JP2017077999A - Hydrogen-containing gas producing apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hydrogen-containing gas producing apparatus that can suppress the reduction of a hydrogen-containing gas producing capability with the elapse of operation time.SOLUTION: Provided is a hydrogen-containing gas producing apparatus configured to execute a start-up temperature-increase process in which operation control means C controls desulfurization unit heating means 21 to temperature-increase a desulfurization treatment catalyst 1c to a start-up desulfurization unit temperature before starting the feed of a raw fuel gas to a desulfurization unit 1 to start the reforming process in a reforming unit 2, and in which there is provided preliminary heating means H for heating the desulfurization treatment catalyst 1c to a desulfurization unit preliminary heating temperature which is lower than the start-up desulfurization unit temperature, and the operation control means C is configured to execute the start-up temperature-increase process after actuating the preliminary heating means H to heat the desulfurization treatment catalyst 1c to a desulfurization unit preliminary heating temperature.SELECTED DRAWING: Figure 1

Description

  In the present invention, a desulfurization treatment catalyst is housed in a catalyst housing space inside a container, and a container-shaped desulfurization section that performs desulfurization treatment on the supplied raw fuel gas, and a part of the desulfurization section are heated from the outside. The desulfurization part heating means for heating the desulfurization process catalyst, and the reforming process catalyst is accommodated and connected to the desulfurization part so as to accept gas, and the raw fuel gas after the desulfurization process supplied from the desulfurization part is reformed A reforming section for generating a reformed gas containing hydrogen gas as a main component and an operation control means for controlling the operation, and the operation control means starts supplying raw fuel gas to the desulfurization section. Hydrogen content configured to perform start-up temperature rise processing to control the desulfurization section heating means to raise the temperature of the desulfurization treatment catalyst to the start-up desulfurization section temperature before starting the reforming process in the reforming section The present invention relates to a gas generator.

Such a hydrogen-containing gas generation device desulfurizes a hydrocarbon-based raw fuel gas in a desulfurization section, and reforms the desulfurized raw fuel gas in a reforming section to generate a hydrogen-containing gas containing hydrogen as a main component. The generated hydrogen-containing gas is consumed by, for example, a fuel cell.
The desulfurization unit is configured in a container shape in which a granular desulfurization treatment catalyst is accommodated in a catalyst accommodating space inside the container.
And start desulfurization treatment catalyst at start-up to speed up the desulfurization process as desired in the desulfurization section and shorten the start-up time required to generate the hydrogen-containing gas with the specified components In order to raise the temperature to the time desulfurization part temperature, a desulfurization part heating means for heating the desulfurization treatment catalyst by heating a part of the container-like desulfurization part from the outside is provided (for example, see Patent Document 1). .

  Further, as disclosed in Patent Document 1, in order to generate a hydrogen-containing gas having a lower carbon monoxide gas concentration, the reformed gas generated by the reforming treatment of the desulfurized raw fuel gas in the reforming section. The gas conversion gas is subjected to a modification process for transforming carbon monoxide into carbon dioxide, and the reformed gas subjected to the modification process in the modification part is subjected to a selective removal process for selectively removing carbon monoxide. A selective removal unit may be provided.

In this case, at the time of start-up, in order to shorten the start-up time in order to shorten the start-up time by accelerating that the metamorphic unit can perform the metamorphic process as desired and speeding up the selective removal process as desired by the selective-removal unit. In order to raise the temperature of the shift treatment catalyst to the start-up shift section temperature, a shift section heating means for heating the shift treatment catalyst by heating a part of the container-shaped shift section from the outside, and selective removal processing at the start-up In order to raise the temperature of the catalyst to the selective removal section at the time of activation, a selective removal section heating means for heating the selective removal treatment catalyst by heating a part of the container-shaped selective removal section from the outside is also provided.
The shift portion is also configured in a container shape in which the granular shift treatment catalyst is accommodated in the catalyst accommodating space inside the container, and the selective removal portion is also accommodated in the catalyst accommodating space inside the container. And configured in a container shape.

As shown in FIG. 6A, for example, the catalyst housing space R of the desulfurization unit 1 is formed in a flat container B, and the desulfurization treatment catalyst 1c is housed in the flat catalyst housing space R.
The container B is, for example, in a state where a rectangular flat plate-shaped partition member 52 is positioned between a pair of rectangular dish-shaped container forming members 51 as viewed in the thickness direction. Are connected by welding, and two flat internal spaces S are defined inside. For example, the desulfurization treatment catalyst 1c is accommodated in the catalyst accommodating space R by using one of the two internal spaces S as the catalyst accommodating space R, whereby the container-shaped desulfurization unit 1 is configured using the container B. The
Although not shown, the metamorphic part and the selective removal part are each configured in a container shape using a flat container B similar to that constituting the desulfurization part.

As shown in FIG. 6A, the desulfurization part heating means 21 is, for example, a rectangular electric heater in the thickness direction, and is constituted by a plate-like electric heater. The desulfurization treatment catalyst 1c is heated by applying a part of the container-shaped desulfurization part 1 from the outside, and is applied to the outer surface of the dish-shaped container forming member 51 that forms the catalyst housing space R. Has been.
Although not shown in the figure, the transformation part heating means and the selective removal part heating means are each configured in the same plate shape as the desulfurization part heating means 21, and like the desulfurization part heating means 21, the flat container B is provided. It is provided for.

JP 2002-356309 A

By the way, while the temperature raising process at the time of starting is executed, a part of the container constituting the desulfurization unit is locally heated from the outside by the desulfurization unit heating means. And the part heated locally in the container expands quickly and greatly in the surface direction compared with other parts, and it expands greatly locally, but the part heated locally Since the warping to the outside of the catalyst housing space is regulated by the desulfurization section heating means, the warping to the inside of the catalyst housing space is performed.
For example, as shown in FIG. 6 (a), when the desulfurization unit 1 is configured using a flat container B, when the startup temperature increase process is executed, as shown in FIG. 6 (b), The part heated by the desulfurization part heating means 21 in the dish-shaped container forming member 51 warps inward of the catalyst housing space R. FIG. 6B exaggerates the warped state in order to easily show the warped state of the dish-shaped container forming member 51.

