JP4909339B2 - Operation method of hydrogen-containing gas generator - Google Patents

Description

  The present invention includes a water vapor generator that vaporizes supplied water to generate water vapor, a raw fuel supply unit that supplies raw fuel containing hydrocarbons, and a mixed gas containing the raw fuel and water vapor. The present invention relates to a method for operating a hydrogen-containing gas generation apparatus including at least a reformer that generates gas.

  Fuel cells generate electricity from hydrogen and oxygen, but usually the oxygen can be obtained from air and hydrogen can be obtained from gases containing alcohols and hydrocarbons. Here, when hydrogen is obtained from a gas containing hydrocarbons, it is necessary to reform the hydrocarbon gas into hydrogen using a hydrogen-containing gas generator.

  In a typical hydrogen-containing gas generator, a raw fuel supply unit that supplies raw fuel and a desulfurization that performs desulfurization of the raw fuel are provided on a main path from the supply of raw fuel containing hydrocarbons to the generation of hydrogen-containing gas. A desulfurizer to be used, a reformer that reacts the raw fuel after desulfurization with water to generate a hydrogen-containing gas, and carbon monoxide contained in the hydrogen-containing gas is converted to carbon dioxide using a carbon monoxide conversion catalyst. And a carbon monoxide selective oxidizer for further reducing the concentration of carbon monoxide contained in the hydrogen-containing gas by oxidizing a small amount of carbon monoxide in the hydrogen-containing gas that has passed through the transformer. It has been.

Here, when the city gas mainly composed of methane (CH ₄ ) is supplied from the raw fuel supply unit as the raw fuel gas, the reforming reaction performed in the reformer is expressed by the following chemical reaction formula. .

[Chemical formula 1]
CH ₄ + H ₂ O → 3H ₂ + CO

  Specifically, a step is performed in which the reforming catalyst provided in the reformer is heated to a temperature at which the reforming reaction is activated, and the raw fuel gas and steam react on the surface of the reforming catalyst. Is called. Then, the conversion process which converts carbon monoxide into carbon dioxide is performed using a copper-zinc-based or iron-chromium-based carbon monoxide conversion catalyst provided in the transformer.

  What should be noted when stopping the operation of the hydrogen-containing gas generation apparatus as described above is to ensure a stop state in which the activity of the catalyst does not decrease during the stop of the operation. In order to prevent oxidation of the catalyst, it is necessary to ensure a stopped state in which outside air (especially oxygen) does not enter the hydrogen-containing gas generator.

Therefore, when the operation is stopped, a method has been proposed in which the interior of the hydrogen-containing gas generating device is replaced with an inert gas such as nitrogen, and the hydrogen-containing gas generating device is filled with the inert gas. Securing the installation location of the inert gas supply facility and maintenance related to its maintenance are necessary.
In order to eliminate the need for securing the installation location of the inert gas supply equipment as described above and for maintenance related to its maintenance, the hydrogen-containing gas generator is sealed as an integral unit when the operation is stopped, and the interior is filled with raw fuel gas. A method of replacing with is proposed.
However, as described above, when the inside of the hydrogen-containing gas generating device is replaced with an inert gas and when it is replaced with the raw fuel gas when the operation is stopped, the large hydrogen-containing gas generating device is used. In this case, it is possible to provide a valve between the steam generator and the reformer to seal only the steam generator, but for example, a small size for use integrally with a polymer electrolyte fuel cell or the like. When a hydrogen-containing gas generation device is required, a space for providing a sealing device (for example, a sealing valve) for sealing only the steam generator cannot be secured. As a result, the above-mentioned problem that the generated water vapor spreads inside the hydrogen-containing gas generating device and the pressure inside the hydrogen-containing gas generating device rises has occurred. When replacing the inside of a hydrogen-containing gas generator with raw fuel gas, water remaining in the steam generator is vaporized by residual heat to become steam, and hydrogen is generated by reaction with the raw fuel gas in the device. As a result, the pressure inside the hydrogen-containing gas generator may increase.

  However, in the operation method as described above, the water present in the hydrogen-containing gas generation device is lowered until the temperature of the hydrogen-containing gas generation device and the catalyst is lowered after the operation is stopped or the water in the steam generator is exhausted. As a result, the pressure inside the sealed hydrogen-containing gas generating device rises, and the device may be damaged. However, even if the pressure inside the apparatus is released to the outside, the raw fuel gas etc. existing inside the hydrogen-containing gas generating apparatus cannot be released to the outside as it is, and the raw fuel gas etc. is burned separately. It was necessary to provide a device for this.

In addition, as described above, the water vapor generated by the progress of vaporization of water after the operation is stopped condenses on the catalyst as the temperature decreases, and the activity of the catalyst decreases, and the performance of generating the hydrogen-containing gas deteriorates. There was also a problem of doing.
Further, when the vaporization of water proceeds, impurities such as silica contained in the water are concentrated and attached as water scale inside the steam generator, thereby causing a problem that the thermal efficiency of the steam generator is lowered.

Next, when replacing the inside of the hydrogen-containing gas generating device with the purge gas when the operation is stopped, the hydrogen-containing gas generating device converts the combustible gas (raw fuel, hydrogen gas) in the gas in the device within the hydrogen-containing gas generating device into the hydrogen-containing gas generating device. A comparative example of the type of combustion using the originally provided configuration will be described.
As shown in FIG. 13 , the hydrogen-containing gas generation device of this comparative example replaces the inside of the hydrogen-containing gas generation device with nitrogen gas as a purge gas when the operation is stopped. When replacing the interior with nitrogen gas, the in-device gas existing inside the hydrogen-containing gas generating device is supplied to the reformer burner 3b for heating the reformer 3, and the raw fuel contained in the in-device gas Gas or hydrogen gas is burned in the reformer burner 3b.

In the figure, 1 is a desulfurizer that desulfurizes the raw fuel gas before being supplied to the reformer 3, and 11 is a raw fuel pump that pumps the raw fuel gas to the desulfurizer 1, 2 is a steam generator that generates steam by vaporizing water supplied through the reformed water supply path 12 using the combustion gas discharged from the reformer burner 3b of the reformer 3 as a heat source. A reformer that transforms carbon monoxide contained in the reformed gas reformed by the reformer 3 into carbon dioxide. Reference numeral 17 denotes a total amount of the transformed gas that is transformed by the transformer 4. A gas cooler that is supplied and cools in order to condense the water vapor in the supplied metamorphic gas, and 18 is a gas that separates the condensed water in which the water vapor in the metamorphic gas is condensed by cooling by the gas cooler 17. The water separator 5 is supplied from the steam separator 18. A carbon monoxide selective oxidizer that selectively oxidizes carbon monoxide contained in the shift gas, and 14 is a hydrogen-containing gas for desulfurization treatment of part of the shift gas from which water vapor has been separated by the steam separator 18 The desulfurization recycling path for mixing and supplying the raw fuel gas, and 22 is a fuel cell supply path for supplying the hydrogen-containing gas from the carbon monoxide selective oxidizer 5 to the fuel cell 8 as a power generation fuel gas. 9 is an off-gas path as a reformer supply path for supplying the exhaust fuel gas discharged from the fuel cell 8 as a combustion gas to the reformer burner 3b.
Then, a nitrogen gas passage 25 for supplying nitrogen gas as a purge gas from the desulfurizer 1 into the hydrogen-containing gas generator is provided, and the battery bypass passage 16 is branched from the fuel cell supply passage 22, and the battery bypass passage is provided. 16 is connected to the off-gas passage 9.

