 of the R and reformed in the reforming process chamber 11 is converted into a reforming section heating flow section 6, a desulfurized raw fuel heating heat exchange section. Ea upstream heat exchange flow part 16, pre-desulfurization raw fuel heating heat exchange part Eb downstream heat exchange flow part 18, CO transformation part T four-stage transformer 3, and selective oxidation part U The selective oxidation reactor 15 is configured to flow in this order.

  The raw fuel supply path 23 is provided with a raw fuel intermittent valve 25 </ b> A for intermittently supplying the raw fuel to the hydrogen-containing gas generator P and a raw fuel adjustment valve 25 </ b> B for adjusting the supply amount of the raw fuel.

  Further, in the gas processing flow path 24, the raw material water flowing through the raw water supply path 26, which will be described later, is connected to the portion where the fourth reformer 3 through which the reforming process gas flows and the selective oxidation reactor 15 are connected. The raw material water preheating heat exchanger 10 for preheating the reformed gas after the transformation treatment, and the drain trap 27 for removing condensed water from the reforming gas, the drain trap 27 for the raw water preheating heat exchanger. It is provided in a state where it is located downstream from 10, and is configured to remove moisture from the reformed gas after the modification treatment while preheating the raw water.

  Incidentally, the oxidizing air supply passage 37 for supplying the selective oxidizing air supplied from the selective oxidizing fan 52 to the selective oxidation reactor 15 is the reforming processing gas 4 in the gas processing passage 24. It is connected to a location downstream of the drain trap 27 in the portion connecting the transformer 3 and the selective oxidation reactor 15 that flow through the second.

(Flow form of raw water)
In FIG.1 and FIG.2, as shown with a continuous line, the raw material water supply path 26 is connected to the water vapor generation chamber 2A of the water vapor generation part S through the raw material water preheating heat exchanger 10.
The raw water supply path 26 is provided with a raw water pump 28, and the raw water pump 28 is configured to pump the raw water for generating steam into the steam generating chamber 2A.

The steam passage 29 through which the steam generated in the steam generation chamber 2A flows is the desulfurized raw fuel flow through the desulfurizer 5 and the desulfurized raw fuel heating heat exchanger Ea in the gas processing flow path 24. It is connected to a portion connecting with the portion 17 and is configured to mix the steam for reforming with the raw fuel after the desulfurization treatment.
Incidentally, a mixing device such as a mixing ejector is provided to mix the reforming steam with the raw fuel after the desulfurization treatment, but in this embodiment, the description of the mixing device is omitted.

(Flow form of combustion exhaust gas)
1 and 2, the combustion chamber 12 of the reforming section R, the exhaust gas flow chamber 2B for heating of the steam generating section S, and the shift catalyst cooler 4 of the CO shift section T are sequentially shown as indicated by broken lines. An exhaust gas passage 30 to be connected is provided.

Therefore, when the combustion exhaust gas of the reforming burner 1 discharged from the combustion chamber 12 flows through the heating exhaust gas flow chamber 2B and the shift catalyst cooler 4, and flows through the heating exhaust gas flow chamber 2B, When the steam generation chamber 2A is heated and the shift catalyst cooler 4 flows, the CO shift catalyst of the shift converter 3 is cooled.
As described above, the combustion exhaust gas flowing through the shift catalyst cooler 4 exhibits the effect of heating the shift converter 3 and raising the temperature when the hydrogen-containing gas generation part P is started.

Further, exhaust gas for flowing the combustion exhaust gas by bypassing the shift catalyst cooler 4 in a form branched from a portion of the exhaust gas passage 30 where the exhaust gas flow chamber 2B for heating and the shift catalyst cooler 4 are connected. A bypass path 30a is provided.
An exhaust gas passage opening / closing valve 30A is provided downstream of the branch point of the exhaust gas bypass passage 30a in the exhaust gas passage 30, and an exhaust gas bypass passage opening / closing valve 30B is provided in the exhaust gas bypass passage 30a.

  Therefore, the exhaust gas passage opening / closing valve 30 </ b> A and the exhaust gas bypass passage opening / closing valve 30 </ b> B are opened and closed to allow the combustion exhaust gas after flowing through the water vapor generating portion S to pass through the shift catalyst cooler 4. It is configured to be able to switch between a cooling flow state and a bypass flow state in which the combustion exhaust gas after flowing through the steam generation unit S in a form that bypasses the shift catalyst cooler 4 is passed.

That is, by switching to the bypass state when starting up the hydrogen-containing gas generator P, it is possible to suppress the generation of dew condensation water inside the transformer 3, the details of which will be described later. .
Incidentally, in the present embodiment, the flow path switching unit J that switches between the cooling flow state and the bypass flow state is configured by the exhaust gas bypass path 30a, the exhaust gas path on / off valve 30A, and the exhaust gas bypass path on / off valve 30B. Become.

  In addition, the flow path switching unit J is configured so that the combustion exhaust gas is less than the dew point of the steam charged in the transformer 3 in the steam replacement process described later after flowing through the steam generation unit S. It functions as the canceling means K that operates to cancel the flow of the shift catalyst cooler 4 at a temperature below the dew point of the water vapor, and the bypass flow state corresponds to the operating state of the canceling means K, and is used for cooling. The flow state corresponds to the stop state of the canceling means K.

(Combustion structure of reformer burner)
An off-gas passage 31 is provided for supplying exhaust gas discharged from the fuel electrode of the fuel cell G (hereinafter also referred to as off-gas) to the reforming burner 1 so that the reforming burner 1 burns off gas as fuel. It is configured.
Further, a gas fuel supply passage 33 is provided for supplying city gas (13A) to the reforming burner 1 as a fuel for combustion, and the reforming burner 1 is combusted supplied from the gas fuel supply passage 33 in addition to the off-gas. It is constituted so that it may burn even for fuel.
The gas fuel supply passage 33 is provided with a fuel interrupt valve 34A and a fuel adjustment valve 34.