  If a part of the container constituting the desulfurization section locally warps inward of the catalyst housing space, a compressive stress is applied to the desulfurization treatment catalyst housed in the catalyst housing space. There is a possibility that the heat treatment promotes the crushing of the desulfurization treatment catalyst, and the desulfurization treatment catalyst becomes finer. As the desulfurization catalyst becomes finer, the raw fuel gas flowing through the catalyst housing space tends to drift, so the area where the raw fuel gas is desulfurized in the catalyst housing space is narrowed. As a result, the processing capability of subjecting the raw fuel gas to the desulfurization treatment is reduced, and the hydrogen-containing gas generation capability is reduced.

  Similarly, in the metamorphic section and the selective removal section, there is a possibility that the conversion process catalyst and the selective removal process catalyst may become finer due to the collapse of the conversion process catalyst or the selective removal process catalyst. There is a possibility that the capacity is lowered, and as a result, the hydrogen-containing gas generation capacity is further lowered.

  This invention is made | formed in view of this situation, The objective is to provide the hydrogen containing gas production | generation apparatus which can suppress the production capability generation | occurrence | production of hydrogen containing gas accompanying progress of operation time.

In order to achieve the above object, a hydrogen-containing gas generating apparatus according to the present invention is a container-shaped device in which a desulfurization treatment catalyst is accommodated in a catalyst accommodating space inside a vessel and desulfurization treatment is performed on the supplied raw fuel gas. A desulfurization section, a desulfurization section heating means for heating the desulfurization treatment catalyst by heating a part of the desulfurization section from the outside, and a reforming treatment catalyst is accommodated and connected to the desulfurization section so as to receive gas, A reforming section for reforming the raw fuel gas after the desulfurization process supplied from the desulfurization section to generate a reformed gas containing hydrogen gas as a main component, and an operation control means for controlling operation;
Before the operation control means starts supplying the raw fuel gas to the desulfurization section and starts the reforming process in the reforming section, the operation control means should raise the temperature of the desulfurization treatment catalyst to the desulfurization section temperature at start-up. A hydrogen-containing gas generation device configured to perform a startup temperature increase process for controlling the desulfurization unit heating means, the characteristic configuration is:
Preheating means for heating the desulfurization treatment catalyst to a desulfurization part preheating temperature lower than the desulfurization part temperature at the start-up is provided,
The operation control means is configured to execute the temperature raising process at the start-up after operating the preheating means to heat the desulfurization treatment catalyst to the desulfurization part preheating temperature.

  According to the above characteristic configuration, after the desulfurization treatment catalyst is heated to the desulfurization part preheating temperature lower than the start-up desulfurization part temperature by the preheating unit, the desulfurization part heating unit performs a part of the container constituting the desulfurization unit. Is heated from the outside, whereby the desulfurization treatment catalyst is heated to the desulfurization part temperature at the time of startup.

That is, to constitute the preheating means, the desulfurization treatment catalyst is configured to be heatable in a state where thermal expansion is spread over a wide range of the container constituting the desulfurization section. Then, by operating the preheating means, the desulfurization treatment catalyst is heated to the desulfurization part preheating temperature in the middle from the normal temperature to the start-up desulfurization part temperature, thereby expanding the thermal expansion over a wide range of the containers constituting the desulfurization part. It becomes possible to spread.
Even if the desulfurization treatment catalyst is heated to the start-up desulfurization section temperature by heating from the outside of a part of the container by the desulfurization section heating means, the temperature of the start-up desulfurization section is increased by the operation of the preheating means. After the thermal expansion of the vessel constituting the desulfurization unit is spread over a wide range as much as possible at the preheating temperature of the desulfurization unit on the way to the desulfurization treatment catalyst by heating from the outside of a part of the vessel by the desulfurization unit heating means The temperature is raised to the desulfurization section temperature at startup. Then, compared with the case where the temperature of the desulfurization treatment catalyst is increased from normal temperature to the desulfurization temperature at start-up by heating from the outside of a part of the container by the desulfurization section heating means, the locality of the container constituting the desulfurization section is increased. Since thermal expansion can be suppressed, it can suppress that the container which comprises a desulfurization part warps locally to the inner side of a catalyst accommodation space.
Therefore, by suppressing the collapse of the desulfurization treatment catalyst at the time of start-up, it is possible to suppress a decrease in the desulfurization treatment capacity in the desulfurization section, and thus hydrogen that can suppress a decrease in the production capacity of the hydrogen-containing gas with the passage of operating time A contained gas generator can be provided.

  The hydrogen-containing gas generator according to the present invention is further characterized in that the preheating means heats the raw fuel gas supplied to the desulfurization section to a raw fuel gas preheating temperature lower than the start-up desulfurization section temperature. Raw fuel gas heating means, and preheating control means for supplying the raw fuel gas heated by the raw fuel gas heating means to the desulfurization section until the desulfurization treatment catalyst is heated to the desulfurization section preheating temperature. It is in the point comprised with.

According to the above characteristic configuration, the raw fuel gas heated to the raw fuel gas preheating temperature by the raw fuel gas heating means flows through the catalyst storage space of the desulfurization section that stores the desulfurization treatment catalyst, so that the catalyst storage space. The desulfurization treatment catalyst contained in the catalyst is heated uniformly over a wide range.
Since the heating of the desulfurization treatment catalyst in such a form is continued until the desulfurization treatment catalyst is heated to the desulfurization part preheating temperature, the vessel constituting the desulfurization part is preheated more uniformly over a wider range. It will be heated to a temperature close to the temperature, and the thermal expansion of the vessel constituting the desulfurization section can be spread over a wider range and evenly.