  V1 is a raw fuel valve for intermittently supplying the raw fuel gas to the hydrogen-containing gas generator, V2 is a generated gas outlet valve provided in the fuel cell supply path 22, and V3 is a reforming valve. A reforming water valve provided in the water supply path 12, V5 is a nitrogen gas valve provided in the nitrogen gas path 25, V6 is a battery outlet valve provided in the off-gas path 9, and V7 is a battery bypass path. 16 is a battery bypass valve, V8 is a desulfurization recycle valve provided in the desulfurization recycle path 14, and V9 is for selective oxidation for intermittently supplying the selective oxidation air to the carbon monoxide selective oxidizer 5. The air valve V10 is a combustion air valve that intermittently supplies the combustion air to the reformer burner 3b.

Next, a procedure when the operation is stopped will be described.
During operation, the raw fuel valve V1, the product gas outlet valve V2, the reforming water valve V3, the battery outlet valve V6, the desulfurization recycle valve V8, the selective oxidation air valve V9 and the combustion air valve V10 are open. The nitrogen gas valve V5 and the battery bypass valve V7 are closed.
When the operation is stopped, the raw fuel valve V1, the generated gas outlet valve V2, the battery outlet valve V6, the desulfurization recycle valve V8 and the selective oxidation air valve V9 are closed, and the battery bypass valve V7 is opened, and the state is changed to the gas in the apparatus. When the set time for discharging the gas in the apparatus is maintained while the set time for discharging elapses, the reforming water valve V3 is closed and the nitrogen gas valve V5 is opened, and further, the set time for nitrogen replacement is passed. The nitrogen gas valve V5 and the battery bypass valve V7 are closed.

  That is, in a state where the steam generation in the steam generator 2 is continued, the in-device gas in the hydrogen-containing gas generation device is pushed into the reformer burner 3b through the battery bypass passage 16 with the generated steam by the steam generator 2. The combustible gas such as raw fuel gas in the gas in the apparatus is combusted, and the combustion gas is discharged outside the apparatus, thereby replacing the inside of the hydrogen-containing gas generating apparatus with water vapor, and further, nitrogen gas as a purge gas The steam in the hydrogen-containing gas generating device is replaced with the hydrogen-containing gas generating device, and the hydrogen-containing gas generating device is sealed and stored. Incidentally, the set time for discharging the gas in the apparatus is set to be more than the time required for supplying the reformer burner 3b with the total amount or almost the entire amount of the gas in the apparatus remaining in the apparatus when the operation is stopped. The nitrogen replacement setting time is set to be longer than the time required to replace the water vapor in the hydrogen-containing gas generator with nitrogen gas.

However, in the operation method of the hydrogen-containing gas generation device of the comparative example, the vaporization of water existing in the hydrogen-containing gas generation device proceeds until the temperature of each catalyst decreases after the operation is stopped. Thus, there still remains a problem that the water vapor remaining in the hydrogen-containing gas generator condenses on each catalyst as the temperature decreases.
By the way, the reforming water valve V3 is closed, but the nitrogen gas valve V5 and the battery bypass valve V7 are kept open so that the nitrogen gas is always kept flowing, and the water vapor is stored outside the apparatus together with the nitrogen gas. Although it is conceivable to eliminate the problem that water vapor is condensed on each catalyst by discharging, there is a drawback in that the running cost becomes high.

Further, in the comparative example shown in FIG. 13 described above, it may be possible to use raw fuel gas as the purge gas instead of using nitrogen gas as the purge gas. In addition, there is a problem that the water vapor remaining in the hydrogen-containing gas generating device condenses on each catalyst as the temperature decreases.

  The present invention has been made in view of the above-described problems, and an object of the present invention is to provide an operation method that does not cause failure or deterioration in the hydrogen-containing gas generation device when the operation is stopped.

The first characteristic configuration of the operation method of the hydrogen-containing gas generation device according to the present invention for solving the above-mentioned problems is that vaporization of supplied water as described in claim 1 in the column of the claims. A steam generator for generating steam, a raw fuel supply unit for supplying a raw fuel containing hydrocarbons, and a reformer for generating a hydrogen-containing gas from a mixed gas containing the raw fuel and the steam. When the hydrogen-containing gas generator is shut down,
In a state in which the generation of water vapor by the water vapor generator is continued, the supply of raw fuel by the raw fuel supply unit is stopped, and a water vapor purge process is performed to discharge the gas in the apparatus within the hydrogen-containing gas generation apparatus,
Next, the supply of water to the steam generator is stopped, the water is discharged from the steam generator, and a gas purge process is performed to supply a purge gas into the hydrogen-containing gas generator,
Next, a sealing process is performed to seal the hydrogen-containing gas generator as a unit,
In the gas purge process, a water vapor separator is provided for separating water vapor remaining in the hydrogen-containing gas generator .

A second characteristic configuration of the operation method of the hydrogen-containing gas generation device according to the present invention for solving the above-described problems is that, in claim 1 , the reforming is performed in claim 1 as described in claim 2 in the column of claims. And configured to reform the raw fuel by heating the burner,
The gas in the apparatus discharged by the steam purge process is supplied to the burner and burned in the burner.

The third characteristic configuration of the operation method of the hydrogen-containing gas generation device according to the present invention for solving the above-mentioned problems is that, in claim 2 , the steam generation is as described in claim 3 in the column of claims. Configured to generate steam using the combustion gas from the burner of the reformer as a heat source,
The steam generation by the steam generator in the steam purge process is continued by supplying the gas in the apparatus to the burner.

A fourth characteristic configuration of the operation method of the hydrogen-containing gas generation device according to the present invention for solving the above-mentioned problems is as described in claim 2 or 3 , as described in claim 4 in the column of claims. Hydrogen-containing gas generator
A desulfurizer that desulfurizes the raw fuel before being supplied to the reformer;
A transformer for transforming carbon monoxide contained in the reformed gas reformed by the reformer into carbon dioxide;
A steam separator that is supplied with all or a part of the shift gas subjected to the shift treatment and separates water vapor in the supplied shift gas;
A carbon monoxide selective oxidizer that selectively oxidizes carbon monoxide contained in the shift gas supplied from the shift converter or the shift gas supplied from the steam separator;
A desulfurization recycle path for mixing and supplying the raw fuel with a part or all of the modified gas from which water vapor has been separated by the water vapor separator as hydrogen-containing gas for desulfurization treatment,
A fuel cell supply path for supplying the fuel cell with the hydrogen-containing gas from the carbon monoxide selective oxidizer as a fuel gas for power generation; and
A reformer supply path for supplying the exhaust fuel gas discharged from the fuel cell as a combustion gas to the burner of the reformer is provided.

A fifth characteristic configuration of the operation method of the hydrogen-containing gas generation device according to the present invention for solving the above-mentioned problems is that, in claim 4 , according to claim 5 , in the gas purging process, the gas purge process is performed. Is that water vapor remaining in the hydrogen-containing gas generator is separated by the water vapor separator.

The sixth characteristic configuration of the operation method of the hydrogen-containing gas generation device according to the present invention for solving the above-described problems is any one of claims 1 to 5 , as described in claim 6 in the column of claims. In the above, the raw fuel is used as the purge gas.

The seventh characteristic configuration of the operation method of the hydrogen-containing gas generation device according to the present invention for solving the above-described problems is any one of claims 1 to 5 , as described in claim 7 in the claims section. In this case, nitrogen gas is used as the purge gas.