  In other words, the reforming burner 1 burns off gas as fuel during normal operation for supplying the reformed gas (hydrogen containing gas) generated in the hydrogen containing gas generating section P to the fuel cell G, and only the off gas. When the amount of heating is insufficient, the combustion fuel supplied from the gas fuel supply path 33 is also burned as fuel, and when the hydrogen-containing gas generation unit P is started, the gas fuel supply path 33 Combustion is performed using the supplied combustion fuel as fuel.

1 and 2, a combustion air supply passage 35 for supplying air from the combustion fan 50 as combustion air to the reforming burner 1 is provided as indicated by a one-dot chain line. The air supply path 36 is provided in a form branched from the combustion air supply path 35.
The air supply path 36 via the oxidation section allows air from the combustion fan 50 to flow through the oxidation section cooling air flow section 7, and passes through the oxidation section cooling air flow section 7. After that, it is connected to the combustion air supply path 35.

A first air path switching on-off valve 38 is provided in the combustion air supply path 35, and a second air path switching on-off valve 39 is provided in the oxidation part air supply path 36.
Then, by opening and closing the first air path switching on-off valve 38 and the second air path switching on-off valve 39, the combustion air from the combustion fan 50 is passed through the oxidization part air supply path 36. The supply state via the oxidation section supplied to the reforming burner 1 and the combustion air from the combustion fan 50 are reformed through the combustion air supply path 35 without passing the oxidation section cooling air flow section 7. It is configured to be able to switch to a direct supply state that supplies directly to the burner 1.
Incidentally, the burning air to the reforming burner 1 is normally supplied in the direct supply state, but when the cooling capacity of the selective oxidation unit U is insufficient, for example, at the high temperature in summer, the oxidation unit The selective oxidation unit U is cooled by the combustion air by switching to the via supply state.

As shown in FIG. 1, the reforming burner 1 of the present embodiment is configured to include two first ejection pipes 1 </ b> A and second ejection pipes 1 </ b> B in which flame holes are formed along the longitudinal direction. .
The off-gas passage 31 is connected to the first ejection pipe 1A, the combustion air supply path 35 is connected to the second ejection pipe 1B, and the gas fuel supply path 33 is connected to the combustion air supply path 35. Yes.

Accordingly, the off gas ejected from the first ejection pipe 1A is configured to burn with the combustion air ejected from the second ejection pipe 1B, and the combustion fuel supplied from the gas fuel supply passage 33 is combusted. It is configured to be ejected from the second ejection pipe 1B and burned in a state of being mixed with industrial air.
Incidentally, at the time of starting the hydrogen-containing gas generation part P, as described later, in a state where the combustion fuel from the gas fuel supply passage 33 is jetted from the second jet pipe 1B in a mixed state with the combustion air and burns. The raw fuel and water vapor flowing through the off-gas passage 31 are ejected from the first ejection pipe 1A, and the raw fuel ejected from the first ejection pipe 1A is combusted together with the combustion fuel.

(Flow path switching configuration)
A fuel gas path 9 that leads the reformed gas (hydrogen-containing gas) from the hydrogen-containing gas generator P to the fuel cell G and an off-gas path 31 that guides the exhaust gas from the fuel cell G to the reformer burner 1 are connected to the fuel cell G. A bypass gas passage 9a connected in a bypassed state is provided.
Further, a fuel gas passage opening / closing valve 9A for opening and closing the fuel gas passage 9 is provided at a location downstream of the branch location of the bypass gas passage 9a in the fuel gas passage 9, and a bypass gas passage is provided in the middle of the bypass gas passage 9a. A bypass gas passage opening / closing valve 9B for opening and closing 9a is provided, and a downstream opening / closing valve 9C for opening and closing the offgas passage 31 is provided at a location upstream of the connection location of the bypass gas passage 9a in the offgas passage 31.

  Therefore, when all of the fuel gas passage opening / closing valve 9A, the bypass gas passage opening / closing valve 9B, and the downstream opening / closing valve 9C are opened, the fluid flowing through the fuel gas passage 9 passes through the fuel cell G and the bypass gas passage 9a. Thus, the gas can flow into the off-gas passage 31. Hereinafter, this state is referred to as a parallel flow state.

  When the fuel gas passage opening / closing valve 9A and the downstream side opening / closing valve 9C are opened and the bypass gas passage opening / closing valve 9B is closed, the fluid flowing through the fuel gas passage 9 is passed through the fuel cell G to the off-gas passage. 31 can be made to flow. Hereinafter, this state is referred to as a normal flow state.

  When the bypass gas passage opening / closing valve 9B is opened and the fuel gas passage opening / closing valve 9A and the downstream opening / closing valve 9C are closed, the fluid flowing through the fuel gas passage 9 bypasses the fuel cell G while bypassing the fuel gas G. It can be made to flow to the off-gas path 31 via the path 9a. Hereinafter, this state is referred to as a bypass flow state.

  Further, when all of the fuel gas passage opening / closing valve 9A, the bypass gas passage opening / closing valve 9B, and the downstream side opening / closing valve 9C are closed, the hydrogen-containing gas generating portion P and the fuel cell G are kept filled with raw fuel. be able to. That is, as described later, the hydrogen-containing gas generation unit P and the fuel cell G are filled with raw fuel when the operation is stopped, and the fuel gas passage opening / closing valve 9A, the bypass gas passage opening / closing valve 9B, and the downstream side By closing all of the on-off valves 9C, the hydrogen-containing gas generating part P and the fuel cell G can be kept filled with raw fuel. Hereinafter, this state is referred to as a sealed state.

  Incidentally, when the control unit C executes a startup process or a stop process, which will be described later, the fuel gas path on / off valve 9A, the bypass gas path on / off valve 9B, and the downstream side on / off valve 9C are controlled to open / close. Details thereof will be described later.

(Starting heating configuration)
When starting the hydrogen-containing gas generating part P, a pair of electric heaters for heating the desulfurizer 5 so that the desulfurizer 5 can be desulfurized and heating the CO shifter T so as to be capable of being subjected to a denatured process. The steam generator 21 and the electric steam generator 51 for heating the steam generating chamber 2A of the steam generating section S so that the steam can be generated are provided.