Then, after the thermal expansion of the vessel constituting the desulfurization part has spread over a wider range and evenly at the desulfurization part preheating temperature in the middle from the normal temperature to the start-up desulfurization part temperature, the desulfurization part heating is performed. By means, a part of the vessel constituting the desulfurization section is heated from the outside, and the desulfurization treatment catalyst is heated to the desulfurization section temperature at the start-up. Then, since the local thermal expansion of the container which comprises a desulfurization part can be further suppressed, the local curvature to the catalyst storage space inner side of the container which comprises a desulfurization part can further be suppressed.
Therefore, it is possible to further suppress the collapse of the desulfurization treatment catalyst at the time of start-up and further suppress the decrease in the desulfurization processing capacity in the desulfurization section, and thus further suppress the decrease in the generation capacity of the hydrogen-containing gas with the lapse of the operation time. be able to.

A further characteristic configuration of the hydrogen-containing gas generation device according to the present invention is that the shift treatment catalyst is accommodated in the catalyst accommodating space inside the container and is connected to the reforming unit so as to receive gas, and supplied from the reforming unit. A container-shaped shift section for performing a shift process for converting carbon monoxide to carbon dioxide with respect to the reformed gas, and a shift process for heating the shift catalyst by heating a part of the shift section from the outside. The selective removal treatment catalyst is housed in the catalyst housing space inside the container and is connected to the shift section so as to receive gas, and the reformed gas supplied from the shift section is supplied to the reformed gas after the shift process. A container-shaped selective removal unit that performs selective removal processing for selectively removing carbon monoxide, and a selective removal unit heating unit that heats the selective removal treatment catalyst by heating a part of the selective removal unit from the outside. Provided,
The operation control means is
In the start-up temperature increase process, the shift unit heating means is controlled to increase the temperature of the shift process catalyst to the start-up shift unit temperature, and the selective removal process catalyst is heated to the start-up selective removal unit temperature. Therefore, the selective removal portion heating means is configured to be controlled.

  According to the above characteristic configuration, the reformed gas generated by reforming the raw fuel gas in the reforming section passes through the shift section and the selective removal section in order, The selective removal section performs selective removal processing for selectively removing carbon monoxide on the reformed gas after the transformation treatment, so that carbon monoxide is transformed into carbon dioxide. A hydrogen-containing gas with a lower carbon oxide concentration is produced.

At the time of start-up, the raw fuel gas heated by the raw fuel gas heating means can pass through the desulfurization section and then flow in the order of the shift section and the selective removal section. Therefore, the container constituting the shift section The containers constituting the selective removal unit can also be heated more uniformly over a wide range, and the thermal expansion of each container can be spread over a wider range and evenly.
Then, after the thermal expansion of the container constituting the metamorphic part has spread over a wider range and evenly, the metamorphic part heating means heats a part of the container constituting the metamorphic part from the outside to start the transformation treatment catalyst. A part of the container constituting the selective removal section by the selective removal section heating means after the temperature is raised to the time-transforming section temperature and the thermal expansion of the container constituting the selective removal section has spread over a wider range and evenly. Is heated from the outside to raise the temperature of the selective removal treatment catalyst to the selective removal portion temperature at startup.
Then, since the local thermal expansion of each of the container constituting the metamorphic part and the container constituting the selective removal part can be suppressed, the catalyst accommodating space of each of the container constituting the metamorphic part and each of the containers constituting the selective removal part Local warping to the inward side can be suppressed.
Therefore, the reforming process and the selective removal process are performed on the reformed gas generated in the reforming unit to reduce the carbon monoxide gas, so that a hydrogen-containing gas having a lower carbon monoxide concentration is generated. The In such a hydrogen-containing gas generator that can generate a hydrogen-containing gas having a lower carbon monoxide concentration, in addition to suppressing a decrease in the desulfurization treatment capacity in the desulfurization section, the shift treatment catalyst and selection at the time of startup By suppressing crushing of the removal treatment catalyst, it is possible to suppress the degradation of the transformation treatment capacity in the transformation section and the selective removal treatment capacity in the selective removal section, thereby suppressing the decrease in the production capacity of the hydrogen-containing gas with the passage of operating time can do.

A further characteristic configuration of the hydrogen-containing gas generation device according to the present invention is a reforming burner for heating the reforming treatment catalyst to a reforming section temperature at startup,
A recycle path is provided in which the raw fuel gas heated by the raw fuel gas heating means is taken out after passing through at least the metamorphic portion and supplied to the reforming burner as combustion fuel. .

According to the above characteristic configuration, after being heated by the raw fuel gas heating means, the raw fuel gas that has passed through the desulfurization section and contributed to the heating of the desulfurization treatment catalyst has passed through at least the shift section and heated the shift treatment catalyst. Then, it is taken out by a recycling path and supplied to the reforming burner as a combustion fuel. Then, the reforming catalyst is heated by burning the raw fuel gas supplied through the recycling path in the reforming burner.
In other words, in order to accelerate the reforming process as desired in the reforming section and shorten the start-up time, the reforming burner is burned at the time of start-up, and the reforming process catalyst is modified at a predetermined start-up time. The temperature is raised to the material temperature.
Therefore, at the time of start-up, in order to suppress local warping of the vessel constituting the desulfurization section, the raw fuel gas heated by the raw fuel gas heating means and supplied to the desulfurization section is at least transformed after passing through the desulfurization section. It can be used for raising the temperature of the reforming catalyst at the time of start-up by taking it out after passing through the section and burning it with a reforming burner.
Therefore, it is possible to suppress a decrease in the hydrogen-containing gas generation capability with the lapse of operating time while suppressing a decrease in energy efficiency in generating the hydrogen-containing gas.