The operation and effect will be described below.
According to the first characteristic configuration of the operation method of the hydrogen-containing gas generation device according to the present invention, when the steam purge process is performed, the gas in the apparatus is discharged outside the apparatus by the steam generated by the steam generator. When the inside of the apparatus is replaced with water vapor, and then the gas purge process is performed, water is discharged from the inside of the water vapor generator, and the water vapor in the apparatus is replaced with the supplied purge gas, and then the sealing process is performed. As a result, the hydrogen-containing gas generating device is hermetically sealed.
In other words, when the steam purge process is performed, the gas in the apparatus containing the raw fuel is replaced with water vapor, the raw fuel does not exist in the apparatus, and the generation of hydrogen due to the reforming of the raw fuel stops. It is possible to prevent an increase in pressure in the apparatus accompanying the generation.
When the gas purge process is performed after the steam purge process, water is discharged from the steam generator and the purge gas is supplied into the apparatus in a state where there is no increase in pressure in the apparatus due to hydrogen generation. Since the water vapor in the inside is replaced with the purge gas, the inside of the apparatus can be appropriately replaced with the purge gas so that the water and the water vapor do not remain or even if they remain.
When the sealing process is performed after the gas purge process, the hydrogen-containing gas generator is sealed with the purge gas sealed in a single state with little or no water and water vapor remaining inside. become.
Therefore, as described above, if the hydrogen-containing gas generating device is sealed as a single unit by the sealing process after sequentially performing the steam purge process and the gas purge process, even if water and steam remain or remain in the apparatus. Since the purge gas is sealed in a slight state, during operation stop, the pressure in the device increases with the progress of water vaporization, precipitation of impurities such as silica, and condensation of water vapor on each catalyst. In addition, it is possible to prevent intrusion of outside air that may adversely affect each catalyst.
In short, it has become possible to provide an operation method that does not cause failure or deterioration in the hydrogen-containing gas generating device when the operation is stopped.
Further, according to the first characteristic configuration, in the gas purge process, the water vapor remaining in the apparatus is separated by the water vapor separator, and the water vapor in the apparatus is replaced with the purge gas.
In other words, while supplying the purge gas in a state of being sealed in the apparatus, the water vapor remaining in the apparatus is separated and removed by the water vapor separator, so that the inside of the apparatus is purged with the purge gas while preventing the purge gas from being discharged to the outside. Can be replaced.
Incidentally, as a process of replacing the water vapor in the apparatus with the purge gas, it is conceivable to replace the inside of the apparatus with the purge gas while discharging the water vapor with the supply of the purge gas. In this case, the purge gas is not discharged to the outside. In order to do so, it is necessary to appropriately determine the timing at which the entire amount of water vapor is discharged, and to close the portion of the hydrogen-containing gas generating device where water vapor is discharged, which complicates the processing.
Therefore, the gas purge process can be simplified.

According to the second characteristic configuration of the operation method of the hydrogen-containing gas generation device according to the present invention, in the reformer, during normal operation, the combustion gas for reforming treatment is supplied to the burner and the combustion is performed. The raw fuel is reformed by heating the burner that burns with the working gas, and in the steam purge process, the exhausted internal gas is supplied to the burner and burned in the burner.
In other words, since the gas in the apparatus discharged by the steam purge process contains combustible gas such as raw fuel and hydrogen, the discharged gas in the apparatus is combusted. In order to heat the reformer so that the reforming process can be performed, a reformer heating burner which is originally provided is used.
Also, the combustible gas such as raw fuel and hydrogen is discharged to the outside by burning the combustible gas such as raw fuel and hydrogen contained in the internal gas when the gas in the device is supplied to the burner. There is no.
Therefore, it is not necessary to separately provide a purge processing dedicated combustion device for combusting the gas in the device discharged in the steam purge processing, so that the cost of the hydrogen-containing gas generation device that implements the operation method of the present invention is reduced. In addition, since combustible gases such as raw fuel and hydrogen are not discharged to the outside, the environment is excellent.

According to the third characteristic configuration of the operation method of the hydrogen-containing gas generator according to the present invention, in the steam generator, during normal operation, the reformer is supplied so as to be heated so as to be reformed. Steam is generated using the combustion gas from the burner that burns with the combustion gas as a heat source, and in the steam purge process, the generation of water vapor is continued using the combustion gas from the burner that burns with the supplied internal gas as the heat source. .
Therefore, it is not necessary to input energy separately for the continuation of the steam generation in the steam generator in the steam purge process, so that the running cost can be reduced.

According to the fourth characteristic configuration of the operation method of the hydrogen-containing gas generation device according to the present invention, in the desulfurizer, the raw fuel is desulfurized, and the desulfurized raw fuel is changed to a reformed gas containing hydrogen in the reformer. In the converter, the carbon monoxide contained in the reformed gas reformed in the reformer is converted to carbon dioxide, and all or a part of the modified gas is steamed. Steam supplied in the supplied shift gas is separated to the separator, and in the carbon monoxide selective oxidizer, it is included in the shift gas supplied from the shift converter or in the shift gas supplied from the steam separator. Carbon monoxide is selectively oxidized to produce a hydrogen-containing gas with a low carbon monoxide concentration, and part or all of the modified gas from which water vapor has been separated by the water vapor separator is mixed and supplied to the raw fuel through the desulfurization recycle path. The desulfurization process Waste gas discharged from a fuel cell, which is used as a power source and is supplied to a fuel cell as a power generation fuel gas through a supply path for the fuel cell. The gas is supplied as a combustion gas to the burner of the reformer through the reformer supply path, and the reforming catalyst is heated.
That is, without supplying hydrogen for desulfurization and energy for reforming treatment separately, for example, city gas or the like to which a sulfur compound as an odorant is added as a raw fuel, hydrogen having a low carbon monoxide concentration. It is possible to generate the contained gas.
Since the hydrogen-containing gas having a low carbon monoxide concentration is supplied to the fuel cell as a power generation fuel gas, for example, compared with a fuel cell of a phosphoric acid electrolyte type or the like, power generation is performed by carbon monoxide contained in the power generation fuel gas. It can also be used for solid polymer fuel cells whose performance tends to deteriorate.
Therefore, by adopting the characteristic configuration of the fourth aspect in the operation method of the second or third aspect, it is possible to use for desulfurization while taking advantage of the fact that failure or deterioration in the hydrogen-containing gas generation device does not occur when the operation is stopped. In a self-sustained operation that does not require the separate supply of hydrogen and energy for reforming treatment, a low carbon monoxide concentration suitable for power generation fuel gas of a polymer electrolyte fuel cell is obtained using raw fuel containing sulfur. It became possible to produce a hydrogen-containing gas.

According to the fifth characteristic configuration of the operation method of the hydrogen-containing gas generation device according to the present invention, the gas purge process uses a steam separator that is originally provided to separate the steam in the shift gas after the shift process. Thus, the water vapor remaining in the apparatus is separated, and the water vapor in the apparatus is replaced with the purge gas.
In other words, as described in the description of the function and effect of the characteristic configuration of claim 1 , in the purge process, the water vapor remaining in the apparatus is separated by the water vapor separator while supplying the purge gas in a state of being confined in the apparatus. Therefore, it is possible to simplify the gas purge process for replacing the inside of the apparatus with the purge gas while preventing the purge gas from being discharged to the outside.
In addition, since the water vapor separator that is originally provided is used for separating the water vapor remaining in the apparatus, it is not necessary to add a new configuration in order to simplify the gas purge process.
Therefore, it is possible to simplify the gas purge process while reducing the cost of the hydrogen-containing gas generation device .

According to the sixth characteristic configuration of the operation method of the hydrogen-containing gas generation device according to the present invention, since the raw fuel is used as the purge gas, the water vapor in the device is replaced by the raw fuel as the purge gas in the gas purge process .
Therefore, since the use of the raw fuel as a purge gas, together because separately there is no need to provide equipment for the purge gas supply, it is possible to achieve a cost reduction of the hydrogen-containing gas generating apparatus for implementing the operating method of the present invention, Running costs can be reduced.