  That is, when starting the hydrogen-containing gas generation part P, in addition to starting combustion of the reforming burner 1, a desulfurizer heater 20, a pair of shifter heaters 21, and a steam generator heater 51 is operated to increase the temperature quickly.

(Temperature detection configuration for operation control)
A reforming temperature sensor T1 that detects the temperature of the reforming processing chamber 11 of the reforming unit R as the reforming unit temperature is provided, and the control unit C operates at startup based on the reforming unit temperature as described later. It is comprised so that a process and an operation process at the time of a stop may be performed.
A combustion chamber temperature sensor T2 that detects the temperature of the combustion chamber 12 as the combustion chamber temperature is provided, and the control unit C executes the combustion control of the reforming burner 1 based on the combustion chamber temperature, as will be described later. It is configured.

A selective oxidation unit temperature sensor T3 for detecting the temperature of the selective oxidation reactor 15 as a selective oxidation treatment temperature is provided, and the control unit C rotates the cooling fan 8 so as to maintain the selective oxidation treatment temperature at a set appropriate temperature. It is configured to control the speed.
Incidentally, even when the control unit C controls the rotational speed of the cooling fan 8 at a high speed, when the selective oxidation treatment temperature becomes higher than the set appropriate temperature, the control unit C sends the combustion air from the combustion fan 50 via the oxidation unit. The cooling capacity of the selective oxidation reactor 15 is increased by switching to the supply state via the oxidation unit supplied to the reforming burner 1 through the air supply path 36.

A combustion exhaust gas temperature sensor T4 as a combustion exhaust gas temperature measuring means for measuring the temperature of the combustion exhaust gas after flowing through the steam generation unit S as the combustion exhaust gas temperature is used for heating the exhaust gas passage chamber for heating the water vapor generation unit S in the exhaust gas passage 30. 2B and the part located between the branch locations of the exhaust gas bypass passage 30a.
Then, as will be described later, when the control unit C performs the start-up process, the flow path switching unit J is switched between the bypass flow state and the cooling flow state based on the combustion exhaust gas temperature, and the inside of the transformer 3 It is configured to suppress the occurrence of dew condensation.

(Normal operation method of hydrogen-containing gas generator)
The control unit C is configured to execute a normal operation process corresponding to the normal operation method when a startup process described later is completed.
In the normal operation process, a target output for performing the main operation for causing the output of the fuel cell G to follow the currently requested power load is set, and in accordance with the target output, the hydrogen-containing gas generation unit A process for controlling P is executed.

  That is, as shown in FIG. 8, the relationship between the target output of the fuel cell G and the target raw fuel flow rate required for the fuel cell G to output the target output is obtained as output vs. raw fuel flow rate information. The target raw fuel flow rate is set to increase as the output increases.

As shown in FIG. 9, the relationship between the target output of the fuel cell G and the target combustion chamber temperature of the combustion chamber 12 for adjusting the temperature of the reforming processing chamber 11 to the set temperature for reforming processing is output versus combustion. The chamber temperature information is set such that the target combustion chamber temperature increases as the target output increases.
That is, when the target output of the fuel cell G increases, the reforming amount of the raw fuel in the reforming process chamber 11 increases, so that the temperature of the reforming process chamber 11 is maintained at the set temperature for reforming process. Increases the combustion amount of the reforming burner 1 and raises the target combustion chamber temperature of the combustion chamber 12.

As shown in FIG. 10, the relationship between the target output of the fuel cell G and the target rotational speed of the raw water pump 28 that supplies the raw water is the output versus raw water pump rotational speed information, and the target output of the fuel cell G is The target rotational speed is set so as to increase as the value increases.
That is, when the target output of the fuel cell G increases, the reforming amount of the raw fuel in the reforming treatment chamber 11 increases, and accordingly, the amount of water vapor mixed with the raw fuel increases. The target rotation speed is increased as the target output of the fuel cell G increases.

Then, as the target output of the fuel cell G increases, the target rotational speed of the raw material water pump 28 is increased, and the ratio (S / C) of the steam supply amount to the raw fuel supply amount to the reforming treatment chamber 11 is set to an appropriate state. Will be maintained.
Incidentally, S / C is set to the range of 2.5-3.0, for example.

As shown in FIG. 11, the relationship between the target output of the fuel cell G and the target rotational speed of the combustion fan 50 indicates that the target rotational speed increases as the target output of the fuel cell G increases as output versus combustion fan rotational speed information. Is set to a high state.
That is, based on the output versus combustion chamber temperature information shown in FIG. 9, the target combustion chamber temperature is set higher as the target output of the fuel cell G increases, and in order to maintain the target combustion chamber temperature, the control unit C The amount of combustion fuel supplied to the reforming burner 1 is controlled. By operating the combustion fan 50 at a target rotational speed set based on output versus combustion fan rotational speed information, the reforming burner 1 is controlled. The air ratio can be maintained in an appropriate state.

As shown in FIG. 12, the relationship between the target output of the fuel cell G and the target rotational speed of the selective oxidation fan 52 is such that the target output of the fuel cell G increases as the output versus selective oxidation fan rotational speed information. It is set in a state where the rotation speed becomes high.
That is, when the target output of the fuel cell G increases, the amount of the reforming gas to be selectively oxidized in the selective oxidation reactor 15 increases, so the flow rate of the selective oxidation air supplied to the selective oxidation reactor 15 In order to increase the target rotational speed of the selective oxidation fan 52 as the target output of the fuel cell G increases.

In the normal operation process, the control unit C sets a target output that follows the currently requested power load.
Then, the target raw fuel flow rate is obtained based on the set target output and the output-to-raw fuel flow rate information, and the opening degree of the raw fuel adjustment valve 25B is adjusted so that the obtained target raw fuel flow rate is obtained.
Incidentally, when the opening degree of the raw fuel adjustment valve 25B is adjusted, a flow rate sensor for detecting the flow rate of the raw fuel flowing through the raw fuel supply passage 23 is provided, and the raw fuel adjustment valve 25B is based on the detected information. However, in this embodiment, detailed description is omitted.