A further characteristic configuration of the hydrogen-containing gas generation device according to the present invention is an operation in which the operation control unit is configured to stop the supply of the raw fuel gas to the desulfurization unit and stop the reforming process in the reforming unit. During the stop, the desulfurization treatment catalyst is configured to perform a standby heating process for controlling the desulfurization unit heating means so as to maintain the desulfurization unit preheating temperature,
The preheating means includes the desulfurization section heating means and the operation control means.

According to the above characteristic configuration, the temperature of the desulfurization treatment catalyst is maintained at the preheating temperature of the desulfurization unit even during the operation stop when the supply of the raw fuel gas to the desulfurization unit is stopped and the reforming process in the reforming unit is stopped. Thus, the desulfurization part heating means is controlled.
Here, when the operation is stopped, after the reforming process is executed, the reforming process is performed for the first time after the hydrogen-containing gas generation device is installed in addition to the operation stop during which the supply of the raw fuel gas to the desulfurization unit is stopped. This includes the time during which the operation is stopped before the processing is performed.

In other words, during operation in which the raw fuel gas is supplied to the desulfurization unit and the reforming process is performed in the reforming unit, the desulfurization treatment catalyst is maintained at a desulfurization processing temperature at which desulfurization processing is possible. Since the container to be heated is heated to a temperature close to the desulfurization treatment temperature evenly over substantially the whole, the thermal expansion of the container constituting the desulfurization part is evenly distributed throughout.
When the operation is stopped in such a state that the thermal expansion of the container constituting the desulfurization unit is evenly distributed throughout the operation, standby heating processing is performed. In other words, when the temperature of the desulfurization treatment catalyst accommodated in the vessel constituting the desulfurization section is lowered near the desulfurization section preheating temperature, the desulfurization section heating is performed so that the temperature of the desulfurization treatment catalyst is maintained at the desulfurization section preheating temperature. Since the means is controlled, the state in which the thermal expansion of the container constituting the desulfurization part is evenly distributed is maintained.
In addition, when the standby heating process is performed before the reforming process is performed for the first time, the desulfurization section heating means is controlled so as to maintain the temperature of the desulfurization process catalyst at the desulfurization section preheating temperature. It is possible to continue the control of the desulfurization section heating means to such an extent that the thermal expansion of the containers constituting the desulfurization section is evenly distributed throughout.

And, at the time of start-up, the desulfurization part heating means is in a state where the thermal expansion of the vessel constituting the desulfurization part is evenly distributed at the desulfurization part preheating temperature in the middle from the normal temperature to the start-up desulfurization part temperature. To further suppress local thermal expansion of the vessel constituting the desulfurization unit by heating a part of the vessel constituting the desulfurization unit from the outside and raising the temperature of the desulfurization treatment catalyst to the desulfurization unit temperature at start-up Therefore, local warpage of the container constituting the desulfurization portion toward the inner side of the catalyst housing space can be further suppressed.
Therefore, it is possible to further suppress the collapse of the desulfurization treatment catalyst at the time of start-up and further suppress the decrease in the desulfurization processing capacity in the desulfurization section, and thus further suppress the decrease in the generation capacity of the hydrogen-containing gas with the lapse of operation time be able to.

  A further characteristic configuration of the hydrogen-containing gas generation device according to the present invention is that the operation control means starts from the time when the supply of the raw fuel gas to the desulfurization unit is stopped, and then the raw fuel to the desulfurization unit. When the operation stop period from the start of the gas supply to the start of the reforming process is longer than a predetermined setting period, the standby heating process is stopped.

According to the above characteristic configuration, when the operation stop period is longer than the predetermined set period, the standby heating process is stopped.
That is, even when the standby heat treatment for operating the desulfurization unit heating means is performed during the operation stop to maintain the temperature of the desulfurization treatment catalyst at the desulfurization unit preheating temperature, the operation stop period is longer than the predetermined set period. When it is long, the standby heating process is stopped, so that excessive consumption of energy can be prevented.
Therefore, it is possible to suppress a decrease in the hydrogen-containing gas generation capability with the lapse of operating time while suppressing a decrease in energy efficiency in generating the hydrogen-containing gas.

A further characteristic configuration of the hydrogen-containing gas generation device according to the present invention is that the shift treatment catalyst is accommodated in the catalyst accommodating space inside the container and is connected to the reforming unit so as to receive gas, and supplied from the reforming unit. A container-shaped shift section for performing a shift process for converting carbon monoxide to carbon dioxide with respect to the reformed gas, and a shift process for heating the shift catalyst by heating a part of the shift section from the outside. The selective removal treatment catalyst is housed in the catalyst housing space inside the container and is connected to the shift section so as to receive gas, and the reformed gas supplied from the shift section is supplied to the reformed gas after the shift process. A container-shaped selective removal unit that performs selective removal processing for selectively removing carbon monoxide, and a selective removal unit heating unit that heats the selective removal treatment catalyst by heating a part of the selective removal unit from the outside. Provided,
The operation control means is
In the start-up temperature increase process, the shift unit heating means is controlled to increase the temperature of the shift process catalyst to the start-up shift unit temperature, and the selective removal process catalyst is heated to the start-up selective removal unit temperature. And configured to control the selective removing unit heating means, and
In the standby heating process, the shift unit heating unit is controlled to maintain the shift process catalyst at a shift unit preheating temperature lower than the start-up shift unit temperature, and the selective removal process catalyst is selected at the start-up time. The selective removal unit heating means is controlled to maintain the selective removal unit preheating temperature lower than the removal unit temperature.