According to the seventh characteristic configuration of the operation method of the hydrogen-containing gas generation device according to the present invention, since nitrogen gas is used as the purge gas, the water vapor in the device is replaced with nitrogen gas as the purge gas in the gas purge process.
Therefore, since excess purge gas is not discharged outside the apparatus, the amount of nitrogen gas as the purge gas required for the gas purge process can be reduced.

First Embodiment
Next, a first embodiment of the present invention will be described.
First, based on FIG. 1 , the structure of the hydrogen-containing gas production | generation apparatus of 1st Embodiment is demonstrated.
In the first embodiment, the hydrogen-containing gas generation device supplies a raw fuel supply passage 21 (corresponding to a raw fuel supply portion) that feeds raw fuel gas by the raw fuel pump 11 and supplies the raw fuel supply passage 21. A desulfurizer 1 that desulfurizes the raw fuel gas, a water vapor generator 2 that vaporizes the supplied water to generate water vapor, and a desulfurized raw fuel gas from the desulfurizer 1 is converted into water vapor from the water vapor generator 2. A reformer 3 that generates a hydrogen-containing gas by reforming, and a transformer 4 that converts carbon monoxide contained in the reformed gas reformed by the reformer 3 into carbon dioxide, The total amount of the metamorphic gas that has been subjected to the metamorphic treatment in the transformer 4 is supplied, the gas cooler 17 is cooled to condense the water vapor in the supplied metamorphic gas, and the gas cooler 17 cools the gas in the metamorphic gas. Moisture and moisture that separates the condensed water condensed with water vapor , A carbon monoxide selective oxidizer that selectively oxidizes carbon monoxide contained in the supplied shift gas by supplying a part of the shift gas from which condensed water is separated by the steam separator 18 5. Desulfurization recycle passage 14 for supplying mixed fuel gas to the raw fuel gas by using the remainder of the transformed gas from which condensed water has been separated by the steam separator 18 as hydrogen-containing gas for desulfurization treatment, carbon monoxide selective oxidizer 5 The reformer 3 can be reformed using the hydrogen-containing gas from the fuel cell as a power generation fuel gas, the fuel cell supply path 22 for supplying the fuel cell 8 and the exhaust fuel gas discharged from the fuel cell 8 as the combustion gas. In this way, an off-gas passage 9 is provided as a reformer supply passage to be supplied to the reformer burner 3b to be heated. Incidentally, the gas cooler 17 is configured to cool the metamorphic gas by heat exchange with water. It should be noted that the gas cooler 17 and the steam separator 18 function to separate water vapor in the shift gas that has been subjected to the shift process in the shift converter 4 during normal operation, and in the gas purge process, A water vapor separator that functions to separate water vapor remaining in the apparatus is configured.

  In addition, the desulfurizer 1, the reformer 3, the transformer 4, the gas cooler 17, the steam separator 18, and the carbon monoxide selective oxidizer 5 are connected in the gas processing flow path 6 in the order described, A steam path 7 for introducing steam from the steam generator 2 is connected to a gas processing flow path 6 that connects the desulfurizer 1 and the reformer 3, and the raw fuel gas and the steam generator desulfurized by the desulfurizer 1. 2 is supplied to the reformer 3 to generate a hydrogen-containing gas, and the hydrogen-containing gas generated in the reformer 3 is supplied to the converter 4 and the carbon monoxide selective oxidizer 5. Passing in order, the carbon monoxide concentration contained in the hydrogen-containing gas is reduced to generate a hydrogen-containing gas having a low carbon monoxide concentration, and the generated hydrogen-containing gas is used as a fuel gas for power generation to supply the fuel cell 22 Is supplied to the fuel cell 8 and is discharged from the fuel cell 8 after the power generation reaction. The reformer burner is burned with combustion air from the combustion air passage 10 in the reformer burner 3b to heat the reforming catalyst so that a reforming reaction is possible. It is constituted as follows.

  The raw fuel supply passage 21 is provided with a raw fuel valve V1 for intermittently supplying the raw fuel gas, the fuel cell supply passage 22 is provided with a product gas outlet valve V2, and the off-gas passage 9 is provided with a reformer burner. A battery outlet valve V6 for intermittently supplying the off gas to 3b is provided, and a combustion air valve V10 for intermittently supplying the combustion air to the reformer burner 3b is provided in the combustion air passage 10.

  Further, the battery bypass passage 16 is branched from a location upstream of the product gas outlet valve V2 in the fuel cell supply passage 22, and the battery bypass passage 16 is further downstream of the battery outlet valve V6 in the offgas passage 9. A battery bypass valve V7 that opens and closes the flow path is provided in the battery bypass path 16 connected to the location.

The steam generator 2 performs heat exchange in a state in which a combustion gas flow portion for allowing the combustion gas discharged from the reformer burner 3b to flow and an evaporation portion to which water is supplied in the reformed water supply path 12 are partitioned. The water is vaporized by using the combustion gas discharged from the reformer burner 3b of the reformer 3 as a heat source, and water vapor is generated. Is provided with a reforming water valve V3 for intermittently supplying the water.
Further, the steam generator 2 is provided with a reforming water discharge passage 13 for discharging the water therein, and the reforming water discharge passage 13 is provided with a reforming water discharge valve V4 for opening and closing the passage. is there.

The desulfurization recycle path 14 is connected to the gas phase portion of the steam separator 18 and the raw fuel supply path 21, and the desulfurization recycle path 14 is provided with a desulfurization recycle valve V8 that opens and closes the flow path.
A selective oxidation air passage 15 for supplying air for selective oxidation to the carbon monoxide selective oxidizer 5 is provided, and the selective oxidation air passage 15 is provided with a selective oxidation air valve V9 for opening and closing the flow passage. .

  The reformer 3 is provided with a temperature sensor 19 so as to detect the temperature at the highest temperature in the reforming reaction region inside the reformer 3, and the fuel cell supply path 22 is supplied with the pressure in the flow path. A pressure sensor 20 is provided for detecting the pressure in the hydrogen-containing gas generator. Fuel supply path 21, gas processing path 6, steam path 7, reformed water supply path 12, reformed water discharge path 13, desulfurizer 1, steam generator 2, reformer 3, transformer 4, carbon monoxide A gas treatment path formed by the selective oxidizer 5 and the fuel cell supply path 22, that is, the carbon monoxide selective oxidizer 5 from the desulfurizer 1 and the steam generator 2 through the reformer 3 and the transformer 4. Since the reformer 3 is at the highest temperature in the gas processing path leading to, the temperature sensor 19 detects the temperature of the highest temperature part in the gas processing path.

  The control part 23 which performs various control of the hydrogen containing gas production | generation apparatus is provided, The control part 23 performs opening / closing control of said each valve V1-V4 and V6-V10, and the temperature sensor 19 and pressure The detection information of each sensor 20 is configured to be input.

Next, of the operation methods of the hydrogen-containing gas generator configured as described above, a method for stopping the operation will be described.
When the operation is stopped, the supply of the raw fuel gas through the raw fuel supply passage 21 is stopped in a state in which the generation of water vapor by the water vapor generator 2 is continued, and the gas in the apparatus in the hydrogen-containing gas generation apparatus is discharged. A steam purge process is performed, and then the water purge to the steam generator 2 is stopped, the water is discharged from the steam generator 2 and the purge gas is supplied to the hydrogen-containing gas generator. Next, the sealing process which seals a hydrogen-containing gas production | generation apparatus integrally is performed. Furthermore, in the first embodiment, after performing the water vapor purge process, a temperature lowering process is performed to wait for the temperature in the hydrogen-containing gas generating device to drop to the set temperature, and the gas purge process is performed after the temperature lowering process. .