  Further, the target rotational speed of the raw material water pump 28 is obtained based on the set target output and the output versus raw material water pump rotational speed information, and the rotational speed of the raw material water pump 28 is controlled so as to be the obtained target rotational speed. To do.

Further, the target rotational speed of the combustion fan 50 is obtained based on the set target output and the output-combustion fan rotational speed information, and the rotational speed of the combustion fan 50 is controlled so as to be the obtained target rotational speed. To do.
Further, based on the set target output and output versus combustion chamber temperature information, the target combustion chamber temperature is obtained, and the fuel control valve 34B is set so that the detected temperature of the combustion chamber temperature sensor T2 becomes the obtained target combustion chamber temperature. The amount of combustion fuel supplied to the reformer burner 1 is adjusted at.

Further, the target rotation speed of the selective oxidation fan 52 is obtained based on the set target output and the output versus selective oxidation fan rotation speed information, and the rotation of the selective oxidation fan 52 is performed so that the obtained target rotation speed is obtained. Control the speed.
Incidentally, the control unit C adjusts the rotation speed of the cooling fan 8 so that the temperature detected by the selective oxidation unit temperature sensor T3 becomes a set appropriate temperature (for example, 80 to 150 ° C.) in the normal operation process, In addition, the first air path switching on-off valve 38 and the second air path switching on-off valve 39 are controlled to open and close as necessary.

(How to stop the reforming unit)
When executing the normal operation process, the control unit C executes the stop process corresponding to the stop operation method at the stop timing.
In the stop-time process, first, in a state where combustion of the reforming burner 1 is stopped, a steam supply process for continuing the supply of steam by the steam generation unit S is performed, and then the temperature of the reforming process chamber 11 is equal to that of the raw fuel. When the raw fuel purge start temperature can be prevented, which prevents thermal decomposition and condensation of water vapor, the supply of water vapor by the water vapor generation unit S is stopped and the raw fuel is supplied from the raw fuel supply passage 23 to generate a hydrogen-containing gas. The raw fuel filling process for filling the part P and the fuel cell G with the raw fuel is performed, and finally the sealing process for sealing the hydrogen-containing gas generation part P and the fuel cell G to the state where the raw fuel is filled is performed. Become.

(Start-up method of reforming unit)
The control unit C is configured to execute a start-up process corresponding to the start-up operation method of starting the hydrogen-containing gas generation unit P and the fuel cell G that are stopped in a state where the raw fuel is filled at the start timing. Has been.

  In the start-up process, first, a combustion start process for starting combustion of the reforming burner 1 is performed, and then the steam supply in which the temperature of the reforming process chamber 11 can prevent thermal decomposition of the raw fuel and steam condensation. When the temperature is raised to the start temperature, supply of water vapor by the water vapor generation unit S is started, and a water vapor replacement process is performed to replace the raw fuel charged in the hydrogen-containing gas generation unit P and the fuel cell G with water vapor, and then When the temperature of the reforming chamber 11 rises to a reforming start temperature at which reforming is possible, the supply of fuel to the fuel cell G is stopped, and the raw fuel mixed with water vapor is converted into the hydrogen-containing gas generator P. The raw fuel supply process to be supplied to is performed.

  Then, when the detour processing set time elapses after starting the raw fuel supply process, a power generation start process for supplying the reformed gas (hydrogen-containing gas) generated by the hydrogen-containing gas generation unit P to the fuel cell G is performed. This is executed to start the power generation of the fuel cell G.

  In addition, when performing the steam replacement process, whether the temperature of the combustion exhaust gas after flowing through the steam generation unit S is below the dew point of the steam charged in the transformer 3 based on the temperature detected by the combustion exhaust gas temperature sensor T4 If the dew point is below the dew point, the flow path switching unit J is switched to the bypass flow state, and if higher than the dew point, the flow path switching unit J is switched to the cooling flow state. The water vapor filled in the transformer 3 is configured to suppress dew condensation.

  Incidentally, in the steam substitution process, the steam from the steam generation unit S is supplied to the reforming process chamber 11 and the raw fuel or fuel filled in the reforming process chamber 11, the transformer 3, and the selective oxidation reactor 15. The raw fuel charged in the battery G is replaced with steam, and the raw fuel replaced with the steam is supplied to the reformer burner 1 through the offgas passage 31 and burned.

  When the raw fuel supply start process is executed, the raw fuel from the raw fuel supply path 23 is supplied to the desulfurizer 5, and the steam that is charged in the reforming treatment chamber 11, the shift converter 3, and the selective oxidation reactor 15. Is replaced with the raw fuel, and the water vapor replaced with the raw fuel is supplied to the reforming burner 1 through the off-gas passage 31 and discharged along with the flow of the combustion exhaust gas.

  When the power generation start process is executed, the reformed gas (hydrogen-containing gas) generated in the hydrogen-containing gas generation unit P is supplied to the fuel cell G, so that the water vapor filled in the fuel cell G is modified. The water vapor that is to be replaced with the quality gas (hydrogen-containing gas) and is replaced with the reformed gas (hydrogen-containing gas) is supplied to the reformer burner 1 through the off-gas passage 31 and flows along with the flow of the combustion exhaust gas. Will be discharged.

(Details of control operation)
Next, based on the flowchart shown in FIGS. 5-7, the control operation | movement of the control part C is demonstrated concretely.
By the way, in the following explanation, when a part of the day is set as the operation time zone and the start time of the operation time zone is reached, the start timing is given as the start command, and the operation time zone A case will be exemplified in which when the end time comes, it is the stop timing at which the stop command is commanded.

(Overall control operation)
As shown in FIG. 5, the control unit C determines whether or not it is a start timing (# 1), executes a start-up process when the start timing comes (# 2), and when the start-up process ends, The operation process is executed (# 3).
Then, it is determined whether or not it is the stop timing in the normal operation process (# 4), and when the stop timing is reached, the stop process is executed (# 5).