  According to the above characteristic configuration, the reformed gas generated by reforming the raw fuel gas in the reforming section passes through the shift section and the selective removal section in order, The selective removal section performs selective removal processing for selectively removing carbon monoxide on the reformed gas after the transformation treatment, so that carbon monoxide is transformed into carbon dioxide. A hydrogen-containing gas with a lower carbon oxide concentration is produced.

  During operation, the shift treatment catalyst is maintained at the shift treatment temperature at which shift treatment is possible, and the selective removal treatment catalyst is maintained at the selective removal treatment temperature at which selective removal treatment is possible. The containers constituting the removal unit are heated to a temperature close to the transformation treatment temperature and a temperature close to the selective removal treatment temperature almost uniformly throughout, so that the thermal expansion of the respective containers is evenly distributed throughout. Yes.

When the operation is stopped, a standby heating process is performed, the shift unit heating means is controlled to maintain the temperature of the shift process catalyst at the shift unit preheating temperature, and the temperature of the selective removal process catalyst is selectively removed. The selective removal unit heating means is controlled so as to maintain the temperature at the partial preheating temperature, so that the thermal expansion of each of the container constituting the metamorphic part and the container constituting the selective removal part is uniformly distributed. Is done.
In addition, when the standby heating process is performed before the reforming process is performed for the first time, the shift unit heating means is controlled so as to maintain the temperature of the shift process catalyst at the shift unit preheating temperature, and the selective removal process is performed. The selective removal unit heating means is controlled so as to maintain the temperature of the catalyst at the selective removal unit preheating temperature, and the control of the transformation unit heating unit and the selective removal unit heating unit is controlled by the transformation unit and the selective removal unit, respectively. It is possible to continue to such an extent that the thermal expansion of the container which comprises is spread over the whole.
And at the time of start-up, in the state where the thermal expansion of the container constituting the metamorphic part is evenly distributed over the whole at the metamorphic part preheating temperature from the normal temperature to the start-time metamorphic part temperature, the metamorphic part heating means To suppress local thermal expansion of the container constituting the shift section by heating a part of the container constituting the shift section from the outside and raising the temperature of the shift treatment catalyst to the start-up shift section temperature. Can do. Similarly, at the time of start-up, in the state where the thermal expansion of the container constituting the selective removal unit is spread evenly at the selective removal unit preheating temperature on the way from room temperature to the selective removal unit temperature at the start, The selective removal section heating means heats a part of the container constituting the selective removal section from the outside, and raises the selective removal treatment catalyst to the selective removal section temperature at start-up. Local thermal expansion can be suppressed. By these things, the local curvature to the catalyst accommodating space inner side of the container which comprises a metamorphic part, and the container which comprises a selective removal part can be suppressed.
Therefore, the reforming process and the selective removal process are performed on the reformed gas generated in the reforming unit to reduce the carbon monoxide gas, so that a hydrogen-containing gas having a lower carbon monoxide concentration is generated. The In such a hydrogen-containing gas generator that can generate a hydrogen-containing gas having a lower carbon monoxide concentration, in addition to suppressing a decrease in the desulfurization treatment capacity in the desulfurization section, the shift treatment catalyst and selection at the time of startup By suppressing crushing of the removal treatment catalyst, it is possible to suppress the degradation of the transformation treatment capacity in the transformation section and the selective removal treatment capacity in the selective removal section, thereby suppressing the decrease in the production capacity of the hydrogen-containing gas with the passage of operating time can do.

In the hydrogen-containing gas generation device according to the present invention, the catalyst containing space of each of the desulfurization unit, the shift conversion unit, and the selective removal unit is formed in a separate flat container,
The plurality of containers that form the catalyst housing spaces of the desulfurization section, the transformation section, and the selective removal section are arranged in a stacked state in the container thickness direction.

According to the above characteristic configuration, since the plurality of flat containers constituting the desulfurization section, the transformation section, and the selective removal section are arranged in a stacked state in the container thickness direction, the hydrogen-containing gas generation device can be made compact. Can be configured.
On the other hand, the containers constituting the desulfurization section, the transformation section, and the selective removal section are arranged in a stacked state, so that a portion that forms a surface perpendicular to the container thickness direction in each container is accommodated in the container thickness direction. Since warping to the outer side of the space is tightly regulated, it is easy to warp to the inner side of the catalyst housing space.
Therefore, by providing a preheating means and operating at the time of start-up, for the containers constituting the desulfurization section, the conversion section, and the selective removal section, the part forming the surface orthogonal to the container thickness direction in each container contains the catalyst. It is possible to effectively suppress warping to the inner side of the space.
Therefore, it is possible to effectively suppress a decrease in the production capacity of the hydrogen-containing gas with the lapse of operating time, while configuring the hydrogen-containing gas generation device in a compact manner.

The block diagram which shows the whole structure of the hydrogen containing gas production | generation apparatus which concerns on 1st Embodiment. A perspective view showing a container-like desulfurization section Longitudinal sectional view in the direction along the thickness direction in the vessel-shaped desulfurization section 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 whole structure of the hydrogen containing gas production | generation apparatus which concerns on 2nd Embodiment. Longitudinal sectional view of a container-shaped desulfurization section explaining a state in which the desulfurization treatment catalyst is crushed

Hereinafter, embodiments of the present invention will be described with reference to the drawings.
[First Embodiment]
First, a first embodiment will be described based on the drawings.
As shown in FIG. 1, the hydrogen-containing gas generation device P contains a granular desulfurization treatment catalyst 1c in the catalyst storage space R inside the container B (B3), and supplies the hydrocarbon-based raw fuel gas supplied thereto. A desulfurization section 1 that performs desulfurization treatment, a desulfurization section heater 21 (an example of a desulfurization section heating means) that heats the desulfurization treatment catalyst 1c by heating a part of the desulfurization section 1 from the outside, and a catalyst housing space R A raw fuel gas after desulfurization treatment (hereinafter referred to as desulfurization raw fuel gas) supplied from the desulfurization unit 1 is stored in the granular reforming catalyst 2c and connected to the desulfurization unit 1 so as to receive gas. ) To generate a reformed gas containing hydrogen gas as a main component, an operation control unit (an example of an operation control means) C for controlling the operation, and the like.