In the first embodiment, each of the processes when stopping the operation is configured to be executed by the control unit 23 as stop control. Hereinafter, the control unit 23 is based on FIGS. 2 and 3 . The control operation of the stop control in will be described.
The controller 23 stores a first set time, a second set time, a set temperature Ts, a first set pressure Ps1, and a second set pressure Ps2 that are set in advance as will be described later.

  During operation, the raw fuel valve V1, the product gas outlet valve V2, the reforming water valve V3, the battery outlet valve V6, the desulfurization recycle valve V8, the selective oxidation air valve V9 and the combustion air valve V10 are open. The reformed water discharge valve V4 and the battery bypass valve V7 are closed. That is, the raw fuel gas flows into the desulfurizer 1, and water is supplied to the steam generator 2 to generate steam, and the generated steam flows into the raw fuel gas desulfurized by the desulfurizer 1. Then, a hydrogen-containing gas having a low carbon monoxide concentration is generated in the reformer 3, the transformer 4, and the carbon monoxide selective oxidizer 5, and the generated hydrogen-containing gas is supplied to the fuel cell 8, and the reformer The burner 3b is supplied with off-gas and combustion air discharged from the fuel cell 8, the reforming catalyst is heated by the combustion of the off-gas, and part of the hydrogen-containing gas flowing out of the transformer 4 is desulfurized. The hydrogen-containing gas generator is operated in a form that is supplied to the desulfurizer 1 for use.

When a stop command is issued from an operation panel or the like (not shown), the control unit 23 closes the raw fuel valve V1, the generated gas outlet valve V2, the battery outlet valve V6, the desulfurization recycle valve V8, and the selective oxidation air valve V9, and Then, the battery bypass valve V7 is opened, the steam purge process start operation is performed, the steam purge process is started, and this state is maintained until the first set time elapses.
When the first set time elapses after the steam purge process start operation is performed, the temperature lowering process start operation is performed to close the battery bypass valve V7, the steam purge process is terminated, and the temperature lowering process is started. 19 is maintained until the detected temperature T becomes equal to or lower than the set temperature Ts.
When the detected temperature T of the temperature sensor 19 becomes equal to or lower than the set temperature Ts after the temperature lowering start operation, the reforming water valve V3 is closed and the reforming water discharge valve V4 is opened, and the raw fuel valve V1 is opened and the combustion is performed. A gas purge process start operation for closing the air valve V10 is performed to end the temperature lowering process and to start the gas purge process. This state is maintained until the second set time elapses. The discharge valve V4 is closed to perform a water discharge end operation for ending the discharge of water from the steam generator 2, and thereafter, when the detected pressure P of the pressure sensor 20 becomes equal to or higher than the first set pressure Ps1, the raw fuel valve V1 is turned on. The closed and sealed process is performed, and the gas purge process is completed.
Thereafter, when the detected pressure P of the pressure sensor 20 becomes equal to or lower than the second set pressure Ps2 lower than the first set pressure Ps1, the raw fuel valve V1 is opened, and when the detected pressure P becomes equal to or higher than the first set pressure Ps1, the raw fuel valve V1 is closed. The internal pressure maintaining process is performed to maintain the internal pressure between the second set pressure Ps2 and the first set pressure Ps1.

That is, in the steam purge process, the supply of the raw fuel gas and the desulfurization process gas to the desulfurizer 1 and the supply of the selective oxidation air to the carbon monoxide selective oxidizer are stopped, and the generation of the hydrogen-containing gas is stopped. Although stopped, the supply of water to the steam generator 2 is continued, so that the generation of steam is continued. Since the generation of water vapor is continued, the in-device gas remaining in the gas processing path by the generated water vapor is supplied to the reformer burner 3b through the battery bypass path 16, and the reformer Since the supply of combustion air to the burner 3b is continued, combustible gas such as raw fuel gas and hydrogen gas in the gas in the apparatus burns in the reformer burner 3b, and the combustion gas generates steam. After passing through the combustion gas flow part of the vessel 2 and contributing to the generation of water vapor, it is discharged, and the gas processing path, that is, the hydrogen-containing gas generation device is replaced with water vapor.
That is, the steam generation by the steam generator 2 in the steam purge process is continued by supplying the apparatus gas to the reformer burner 3b.

Then, when the steam purge processing start operation is performed, the entire amount or substantially the entire amount of the gas in the apparatus remaining in the gas processing path is supplied to the reformer burner 3b, and the combustible gas is combusted. Since it is desirable, the first set time is set to be equal to or longer than the time required for supplying the reformer burner 3b with the entire or substantially the entire amount of the residual apparatus gas when the steam purge processing start operation is performed. . Therefore, if the first setting time is too short, the pressure in the apparatus is likely to increase, and if it is too long, the pressure in the apparatus is too low, and the inside of the apparatus may be at a negative pressure.
Further, even if the steam purge process is performed, the combustible gas is not discharged outside the apparatus, so that it is not necessary to separately provide a dedicated combustion apparatus for the purge process for processing the combustible gas.

  After the steam purge process, the supply of the gas in the apparatus to the reformer burner 3b is stopped and the temperature lowering process is performed. In the temperature lowering process, the combustion of the reformer burner 3b is stopped, but the steam generator 2 Since the water supply to the water is continued, water is vaporized by the heat storage of the device, the temperature of the device is accelerated by the heat of vaporization, and the water vapor is filled in the device, so the inside of the device has a negative pressure. Thus, outside air can be prevented from entering the apparatus. Further, since the supply of combustion air to the reformer burner 3b is continued, the heat of the reformer 3 is carried by the combustion air and used as a heat source for water vaporization. The temperature drop will be further promoted.

Then, after the temperature lowering process, a gas purge process is performed in which the raw fuel gas is supplied into the apparatus as a purge gas. The raw fuel gas is at a high temperature and the amount of water vapor is insufficient for the reforming reaction. If the fuel is supplied, the raw fuel gas will be thermally decomposed and carbon will be deposited, which may be attached to each catalyst for desulfurization, modification and carbon monoxide selective oxidation including the reforming catalyst and deteriorate. The supply of the raw fuel gas as the purge gas must be performed in a state where the temperature in the apparatus is lowered to a temperature at which carbon deposition due to thermal decomposition can be prevented, and if the temperature falls too much, residual steam in the apparatus Therefore, it is necessary to supply the raw fuel gas as the purge gas in a state where the temperature in the apparatus is maintained at a temperature at which the condensation of water vapor can be prevented.
Therefore, the set temperature Ts is obtained by measuring the temperature distribution in the gas processing path in advance and obtaining the correlation between the temperature of the highest temperature portion and the temperature distribution, and the entire area in the gas processing path is thermally decomposed of the raw fuel gas. It is set within the temperature range of the highest temperature part when the temperature reaches a temperature at which the precipitation of carbon due to water vapor can be prevented and the condensation of water vapor can be prevented.
That is, the set temperature Ts is set to a temperature at which carbon deposition due to thermal decomposition of the raw fuel gas can be prevented and water vapor condensation can be prevented.
By the way, in the hydrogen-containing gas generator of the first embodiment, when using 13A city gas as the raw fuel gas, the set temperature is preferably set in the range of 150 to 450 ° C, and is preferably 250 to 350 ° C. It is more preferable to set the range.