(Control operation for startup processing)
As shown in FIG. 6, in the startup process, first, a combustion start process for starting combustion of the reforming burner 1 is executed (# 11).
In this combustion start processing, the fuel intermittent valve 34A is opened to start supplying fuel for combustion, and the target output is set to a preset start output, and the set start output and output versus combustion fan rotation speed are set. Based on the information, the target rotational speed of the combustion fan 50 is obtained, and the operation of the combustion fan 50 is started in such a manner that the rotational speed of the combustion fan 50 is controlled so as to be the obtained target rotational speed.

In addition, the fuel control valve calculates the target combustion chamber temperature based on the set output for starting and output versus combustion chamber temperature information so that the detected temperature of the combustion chamber temperature sensor T2 becomes the calculated target combustion chamber temperature. The amount of combustion fuel supplied to the reforming burner 1 is adjusted by adjusting the opening of 34B.
Although not illustrated, when starting the supply of combustion fuel, an igniter such as a spark plug is operated until ignition is detected by the ignition sensor.

Further, in order to cause the combustion exhaust gas of the reforming burner 1 to flow through the shift catalyst cooler 4, the exhaust gas passage opening / closing valve 30A of the flow path switching unit J is opened and the exhaust gas bypass passage opening / closing valve 30B is closed.
Incidentally, although illustration is omitted, in the combustion start process, the fuel gas path on / off valve 9A, the bypass gas path on / off valve 9B, and the downstream side on / off valve 9C are all kept in a sealed state.

  Incidentally, although not shown in FIG. 6, for the combustion to the reformer burner 1 by adjusting the opening degree of the fuel control valve 34B so that the detected temperature of the combustion chamber temperature sensor T2 becomes the calculated target combustion chamber temperature. The control operation for adjusting the fuel supply amount is repeatedly performed while the startup process is executed.

After executing the combustion start process, it is determined whether the reforming section temperature detected by the reforming temperature sensor T1 is equal to or higher than the steam supply start temperature (# 12), and the reforming section temperature is the steam supply. When the temperature is equal to or higher than the start temperature, the water vapor replacement process is executed (# 13).
The steam supply start temperature is a temperature at which the raw fuel can be prevented from being thermally decomposed and the steam can be prevented from condensing, and is set to, for example, 220 to 250 ° C.

In the steam replacement process, the fuel gas path on / off valve 9A, the bypass gas path on / off valve 9B, and the downstream side on / off valve 9C are all switched to a parallel flow state and the operation of the raw material water pump 28 is started.
That is, the target rotational speed of the raw material water pump 28 is obtained based on the set output for starting and output versus raw material water pump rotational speed information, and the rotational speed of the raw material water pump 28 is set so as to be the obtained target rotational speed. The raw material water pump 28 is started to be controlled.

Thereafter, it is determined whether the combustion exhaust gas temperature detected by the combustion exhaust gas temperature sensor T4 is equal to or lower than the dew point temperature of water vapor (# 14).
When the combustion exhaust gas temperature is higher than the dew point temperature of water vapor (100 ° C.), the flow path switching unit J is switched to a cooling flow state in which the exhaust gas path on / off valve 30A is opened and the exhaust gas bypass path on / off valve 30B is opened (# 15 On the contrary, when the combustion exhaust gas temperature is equal to or lower than the dew point temperature of water vapor, the flow path switching unit J is switched to a bypass flow state in which the exhaust gas path on / off valve 30A is closed and the exhaust gas bypass path on / off valve 30B is opened (# 16). ).

Next, it is determined whether or not the reforming section temperature detected by the reforming temperature sensor T1 is equal to or higher than the reforming processing start temperature (# 17).
When the reforming part temperature is lower than the reforming process start temperature, the process proceeds to the process of # 14 and the process of switching the flow path switching part J is continued, and the reforming part temperature is reformed. When the temperature reaches the processing start temperature or higher, the raw fuel supply processing is executed (# 18).
The reforming process start temperature is a temperature at which the reforming process of the raw fuel can be performed, and is set to 600 ° C., for example.

In the raw fuel supply process, the fuel gas path on / off valve 9A and the downstream side on / off valve 9C are closed and the bypass gas path on / off valve 9B is switched to the bypass flow state, and the exhaust gas path on / off valve 30A is opened and the exhaust gas bypass is opened. Maintain the flow state for cooling that opens the on-off valve 30B in the flow path switching section J. In addition, open the raw fuel intermittent valve 25A and adjust the opening of the raw fuel regulating valve 25B to start the supply of raw fuel To do.
That is, a mode in which the target raw fuel flow rate is obtained based on the set start output and output versus raw fuel flow rate information, and the opening degree of the raw fuel adjustment valve 25B is adjusted so as to obtain the obtained target raw fuel flow rate. Then, the supply of raw fuel is started.

Next, it is determined whether or not the elapsed time from the start of the raw fuel supply process has passed the detour processing set time (# 19), and if the detour processing set time has elapsed, A start process is executed (# 20).
The detour processing set time is such that after the raw fuel supply starts, the processes in the desulfurization section D, reforming section R, CO conversion section T, and selective oxidation section U are normally in a stable state, and the hydrogen-containing gas is generated. The time required for the reformed gas (hydrogen-containing gas) generation in the part P to be normally stable is set to, for example, 2 to 10 minutes.

In the power generation start process, a process of opening the fuel gas path on-off valve 9A and the downstream side on-off valve 9C and switching to the normal flow state in which the bypass gas path on-off valve 9B is closed is executed.
By this power generation start processing, the reformed gas (hydrogen-containing gas) generated in the hydrogen-containing gas generation unit P is supplied to the fuel cell G, and power generation of the fuel cell G is started. Thereafter, normal operation processing for adjusting the generation amount of the reformed gas according to the target output of the fuel cell G is executed.