  The hydrogen-containing gas generation device P includes a steam generation unit J that generates steam by heating the reforming water supplied through the reforming water supply path 31 by the reforming water pump 30, and the reforming unit 2. A combustion unit 4 including a reforming burner 3 for heating the reforming catalyst 2c is provided.

  Further, in the hydrogen-containing gas generating device P, the granular shift treatment catalyst 5c is accommodated in the catalyst accommodating space R inside the container B (B4, B5, B6) and connected to the reforming unit 2 so as to receive gas. The reforming gas supplied from the reforming unit 2 is subjected to a shift process for converting carbon monoxide into carbon dioxide, and a part of the shift unit 5 is heated from outside to convert the catalyst. A shift portion heater 22 (an example of a shift portion heating means) that heats 5c, and a granular selective oxidation treatment catalyst (an example of a selective removal treatment catalyst) 6c are accommodated in a catalyst housing space R inside the container B (B7); Selection for selectively oxidizing carbon dioxide (an example of selective removal processing) for selectively oxidizing carbon monoxide to the reformed reformed gas supplied from the metamorphic section 5 and connected to the metamorphic section 5 so as to accept gas Oxidation part (an example of selective removal part) 6 and selection A selective oxidation section heater 23 (an example of the selective removal portion heating means) for heating the selective oxidation catalyst 6c by heating a portion of the unit 6 from the outside. And it is comprised so that hydrogen-rich hydrogen containing gas with a low carbon monoxide gas density | concentration (for example, 10 ppm or less) may be produced | generated.

The hydrogen-containing gas generated by the hydrogen-containing gas generation device P is supplied as fuel gas to the fuel cell G through the fuel gas supply path 32.
Since this fuel cell G is well known, a detailed description and illustration thereof will be omitted. For example, the fuel cell G is configured in a solid polymer type in which a plurality of cells each having a solid polymer membrane as an electrolyte layer are provided in a stacked state. The fuel gas is supplied to the fuel electrode of each cell from the hydrogen-containing gas generator P through the fuel gas supply path 32, and the air is supplied to the oxygen electrode of each cell by the reaction air blower 33, so that the electricity between hydrogen and oxygen is supplied. It is configured to generate electricity through a chemical reaction.

  Although not shown, an exhaust heat recovery unit that recovers the heat generated from the fuel cell G and heats the hot water in the hot water storage tank using the recovered heat to store the hot water in the hot water storage tank is also provided in the cogeneration system. It is configured.

  The raw fuel gas is supplied to the desulfurization unit 1 through the raw fuel gas supply path 35 by the raw fuel gas pump 34, and supplied to the desulfurization unit 1 to adjust the output power of the fuel cell G to the raw fuel gas supply path 35. A raw fuel gas flow rate adjusting valve 36 for adjusting the flow rate of the raw fuel gas is provided.

Next, based on FIG. 1, description will be added about each part of the hydrogen containing gas production | generation apparatus P. FIG.
The desulfurization unit 1 hydrogenates the sulfur compound in the raw fuel gas and adsorbs the hydride in a state where the desulfurization treatment catalyst 1c is heated to a predetermined desulfurization treatment temperature (for example, a range of 200 to 300 ° C.). And desulfurize. The desulfurization treatment catalyst 1c is configured by supporting a catalytic substance on a porous granular material such as ceramic. Incidentally, the desulfurization reaction in the desulfurization part 1 is an exothermic reaction.

Desulfurization raw fuel gas is supplied to the catalyst housing space R of the reforming unit 2 in a state where the steam generated by the steam generating unit J is mixed.
The reforming unit 2 then converts the hydrocarbon-based raw fuel gas into hydrogen gas and carbon monoxide in a state in which the reforming catalyst 2c is heated to a predetermined reforming processing temperature (for example, in the range of 600 to 700 ° C.). The reforming process is performed to a reformed gas containing the gas. For example, when the raw fuel gas is a natural gas-based city gas (for example, 13A) mainly composed of methane gas, the reforming process is performed by reacting the methane gas with water vapor according to the following reaction formula. The reforming treatment catalyst 2c is configured by supporting a catalytically acting substance such as ruthenium, nickel, platinum or the like on a porous granular material made of ceramic or the like. Incidentally, the reforming reaction in the reforming unit 2 is an endothermic reaction.

CH ₄ + H ₂ O → CO + 3H ₂

  In the state where the shift treatment catalyst 5c is heated to a predetermined shift treatment temperature (for example, in the range of 180 to 250 ° C.), the shift unit 5 converts the carbon monoxide gas in the reformed gas into steam with the following reaction formula. It is reacted and transformed into carbon dioxide gas. The shift treatment catalyst 5c is configured by carrying a catalytic substance such as platinum, ruthenium, rhodium, etc. on a porous granular material such as ceramic. Incidentally, the metamorphic reaction in the metamorphic part 5 is an exothermic reaction.

CO + H ₂ O → CO ₂ + H ₂

  The selective oxidation unit 6 is a monoxide remaining in the reformed gas after the shift treatment in a state where the selective oxidation treatment catalyst 6c is heated to a predetermined selective oxidation treatment temperature (for example, in the range of 80 to 150 ° C.). Carbon gas is selectively oxidized. The selective oxidation treatment catalyst 6c is configured by supporting a catalytic substance such as platinum, ruthenium, rhodium, etc. on a porous granular material made of ceramic or the like. Incidentally, the oxidation reaction in the selective oxidation unit 6 is an exothermic reaction.