In the gas purge process, water remaining in the steam generator 2 and the reformed water discharge passage 13 is discharged, so that there is almost no steam in the reformer 3, so that the raw fuel gas is supplied. However, the reforming reaction does not proceed, hydrogen is not generated, and the pressure in the apparatus can be prevented from rising.
Further, in the gas purge process, the raw fuel gas is used as a purge gas in the state where there is no gas outlet in parallel with the discharge of the water remaining in the steam generator 2 and the reforming water discharge passage 13. Most of the water vapor remaining in the apparatus before the raw fuel gas is supplied as the purge gas is condensed in the gas cooler 17 and the condensed water. Is separated by the steam separator 18 and discharged to the outside, so that even if the operation is stopped and the temperature in the apparatus is lowered, it is possible to prevent the problem that water vapor is condensed on each catalyst. .
In addition, when the temperature in the apparatus is reduced by the pressure maintaining process in the apparatus and the detected pressure P of the pressure sensor 20 becomes equal to or lower than the second set pressure Ps2, the raw fuel gas is injected, so the concentration of moisture in the apparatus Therefore, the problem that water vapor is condensed on each catalyst can be prevented more reliably.

Further, the reformed water discharge valve V4 is opened, and the water remaining in the steam generator 2 and the reformed water discharge path 13 is discharged through the reformed water discharge path 13. Since the pressure is applied by the raw fuel gas supplied as the purge gas, the discharge of the residual water from the steam generator 2 is promoted. Incidentally, the supply flow rate of the raw fuel gas is adjusted to a flow rate at which the pressure in the apparatus does not exceed the design pressure.
The second set time is set to be equal to or longer than the time required for the entire or substantially the entire amount of water remaining in the steam generator 2 to be discharged outside the apparatus.

  In the state where the inside of the apparatus is purged with the purge gas, it is necessary to prevent the outside air from entering the apparatus. Therefore, the first set pressure Ps1 and the second set pressure Ps2 are both positive pressures and the apparatus Set below the design pressure.

  In the state where the sealing process is performed, water is not generated in the steam generator 2, so that steam is not generated, so that the internal pressure of the hydrogen-containing gas generator is increased during the shutdown of the hydrogen-containing gas generator. In addition, since the gas treatment path is replaced with the raw fuel gas as the purge gas and there is almost no water vapor, water vapor does not condense on the catalyst, so that the catalyst used is deteriorated. There is nothing. In addition, since the raw fuel gas as the purge gas is sealed in the apparatus at a pressure higher than that of the outside air, the catalyst used or the like is not exposed to the outside air.

  Incidentally, the raw fuel supply path 21, the gas processing path 6, the steam path 7, the reformed water supply path 12, the reformed water discharge path 13, the desulfurizer 1, the steam generator 2, the reformer 3, the transformer 4, It is formed by the carbon monoxide selective oxidizer 5 and the fuel cell supply path 22, etc., and reaches from the desulfurizer 1 and the steam generator 2 to the carbon monoxide selective oxidizer 5 via the reformer 3 and the transformer 4. The state in which the gas processing path is sealed corresponds to the state in which the hydrogen-containing gas generation device is sealed together.

  When the operation of the hydrogen-containing gas generator is stopped, the product gas outlet valve V2 and the battery outlet valve V6 are closed, and the hydrogen-containing gas is sealed in the fuel cell 8, so that the fuel cell 8 is operated. As a process for stopping, a discharge operation is performed and a process of consuming residual hydrogen-containing gas is performed.

Hereinafter, the second to fourth embodiments of the present invention will be described, but the same components and components having the same functions as those of the first embodiment are denoted by the same reference numerals in order to avoid redundant description. The description is omitted, and a configuration different from the first embodiment will be mainly described.

[ Second Embodiment]
The second embodiment will be described below.
First, based on FIG. 4 , the structure of the hydrogen containing gas production | generation apparatus of 2nd Embodiment is demonstrated.
In the previous first embodiment, the gas cooler 17 and the steam / water separator 18 are provided in the gas processing flow path 6 that connects the transformer 4 and the carbon monoxide selective oxidizer 6, and the shift treatment is performed. In the second embodiment, the gas cooler 17 and the steam separator 18 are connected to the desulfurization recycle passage 14 in such a manner that the entire amount of the processing gas is supplied to the gas cooler 17 and the steam separator 18. Provided upstream of the desulfurization recycle valve V8, a part of the shift gas subjected to shift conversion is supplied to the gas cooler 17 and the steam / water separator 18, and the condensed water is separated by the steam / water separator 18. The entire modified gas is configured to be supplied to the recycle path 14, and the product gas discharge path 24 is branched from a location between the steam separator 18 and the desulfurization recycle valve V 8 in the desulfurization recycle path 14. That The formed gas discharge channel 24 connected to the reformer burner 3b via the off-gas passage 9, in its product gas discharge passage 24 is provided with a product gas discharge valve V11.
Hydrogen-containing gas generating device of the second embodiment, except that different from the first embodiment described above in terms of the above, are constituted similarly to the first embodiment.

Next, of the operation methods of the hydrogen-containing gas generator configured as described above, a method for stopping the operation will be described.
Also in the second embodiment, as in the first embodiment, when the operation is stopped, the supply of the raw fuel gas through the raw fuel supply path 21 is stopped in a state in which the generation of water vapor by the water vapor generator 2 is continued. A steam purge process for discharging the gas in the apparatus within the hydrogen-containing gas generator, and then stopping the supply of water to the steam generator 2 and discharging the water from the steam generator 2; and Then, a gas purge process for supplying a purge gas into the hydrogen-containing gas generator is performed, and then a sealing process for sealing the hydrogen-containing gas generator integrally is performed. Further, in the second embodiment, as in the first embodiment, after the steam purge process is performed, a temperature lowering process is performed to wait for the temperature in the hydrogen-containing gas generating device to drop to the set temperature. A gas purge process is performed after the process.

Also in the second embodiment, each process when stopping the operation is configured to be executed by the control unit 23 as stop control. Hereinafter, the control unit 23 is based on FIGS. 5 and 6 . The control operation of the stop control in will be described.
The control unit 23 stores the first set time, the second set time, the set temperature T, the first set pressure Ps1, and the second set pressure Ps2 as in the third embodiment.

During operation, the raw fuel valve V1, the product gas outlet valve V2, the reforming water valve V3, the battery outlet valve V6, the desulfurization recycle valve V8, the selective oxidation air valve V9 and the combustion air valve V10 are open. The reformed water discharge valve V4, the battery bypass valve V7, and the product gas discharge valve V1 are in a closed state, and a hydrogen-containing gas is generated as in the first embodiment.

When the stop command is issued, the control unit 23 closes the raw fuel valve V1, the generated gas outlet valve V2, the battery outlet valve V6, the desulfurization recycle valve V8, and the selective oxidation air valve V9, and the generated gas discharge valve V11. Is opened, the steam purge process start operation is performed, the steam purge process is started, and this state is maintained until the first set time elapses.
When the first set time elapses after the steam purge process start operation is performed, the temperature drop process start operation is performed to close the product gas discharge valve V11, and the steam purge process is terminated and the temperature decrease process is started. This is maintained until the detected temperature T of the sensor 19 becomes equal to or lower than the set temperature Ts.
When the detected temperature T of the temperature sensor 19 becomes equal to or lower than the set temperature Ts after the temperature lowering start operation, the reforming water valve V3 is closed and the reforming water discharge valve V4 is opened, and the raw fuel valve V1 is opened and the combustion is performed. A gas purge process start operation for closing the air valve V10 is performed to end the temperature lowering process and to start the gas purge process. This state is maintained until the second set time elapses. The discharge valve V4 is closed to perform a water discharge end operation for ending the discharge of water from the steam generator 2, and thereafter, when the detected pressure P of the pressure sensor 20 becomes equal to or higher than the first set pressure Ps1, the raw fuel valve V1 is turned on. The closed and sealed process is performed, and the gas purge process is completed.
Thereafter, when the detected pressure P of the pressure sensor 20 becomes equal to or lower than the second set pressure Ps2, the raw fuel valve V1 is opened. When the detected pressure P becomes equal to or higher than the first set pressure Ps1, the raw fuel valve V1 is closed. An in-apparatus pressure maintaining process is performed between Ps2 and the first set pressure Ps1.