  In addition, since the control content of a normal driving process is clear from the above-mentioned description, in this embodiment, description of the control operation of a normal driving process with a flowchart is abbreviate | omitted.

(Control operation for stop processing)
As shown in FIG. 7, in the stop process, first, a steam supply process for continuing the supply of steam with the combustion of the reforming burner 1 stopped is performed (# 31).
In this steam supply process, the fuel intermittent valve 34A is closed, the combustion fan 50 is stopped, the combustion of the reforming burner 1 is stopped, the raw fuel intermittent valve 25A is closed, and the supply of raw fuel is stopped. However, the operation of the raw material water pump 28 is continued, and the supply of water vapor is continued.

  Further, in this water vapor supply process, the hydrogen gas generating part P and the fuel cell are set in a parallel flow state in which all of the fuel gas path opening / closing valve 9A, the bypass gas path opening / closing valve 9B, and the downstream side opening / closing valve 9C are opened. G is filled with water vapor.

Next, it is determined whether or not the reforming section temperature detected by the reforming temperature sensor T1 is equal to or lower than the raw fuel purge start temperature (# 32), and the reforming section temperature is equal to or lower than the raw fuel purge start temperature. In this case, the raw fuel filling process is executed.
The raw fuel purge start temperature is a temperature at which thermal decomposition of the raw fuel can be prevented and water vapor can be prevented from condensing, and is set to 400 ° C., for example.

  In the raw fuel filling process, the raw water pump 28 is stopped, the raw fuel intermittent valve 25A is opened, and the opening degree of the raw fuel adjustment valve 25B is adjusted so that the flow rate of the raw fuel becomes a preset filling flow rate. .

Thereafter, it is determined whether or not the time since the start of the raw fuel filling process has passed the set time for raw fuel purge (# 34). Execute stop processing.
The set time for purging the raw fuel is that the steam filled in the hydrogen-containing gas generator P and the fuel cell G is reformed by the raw fuel after the raw fuel intermittent valve 25A is opened and the supply of the raw fuel is started. The time required for the raw fuel to reach the reforming burner 1 after being pushed out from the burner 1 is set to a time slightly longer than that time.

  In the sealing process, the raw fuel intermittent valve 25A is closed, and the fuel gas path on / off valve 9A, the bypass gas path on / off valve 9B, and the downstream side on / off valve 9C are all closed so as to close the raw fuel. The state in which the hydrogen-containing gas generation part P and the fuel cell G are filled is maintained.

[First Embodiment]
Next, although 1st another embodiment is described, this 1st another embodiment shows another control form for switching the flow-path switching part J in the said embodiment to the flow state for cooling, and a bypass flow state. Since the other configuration is the same as that of the above embodiment, only the configuration different from the above embodiment will be described below.

That is, the temperature rises until the temperature of the combustion exhaust gas after flowing through the steam generation unit S becomes higher than the dew point of the steam charged in the transformer 3 in the steam replacement process after the combustion start process is performed. The elapsed time for use is predetermined.
And when the control part C performs a process at the time of starting, it is made to flow through the water vapor generation part S based on whether or not the elapsed time from the execution of the combustion start process exceeds the elapsed time for temperature increase. It is determined whether or not the temperature of the combustion exhaust gas after the heat treatment is equal to or lower than the dew point of the water vapor charged in the transformer 3, and based on the determination result, the flow path switching unit J is in a cooling flow state and a bypass flow state. It is comprised so that it may switch to.

Next, description is added based on the flowchart shown in FIG.
Incidentally, the processing of # 41 to # 43 and the processing of # 47 to # 50 in the flowchart of FIG. 13 are the same as the processing of # 11 to # 13 and the processing of # 17 to # 20 in the flowchart of FIG. Since the processes of # 44 to # 46 in the flowchart of FIG. 13 are different from the processes of # 14 to # 16 in the flowchart of FIG. 6, the processes of # 44 to # 46 in the flowchart of FIG.

That is, after the steam replacement process is performed in # 43, it is determined whether or not the elapsed time after the combustion start process has exceeded the temperature increase elapsed time (# 44).
When the elapsed time since the start of the combustion process exceeds the elapsed time for temperature increase, the flow path is changed to a cooling flow state in which the exhaust gas passage opening / closing valve 30A is opened and the exhaust gas bypass passage opening / closing valve 30B is opened. When the switching section J is switched (# 45) and the elapsed time since the start of combustion processing does not exceed the elapsed time for temperature increase, the exhaust gas passage opening / closing valve 30A is closed and the exhaust gas bypass passage is opened / closed. The flow path switching unit J is switched to the bypass flow state in which the valve 30B is opened (# 46).

  Elapsed time for temperature rise is determined by passing the water vapor generation unit S under the condition that the hydrogen-containing gas generation unit P is equal to the environmental temperature in the coldest environment assumed when the hydrogen-containing gas generation device is installed. It is determined as the time required for the temperature of the flue gas after flowing to exceed the dew point of the water vapor charged in the transformer 3 after the combustion start process is executed.

  Incidentally, the coldest environment assumed when the hydrogen-containing gas generating device is installed is, for example, an environment of 0 ° C., and the state in which the hydrogen-containing gas generating unit P is equal to the environmental temperature is, for example, four The temperature of the portion corresponding to the outlet of the reforming process gas in the transformer 3 through which the reforming process gas first flows is set equal to the environmental temperature (zero ° C.).

[Second Embodiment]
Next, a second alternative embodiment will be described. This second alternative embodiment exemplifies another form of the canceling means K in the above embodiment, and the other configuration is the same as the above embodiment. Therefore, only the configuration different from the above embodiment will be described below.

As shown in FIG. 14, the combustion exhaust gas composed of a heater-type heater provided with an electric heater in a portion of the exhaust gas passage 30 connecting the heating exhaust gas flow chamber 2 </ b> B and the shift catalyst cooler 4. A heating means L is provided.
This combustion exhaust gas heating means L includes a heating state in which the combustion exhaust gas after flowing through the steam generation unit S is heated to a temperature higher than the dew point of the steam charged in the transformer 3, and after passing through the steam generation unit S It is configured to be switchable to a heating stop state in which heating to the combustion exhaust gas is stopped.