  The steam generation part J is supplied through a reforming water supply path 31 by a heating exhaust gas flow part 7 for passing the combustion gas of the reforming burner 3 discharged from the combustion part 4 and a reforming water pump 30. And an evaporating unit 8 for evaporating the reforming water by heating with the heating exhaust gas flow unit 7.

  Furthermore, the hydrogen-containing gas generator P includes a heat exchanger Ea for desulfurized raw fuel that heats the desulfurized raw fuel gas desulfurized in the desulfurization unit 1 by the high-temperature reformed gas discharged from the reforming unit 2. The raw fuel heat exchanger Eb before desulfurization for heating the raw fuel gas to be desulfurized in the desulfurization section 1 by the reformed gas after heat exchange in the raw fuel heat exchanger Ea after desulfurization, and the exhaust gas flow for heating There is provided a cooling exhaust gas flow passage portion 9 for allowing the combustion gas discharged from the portion 7 to flow and cooling the shift portion 5 with the combustion gas.

  The desulfurized raw fuel heat exchanger Ea includes an upstream reformed gas flow section 10 through which the reformed gas discharged from the reforming section 2 flows, and a desulfurized raw fuel gas supplied to the reformed section 2. The desulfurized raw fuel flow section 11 is made to be able to exchange heat, and the pre-desulfurized raw fuel heat exchanger Eb flows the reformed gas discharged from the upstream reformed gas flow section 10. The downstream reformed gas flow section 12 to be made to flow and the raw fuel gas flow section 13 before desulfurization to flow the raw fuel gas to be supplied to the desulfurization section 1 are provided so as to be able to exchange heat.

In this embodiment, the reforming unit M is configured by integrally assembling the reforming unit 2, the combustion unit 4 and the like.
Based on FIG. 1, the reformer M will be described.
In the reformer M, a cylindrical inner cylinder 14 and an outer cylinder 15 are arranged coaxially, and both ends thereof are closed by an upper plate 16 and a bottom plate 17, and further, inside the inner cylinder 14, A cylindrical radiation tube 18 is configured to be coaxial with the inner tube 14 with one end fixed to the upper plate 16 and the other end separated from the bottom plate 17.
An annular catalyst housing space R is formed between the inner cylinder 14 and the outer cylinder 15, and the reforming catalyst 2c is filled in the catalyst housing space R. The inner cylinder 14, the outer cylinder 15, the upper plate 16, and the bottom plate 17 or the like constitutes the reforming unit 2.
The reforming burner 3 is provided so that the space in the inner cylinder 14 is a combustion space while being supported by the upper plate 16 coaxially with the inner cylinder 14, and the inner cylinder 14, the upper plate 16 and Combustion unit 4 is constituted by bottom plate 17 and the like.

The reformer M is arranged with the upper plate 16 facing upward.
The reforming burner 3 is connected with a combustion gas fuel supply passage 38 for supplying combustion gas fuel, and the combustion gas fuel pump 39 uses the city gas (13A, etc.) as the combustion gas fuel. It is provided to supply to the supply path 38. Further, an offgas passage 40 that guides offgas discharged from the fuel electrode of the fuel cell G in a state where hydrogen remains as combustion gas fuel, and a combustion air supply passage 42 that guides combustion air from the combustion air blower 41. Is connected to the combustion gas fuel supply passage 38 via the mixer 43.
Further, the combustion gas fuel supply passage 38 is provided with a combustion gas fuel flow rate adjustment valve 44 for adjusting the flow rate of the city gas.

In the upper plate 16, a gas processing flow path 45 through which the desulfurized raw fuel gas mixed with water vapor is communicated with the catalyst housing space R between the outer cylinder 15 and the inner cylinder 14 and is modified. Combustion gas passages 46 through which the combustion gas of the quality burner 3 flows are connected in a state where they communicate with the annular space between the inner cylinder 14 and the radiation cylinder 18.
Further, the reformer temperature sensor 27 is supported on the upper plate 16 so as to detect the temperature of the reforming catalyst 2c accommodated in the catalyst accommodating space R.
Further, the gas treatment flow path 45 through which the reformed gas reformed in the reforming unit 2 flows is communicated with the catalyst housing space R between the outer cylinder 15 and the inner cylinder 14 in the bottom plate 17. Connected with.

Then, the combustion gas fuel from the combustion gas fuel supply path 38 and the combustion air from the combustion air supply path 42 are mixed by the mixer 43 and the mixture is burned by the reforming burner 3. Thus, after the combustion gas flows downward in the radiation cylinder 18, it collides with the bottom plate 17 and flows upward in the annular space between the inner cylinder 14 and the radiation cylinder 18 and enters the combustion gas flow path 46. The exhausted heat of the combustion gas and the radiant heat from the radiant cylinder 18 are transferred to the inner cylinder 14 to heat the reforming catalyst 2c.
When heating the reforming treatment catalyst 2c to a reforming treatment temperature at which the reforming treatment is possible, the city gas flow rate is adjusted by the combustion gas fuel flow rate adjusting valve 44 so that the shortage of the off gas alone is compensated by the city gas. Is adjusted.

As shown in FIGS. 1 to 3, among the parts constituting the hydrogen-containing gas generation device P, each part other than the reformer M uses a flat container B that forms a flat internal space S therein. Configured.
The hydrogen-containing gas generation device P arranges the reformer M and the plurality of containers B in a stacked state in the container thickness direction with the reformer M positioned in the middle, and the plurality of containers B are disposed in the container. It is configured by pressing from both sides in the alignment direction (corresponding to the container thickness direction) by pressing means (not shown). The hydrogen-containing gas generation device P configured as described above is installed in a posture in which the container arrangement direction is substantially horizontal.