The effect of each treatment is that the gas in the apparatus remaining in the gas treatment path when the steam purge treatment start operation is performed passes through the desulfurization recycle path 14, the product gas discharge path 24, and the offgas path 9, and the reformer burner 3b. Since it is the same as that of 1st Embodiment except being supplied to, it abbreviate | omits description.

[ Third Embodiment]
Hereinafter, a third embodiment will be described.
First, based on FIG. 7 , the structure of the hydrogen containing gas production | generation apparatus of 3rd Embodiment is demonstrated.
In the first embodiment, the raw fuel gas is used as the purge gas. In the fifth embodiment, the third embodiment is different from the first embodiment in that nitrogen gas is used as the purge gas. Different.
That is, in the third embodiment, a nitrogen gas passage 25 is connected to the raw fuel supply passage 21 for supplying raw fuel gas to the desulfurizer 1, and a nitrogen gas valve V5 is provided in the nitrogen gas passage 25, and the nitrogen gas valve V5 is provided. Is configured to supply nitrogen gas as a purge gas into the hydrogen-containing gas generator.
In the third embodiment, since nitrogen gas is used as the purge gas as described above, carbon deposition is prevented as in the case where the raw fuel gas is used as the purge gas as in the first embodiment. Since there is no need, nitrogen gas as the purge gas can be supplied regardless of the temperature in the apparatus, and the temperature sensor 19 provided in the first embodiment is omitted.
The hydrogen-containing gas generation apparatus of the third embodiment is configured in the same manner as in the first embodiment, except that the above-described point differs from the previous first embodiment.

Next, of the operation methods of the hydrogen-containing gas generator configured as described above, a method for stopping the operation will be described.
Also in the third embodiment, as in the first embodiment, when the operation is stopped, the supply of the raw fuel gas through the raw fuel supply path 21 is stopped in a state in which the generation of water vapor by the water vapor generator 2 is continued. A steam purge process for discharging the gas in the apparatus within the hydrogen-containing gas generator, and then stopping the supply of water to the steam generator 2 and discharging the water from the steam generator 2; and Then, a gas purge process for supplying a purge gas into the hydrogen-containing gas generator is performed, and then a sealing process for sealing the hydrogen-containing gas generator integrally is performed. However, in the third embodiment, since the nitrogen gas is used as the purge gas, the temperature lowering process performed in the first embodiment is not performed.

Also in the third embodiment, each process when stopping the operation is configured to be executed by the control unit 23 as stop control. Hereinafter, the control unit 23 is based on FIGS. 8 and 9 . The control operation of the stop control in will be described.
The control unit 23 stores the first set time, the second set time, the first set pressure Ps1, and the second set pressure Ps2 as in the first embodiment.

During operation, the raw fuel valve V1, the product gas outlet valve V2, the reforming water valve V3, the battery outlet valve V6, the desulfurization recycle valve V8, the selective oxidation air valve V9 and the combustion air valve V10 are open. The reformed water discharge valve V4, the nitrogen gas valve V5, and the battery bypass valve V7 are in a closed state, and a hydrogen-containing gas is generated as in the first embodiment.

When the stop command is issued, the control unit 23 closes the raw fuel valve V1, the generated gas outlet valve V2, the battery outlet valve V6, the desulfurization recycle valve V8, and the selective oxidation air valve V9, and the battery bypass valve V7. Open, perform the steam purge process start operation, start the steam purge process, and maintain this state until the first set time elapses.
When the first set time elapses after the steam purge processing start operation is performed, the nitrogen gas valve V5 and the reforming water discharge valve V4 are opened, and the reforming water valve V3, the battery bypass valve V7, and the combustion air valve V10 are opened. The gas purge process start operation is performed to end the steam purge process and the gas purge process. This state is maintained until the second set time elapses, and when the second set time elapses, the reformed water discharge valve V4. Is closed, and the water discharge end operation for ending the discharge of water from the steam generator 2 is performed. After that, when the detected pressure P of the pressure sensor 20 becomes equal to or higher than the first set pressure Ps1, the nitrogen gas valve V5 is closed and the sealing process is performed. To finish the gas purge process.
Thereafter, when the detected pressure P of the pressure sensor 20 becomes equal to or lower than the second set pressure Ps2, the raw fuel valve V1 is opened. When the detected pressure P becomes equal to or higher than the first set pressure Ps1, the raw fuel valve V1 is closed. An in-apparatus pressure maintaining process is performed between Ps2 and the first set pressure Ps1.

The effect of each process is that nitrogen gas is supplied as purge gas into the apparatus, and when the water vapor purge process is completed, the gas purge process is performed immediately, and the temperature lowering process performed in the first embodiment is omitted. in point, except that different from the first embodiment, the description thereof is omitted because it is similar to the first embodiment.
That is, in the third embodiment, since nitrogen gas is used as the purge gas, as in the case of using the raw fuel gas as the purge gas as in the first embodiment, the temperature in the apparatus causes carbon deposition due to thermal decomposition of the raw fuel gas. Since there is no need to wait for the temperature to fall to a temperature at which it can be prevented and condensation of water vapor can be prevented, nitrogen gas can be supplied into the apparatus as a purge gas as soon as the water vapor purge process is completed.

[ Fourth Embodiment]
Hereinafter, the fourth embodiment will be described.
First, based on FIG. 10 , the structure of the hydrogen-containing gas production | generation apparatus of 4th Embodiment is demonstrated.
The fourth embodiment is configured in the same manner as in the first embodiment, except that the battery bypass path 16 and the battery bypass valve V7 provided in the previous first embodiment are omitted.

Next, of the operation methods of the hydrogen-containing gas generator configured as described above, a method for stopping the operation will be described.
Also in the fourth embodiment, similarly to the first embodiment, when the operation is stopped, the supply of the raw fuel gas through the raw fuel supply path 21 is stopped in a state in which the generation of water vapor by the water vapor generator 2 is continued. A steam purge process for discharging the gas in the apparatus within the hydrogen-containing gas generator, and then stopping the supply of water to the steam generator 2 and discharging the water from the steam generator 2; and Then, a gas purge process for supplying a purge gas into the hydrogen-containing gas generator is performed, and then a sealing process for sealing the hydrogen-containing gas generator integrally is performed. Furthermore, in the fourth embodiment, similarly to the first embodiment, after performing the steam purge process, a temperature lowering process is performed to wait for the temperature in the hydrogen-containing gas generation device to drop to the set temperature, and the temperature decrease A gas purge process is performed after the process.

Also in the fourth embodiment, each process when stopping the operation is configured to be executed by the control unit 23 as the stop control. Hereinafter, the control unit 23 is based on FIGS. 11 and 12 . The control operation of the stop control in will be described.
As in the first embodiment, the control unit 23 stores the first set time, the second set time, the set temperature Ts, the first set pressure Ps1, and the second set pressure Ps2.

During operation, the raw fuel valve V1, the product gas outlet valve V2, the reforming water valve V3, the battery outlet valve V6, the desulfurization recycle valve V8, the selective oxidation air valve V9 and the combustion air valve V10 are open. The reforming water discharge valve V4 is in a closed state, and a hydrogen-containing gas is generated as in the first embodiment.