  When the control unit C determines whether or not the combustion exhaust gas temperature detected by the combustion exhaust gas temperature sensor T4 is equal to or lower than the dew point temperature of the water vapor after performing the water vapor replacement process in the above-described startup process. When the flue gas temperature is higher than the dew point temperature of water vapor (100 ° C.), the flue gas heating means L is switched to the heating stop state. When the temperature is equal to or lower than the dew point temperature of the water vapor, the combustion exhaust gas heating means L is switched to a heating state.

  That is, when the temperature of the combustion exhaust gas after flowing through the steam generation unit S is equal to or lower than the dew point of the steam charged in the transformer 3 in the steam replacement process, the combustion exhaust gas heating means L It functions as a canceling means K that operates to cancel the flow of the shift catalyst cooler 4 at a temperature below the dew point, the heating state corresponds to the operating state of the canceling means K, and the heating stop state is This corresponds to the stop state of the canceling means K.

  Incidentally, the case where the flue gas heating means L is switched based on the detection information of the flue gas temperature sensor T4 in the same manner as in the above-described embodiment when switching the flue gas heating means L between the heating state and the heating stop state has been described. Similarly to the embodiment, switching may be performed based on whether or not the elapsed time since the combustion start process has exceeded the elapsed temperature increase time.

  Further, as the combustion exhaust gas heating means L, the configuration of the combustion exhaust gas heating means L such as a combustion type heater provided with a heating burner instead of a heater type heater provided with an electric heater is Various changes can be made.

[Other alternative embodiments]
Next, another embodiment will be described.
(A) In the above-described embodiment, the first alternative embodiment, and the second alternative embodiment, the case where the main operation for causing the fuel cell G to follow the power load has been described. You may implement with the form operated by a power generation output.
In this case, the hydrogen-containing gas generation unit P is operated so as to generate an amount of reformed gas (hydrogen-containing gas) corresponding to the rated power generation output.

(B) In the above embodiment, the first and second embodiments, the case where the reformed gas (hydrogen-containing gas) generated by the hydrogen-containing gas generation unit P is supplied to the fuel cell G has been described. However, the present invention can also be applied to the case where the reformed gas (hydrogen-containing gas) generated by the hydrogen-containing gas generator P is supplied to various reformed gas consuming apparatuses different from the fuel cell G.

(C) In the above embodiment, the first different embodiment, and the second different embodiment, the case where the hydrogen-containing gas generation unit P includes the selective oxidation unit U has been exemplified. The present invention can also be applied to a hydrogen-containing gas generation unit P that does not include

(D) In the above embodiment, the first different embodiment, and the second different embodiment, the case where the hydrogen-containing gas generation part P is configured in a form in which flat rectangular plate-like containers B are arranged in parallel is illustrated. However, the specific configuration of the hydrogen-containing gas generation unit P can be variously changed.

(E) In the above-described embodiment, the first alternative embodiment, and the second alternative embodiment, the raw fuel and water vapor charged in the hydrogen-containing gas generation part P and the fuel cell G are supplied to the reforming burner 1. Although illustrated, the raw fuel and water vapor filled in the hydrogen-containing gas generation part P and the fuel cell G may be caused to flow to a different location from the reforming burner 1 and discharged to the outside.
In this case, the raw fuel is burned by an external discharge burner and discharged as combustion exhaust gas.

(F) In the above-described embodiment, the first alternative embodiment, and the second alternative embodiment, the case where four transformers 3 are provided has been illustrated. However, in the case where a plurality of transformers 3 are provided as described above, The number of installations is not limited to four, but two, three, or five or more may be provided, or a single transformer 3 may be provided.

(G) In the above-described embodiment, first separate embodiment, and second separate embodiment, the steam generating section S, the reforming section R, the heat exchange section Ea for heating the raw fuel after desulfurization, and the heat exchange for heating the raw fuel before desulfurization The parts Eb and the CO conversion part T are arranged in the order of the steam generation part S, the reforming part R, the heat exchange part Ea for heating the raw fuel after desulfurization, and the CO conversion part T in a state where heat can be transferred between the adjacent parts. In the embodiment, the steam generation unit S, the reforming unit R, the heat exchange unit Ea for heating the raw fuel after desulfurization, the heat exchange unit Eb for heating the raw fuel before desulfurization, and the CO conversion unit T are provided in a separated state. You may carry out with.

(H) In the above-described embodiment, the first and second embodiments, the hydrogen-containing gas generation unit P is illustrated with a case where the desulfurization unit D including the desulfurizer 5 is integrally assembled. However, you may implement with the form which provides and comprises the desulfurization part D provided with the desulfurizer 5 separately.
Moreover, when using the raw fuel which does not need to remove sulfur content, you may implement by the form which abbreviate | omits the desulfurization part D. FIG.
That is, when a hydrocarbon-based raw fuel that does not contain a sulfur compound or has a small sulfur compound content is used, the desulfurization part D can be omitted.

(I) In the above embodiment, the first alternative embodiment, and the second alternative embodiment, the case of using natural gas-based city gas (13A) as the hydrocarbon-based raw fuel has been exemplified. For example, various substances such as propane gas and alcohols such as methanol can be used.

DESCRIPTION OF SYMBOLS 1 Reforming burner 3 Transformer 4 Transformation catalyst cooler 11 Reforming process chamber C Operation control means P Hydrogen-containing gas generating part J Flow path switching part K Canceling means L Combustion exhaust gas heating means S Steam generating part T1 Reforming temperature measuring means T4 Combustion exhaust gas temperature measurement means

Claims (6)

A reforming treatment chamber for generating a reforming treatment gas mainly composed of hydrogen gas by reforming a hydrocarbon-based raw fuel supplied in a mixed state of steam in a heating state by a reforming burner, the reforming treatment A steam generating section for generating steam mixed with the raw fuel supplied to the chamber by heating the water from the combustion exhaust gas of the reforming burner, and carbon monoxide contained in the reforming processing gas from the reforming processing chamber as a CO conversion catalyst And a hydrogen-containing gas generation unit including a conversion catalyst that converts the CO conversion catalyst by the flow of combustion exhaust gas after flowing through the water vapor generation unit,
When starting the hydrogen-containing gas generation unit that is stopped in a state in which the reforming chamber and the transformer are filled with raw fuel, a combustion start process for starting combustion of the reforming burner is performed, Thereafter, when the temperature of the reforming chamber is raised to a steam supply start temperature that can prevent thermal decomposition of the raw fuel and condensation of water vapor, the steam from the steam generator is supplied to the reforming chamber. Then, a steam replacement process is performed to replace the raw fuel charged in the reforming process chamber and the transformer with steam, and then the temperature of the reforming process chamber rises to a reforming process start temperature. A start-up operation method for a hydrogen-containing gas generation device that performs raw fuel supply processing for supplying raw fuel to the reforming treatment chamber in a mixed state of steam,
When the temperature of the combustion exhaust gas after flowing through the steam generation unit is equal to or lower than the dew point of the steam charged in the transformer in the steam replacement treatment, the combustion exhaust gas is cooled at a temperature equal to or lower than the dew point of the steam. A canceling means that operates to cancel the flow of the vessel is provided to be switchable between an operating state and a stopped state,
When the temperature of the combustion exhaust gas after flowing through the water vapor generating part is equal to or lower than the dew point of the water vapor charged in the transformer, the canceling means is switched to an operating state, and after flowing through the water vapor generating part When the temperature of the combustion exhaust gas is higher than the dew point of the water vapor charged in the transformer, the start-up operation method of the hydrogen-containing gas generation device that switches the elimination means to the stop state.   The canceling means includes, as the working state, a bypass flow state in which the flue gas after flowing through the steam generation part bypassing the shift catalyst cooler is passed, and the shift catalyst cooler as the stop state. 2. The start-up operation method for a hydrogen-containing gas generation device according to claim 1, wherein the flow-path switching unit is switchable to a cooling fluid state in which the combustion exhaust gas is allowed to flow after flowing through the water vapor generating unit.   As the working state, the canceling means heats the combustion exhaust gas after flowing through the water vapor generating section to a temperature higher than the dew point of the water vapor charged in the transformer, and the stop state includes the water vapor. 2. The start-up operation method for a hydrogen-containing gas generation apparatus according to claim 1, wherein the combustion exhaust gas heating means is switchable to a heating stop state in which heating to the combustion exhaust gas after flowing through the generator is stopped. Combustion exhaust gas temperature measuring means for measuring the temperature of the combustion exhaust gas after flowing through the water vapor generation unit is provided,
2. It is determined whether or not the temperature of the combustion exhaust gas after flowing through the steam generation unit is equal to or lower than the dew point of the steam charged in the transformer, based on the measurement result of the combustion exhaust gas temperature measuring means. The start operation method of the hydrogen-containing gas production | generation apparatus of any one of -3. Temperature rise until the temperature of the flue gas after flowing through the water vapor generating part becomes higher than the dew point of the water vapor charged in the transformer in the water vapor replacement process after the combustion start process is executed Predetermined elapsed time for use,
Based on whether or not the elapsed time since the start of the combustion process exceeds the elapsed time for temperature increase, the temperature of the combustion exhaust gas after flowing through the water vapor generating part is charged into the transformer. The start operation method of the hydrogen-containing gas production | generation apparatus of any one of Claims 1-3 which determines whether it is below the dew point of the water vapor | steam. A reforming treatment chamber for generating a reforming treatment gas mainly composed of hydrogen gas by reforming a hydrocarbon-based raw fuel supplied in a mixed state of steam in a heating state by a reforming burner, the reforming treatment A steam generating section for generating steam mixed with the raw fuel supplied to the chamber by heating the water from the combustion exhaust gas of the reforming burner, and carbon monoxide contained in the reforming processing gas from the reforming processing chamber as a CO conversion catalyst And a hydrogen-containing gas generation unit including a conversion catalyst that converts the CO conversion catalyst by the flow of combustion exhaust gas after flowing through the water vapor generation unit,
When starting the hydrogen-containing gas generation unit that is stopped in a state in which the reforming chamber and the transformer are filled with raw fuel, a combustion start process for starting combustion of the reforming burner is performed, Thereafter, when the temperature of the reforming chamber is raised to a steam supply start temperature that can prevent thermal decomposition of the raw fuel and condensation of water vapor, the steam from the steam generator is supplied to the reforming chamber. Then, a steam replacement process is performed to replace the raw fuel charged in the reforming process chamber and the transformer with steam, and then the temperature of the reforming process chamber rises to a reforming process start temperature. A hydrogen-containing gas generation device that performs raw fuel supply processing for supplying raw fuel to the reforming chamber in a mixed state of steam,
Reforming temperature measuring means for measuring the temperature of the reforming treatment chamber is provided,
The operation control means for controlling the operation of the hydrogen-containing gas generating section executes the combustion start processing when an activation command is issued, and then, based on the measurement result of the reforming temperature measuring means, the steam replacement Configured to perform a process and the raw fuel supply process,
When the temperature of the combustion exhaust gas after flowing through the steam generation unit is equal to or lower than the dew point of the steam charged in the transformer in the steam replacement treatment, the combustion exhaust gas is cooled at a temperature equal to or lower than the dew point of the steam. The canceling means that operates to cancel the flow of the vessel is provided to be switchable between an operating state and a stopped state,
When the operation control means has a temperature of the combustion exhaust gas after flowing through the water vapor generating section is equal to or lower than a dew point of water vapor charged in the transformer, the canceling means is switched to an operating state, and the water vapor generation is performed. When the temperature of the combustion exhaust gas after flowing through the section is higher than the dew point of the water vapor charged in the transformer, the hydrogen-containing gas generating device is configured to switch the elimination means to a stopped state.

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