When the stop command is issued, the control unit 23 closes the raw fuel valve V1, the desulfurization recycle valve V8, and the selective oxidation air valve V9, performs the steam purge process start operation, and starts the steam purge process. The state is maintained until the first set time has elapsed.
When the first set time has elapsed after performing the steam purge processing start operation, the temperature lowering processing start operation is performed to close the product gas outlet valve V2 and the battery outlet valve V6, and the steam purge processing is terminated and the temperature lowering processing is started. This state is maintained until the detected temperature T of the temperature sensor 19 becomes equal to or lower than the set temperature Ts.
When the detected temperature T of the temperature sensor 19 becomes equal to or lower than the set temperature Ts after the temperature lowering start operation, the reforming water valve V3 is closed and the reforming water discharge valve V4 is opened, and the raw fuel valve V1 is opened and the combustion is performed. A gas purge process start operation for closing the air valve V10 is performed to end the temperature lowering process and to start the gas purge process. This state is maintained until the second set time elapses. The discharge valve V4 is closed to perform a water discharge end operation for ending the discharge of water from the steam generator 2, and then when the detected pressure P of the pressure sensor 20 becomes equal to or higher than the first set pressure Ps1, the nitrogen gas valve V5 is closed. The sealing process is performed, and the gas purge process is completed.
Thereafter, when the detected pressure P of the pressure sensor 20 becomes equal to or lower than the second set pressure Ps2, the raw fuel valve V1 is opened. When the detected pressure P becomes equal to or higher than the first set pressure Ps1, the raw fuel valve V1 is closed. An in-apparatus pressure maintaining process is performed between Ps2 and the first set pressure Ps1.

The effect of each process is that, in the steam purge process, the gas in the apparatus remaining in the gas process path at the time when the steam purge process start operation is performed passes through the fuel cell 8 and is changed through the off-gas path 9. Since it is the same as that of 1st Embodiment except being supplied to the quality organ burner 3b, description is abbreviate | omitted.

<Another Example>
< 1 >
In each of the first to fourth embodiments, the in-apparatus pressure maintaining process can be omitted. < 2 >
In each of the first to fourth embodiments described above, the opening / closing operation of each valve in executing each process is illustrated as being automatically performed using the control unit 23, but is performed manually. You may do it.

< 3 >
The purge gas is not limited to the raw fuel gas and the nitrogen gas exemplified in the above embodiment, and an inert gas such as argon or carbon dioxide gas can be used.

< 4 >
In each of the above embodiments, when the operation method of the present invention is carried out in a hydrogen-containing gas generation apparatus provided with the desulfurizer 1, the shift converter 4, and the carbon monoxide selective oxidizer 5 in addition to the reformer 3. However, the operation method of the present invention is to produce a hydrogen-containing gas in which any one, two, or all of the desulfurizer 1, the transformer 4 and the carbon monoxide selective oxidizer 5 are omitted. It can also be implemented in an apparatus.

Block diagram showing the configuration of a hydrogen-containing gas generator according to a first implementation embodiment The figure which shows the control action of the hydrogen containing gas production | generation apparatus which concerns on 1st Embodiment. The figure which shows the flowchart of control operation | movement of the hydrogen containing gas production | generation apparatus which concerns on 1st Embodiment. The block diagram which shows the structure of the hydrogen containing gas production | generation apparatus which concerns on 2nd Embodiment. The figure which shows the control action of the hydrogen containing gas production | generation apparatus which concerns on 2nd Embodiment. The figure which shows the flowchart of control operation | movement of the hydrogen containing gas production | generation apparatus which concerns on 2nd Embodiment. The block diagram which shows the structure of the hydrogen containing gas production | generation apparatus which concerns on 3rd Embodiment. The figure which shows the control action of the hydrogen containing gas production | generation apparatus which concerns on 3rd Embodiment. The figure which shows the flowchart of control operation | movement of the hydrogen containing gas production | generation apparatus which concerns on 3rd Embodiment. The block diagram which shows the structure of the hydrogen containing gas production | generation apparatus which concerns on 4th Embodiment. The figure which shows the control action of the hydrogen containing gas production | generation apparatus which concerns on 4th Embodiment. The figure which shows the flowchart of control operation | movement of the hydrogen containing gas production | generation apparatus which concerns on 4th Embodiment. Block diagram showing the configuration of a hydrogen-containing gas generating device according to a comparative example

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Desulfurizer 2 Steam generator 3 Reformer 3b Burner 4 Transformer 5 Carbon monoxide selective oxidizer 9 Reformer supply path 14 Desulfurization recycle path 17, 18 Steam separator 21 Raw fuel supply section 22 Fuel cell supply path

Claims (7)

Generates a hydrogen-containing gas from a water vapor generator that vaporizes the supplied water to generate water vapor, a raw fuel supply unit that supplies a raw fuel containing hydrocarbons, and a mixed gas containing the raw fuel and the water vapor At the time of shutdown of the hydrogen-containing gas generator comprising at least a reformer,
In a state in which the generation of water vapor by the water vapor generator is continued, the supply of raw fuel by the raw fuel supply unit is stopped, and a water vapor purge process is performed to discharge the gas in the apparatus within the hydrogen-containing gas generation apparatus,
Next, the supply of water to the steam generator is stopped, the water is discharged from the steam generator, and a gas purge process is performed to supply a purge gas into the hydrogen-containing gas generator,
Next, a sealing process is performed to seal the hydrogen-containing gas generator as a unit,
A method for operating a hydrogen-containing gas generation apparatus, wherein a steam separator for separating water vapor remaining in the hydrogen-containing gas generation apparatus is provided in the gas purge process. The reformer is configured to reform the raw fuel by heating a burner,
The method for operating a hydrogen-containing gas generation apparatus according to claim 1, wherein the gas in the apparatus discharged by the steam purge process is supplied to the burner and burned in the burner. The steam generator is configured to generate steam using a combustion gas from the burner of the reformer as a heat source,
The operation method of the hydrogen-containing gas generation device according to claim 2, wherein the steam generation by the steam generator in the steam purge process is continued by supplying the gas in the device to the burner. The hydrogen-containing gas generating device,
A desulfurizer that desulfurizes the raw fuel before being supplied to the reformer;
A transformer for transforming carbon monoxide contained in the reformed gas reformed by the reformer into carbon dioxide;
A steam separator that is supplied with all or a part of the shift gas subjected to the shift treatment and separates water vapor in the supplied shift gas;
A carbon monoxide selective oxidizer that selectively oxidizes carbon monoxide contained in the shift gas supplied from the shift converter or the shift gas supplied from the steam separator;
A desulfurization recycle path for mixing and supplying the raw fuel with a part or all of the modified gas from which water vapor has been separated by the water vapor separator as hydrogen-containing gas for desulfurization treatment,
A fuel cell supply path for supplying the fuel cell with the hydrogen-containing gas from the carbon monoxide selective oxidizer as a fuel gas for power generation; and
The hydrogen-containing gas generation according to claim 2 or 3, comprising a reformer supply path for supplying exhaust fuel gas discharged from the fuel cell as a combustion gas to the burner of the reformer. How to operate the device.   The operation method of the hydrogen-containing gas generation device according to claim 4, wherein in the gas purge process, water vapor remaining in the hydrogen-containing gas generation device is separated by the water vapor separator.   The operation method of the hydrogen-containing gas generation device according to claim 1, wherein the raw fuel is used as the purge gas.   The operation method of the hydrogen-containing gas generating apparatus according to claim 1, wherein nitrogen gas is used as the purge gas.