Each container B is made of a heat-resistant metal having heat conductivity such as stainless steel, and has a thickness between a pair of rectangular dish-shaped container forming members 51 as viewed in the thickness direction, as shown in FIGS. In a state where the rectangular flat plate-shaped partition member 52 is positioned in a direction view, the peripheral portion is welded and connected, and two flat internal spaces S are partitioned and formed inside.
The partition member 52 of the container B is provided with a communication port 53 that communicates the internal spaces S on both sides as necessary.

In this embodiment, the hydrogen-containing gas generation device P is configured using seven containers B. In addition, in order to clarify the distinction of the seven containers B, for the sake of convenience, reference numerals 1, 2, 3,... 7 indicating the arrangement order from the left in FIG. .
2 and 3 show the third container B3 from the left. Although details will be described later, this container B3 constitutes the desulfurization section 1 and the raw fuel flow section 13 before desulfurization. is there.

  As shown in FIG. 1, the exhaust gas flow passage 7 for heating is configured in the portion having the left internal space S in the leftmost container B1, and the evaporation processing unit 8 is configured in the portion having the right internal space S. ing. That is, the water vapor generating part J is configured by the leftmost container B1.

  The upstream reformed gas flow passage 10 is configured by the portion having the left internal space S in the second container B2 from the left, and the raw fuel flow passage 11 after desulfurization is formed by the portion having the right internal space S. Is configured. That is, the desulfurized raw fuel heat exchanger Ea is configured by the second container B2 from the left.

As shown in FIGS. 2 and 3, the left inner space S of the third container B3 from the left is used as a catalyst housing space R, and the desulfurization treatment catalyst 1c is housed in the catalyst housing space R so that the left inner space S The desulfurization part 1 is comprised by the part which has the space S, and the raw fuel flow part 13 before desulfurization is comprised by the part which has the internal space S of the right side.
The desulfurization section heater 21 is a plate-shaped electric heater having a rectangular shape in the thickness direction. This desulfurization section heater 21 is the left side of the third container B3 from the left, that is, the desulfurization section 1. It is provided in contact with the dish-shaped container forming member 51 that forms the side surface.
As shown in FIGS. 2 and 3, the dish-shaped container forming member 51 that forms the side surface of the desulfurization unit 1 is provided with a recess 51 d for inserting the desulfurization unit heater 21. In a state of being inserted into 51d, it is applied to the dish-shaped container forming member 51.

  A desulfurization part temperature sensor 24 is supported in the container B3 constituting the desulfurization part 1 so as to detect the temperature of the desulfurization treatment catalyst 1c accommodated in the catalyst accommodation space R.

The portion having the left internal space S in the fourth container B4 from the left constitutes the downstream reformed gas flow section 12, and the right internal space S is defined as the catalyst storage space R. The shift portion 5 is configured by the portion having the right internal space S that accommodates the shift treatment catalyst 5c.
The left inner space S in the fifth container B5 from the left is defined as a catalyst housing space R, the shift treatment catalyst 5c is housed in the catalyst housing space R, and the shift section 5 is configured by a portion having the left inner space S. The portion having the right internal space S constitutes the cooling exhaust gas flow portion 9.

The left and right internal spaces S in the sixth container B6 from the left are defined as catalyst housing spaces R, the shift treatment catalyst 5c is housed in each catalyst housing space R, and the shift section 5 is accommodated by the sixth container B6 from the left. Is configured.
That is, the metamorphosis part 5 comprised of the fourth container B4 from the left, the metamorphosis part 5 comprised of the fifth container B5 from the left, and the metamorphosis comprised of the sixth container B6 from the left The parts 5 are configured as a first stage, a second stage, and a third stage, respectively, so that the reformed gas is allowed to flow in order, and the transformation section 5 is provided in three stages.

  In the sixth container B6 from the left constituting the shift unit 5, the shift unit temperature sensor 25 is supported so as to detect the temperature of the shift process catalyst 5c stored in the catalyst storage space R.

The transformer heater 22 is also a plate-shaped electric heater having a rectangular shape in the thickness direction, and this transformer heater 22 is located between the fourth container B4 and the fifth container B5 from the left. Are provided in contact with the dish-shaped container forming member 51 that forms the side surfaces of the transformation parts 5 on both sides, and the same transformation part heater 22 is provided on the right side surface of the sixth container B6 from the left, that is, It is provided in contact with a dish-shaped container forming member 51 that forms the side surface of the transformation section 5.
Although not shown in the figure, the dish-shaped container forming member 51 to which the shift section heater 22 is applied is also provided with a recess 51d similar to the dish-shaped container forming member 51 to which the desulfurization section heater 21 is applied. In a state of being inserted into the recess 51d, the plate-shaped container forming member 51 is provided so as to be applied.

The seventh portion from the left, that is, the portion having the left inner space S in the rightmost container B7 is used for heat transfer adjustment without being used for anything, and the right inner space S is used as the catalyst housing space R, and the catalyst housing. The selective oxidation treatment catalyst 6c is accommodated in the space R, and the selective oxidation unit 6 is configured by a portion having the right internal space S.

  The selective oxidation unit temperature sensor 26 is supported in the rightmost container B7 constituting the selective oxidation unit 6 so as to detect the temperature of the selective oxidation treatment catalyst 6c accommodated in the catalyst accommodation space R.

The selective oxidation unit heater 23 is also a plate-shaped electric heater having a rectangular shape in the thickness direction. This selective oxidation unit heater 23 is the right side surface of the seventh container B7 from the left, that is, the selective oxidation unit. It is provided in a state of being applied to the dish-shaped container forming member 51 that forms the side surface of the portion 6.
Although not shown, the dish-shaped container forming member 51 to which the selective oxidation unit heater 23 is applied is also provided with a recess 51d similar to the dish-shaped container forming member 51 to which the desulfurization unit heater 21 is applied. Is provided in contact with the dish-shaped container forming member 51 in a state of being inserted into the recess 51d.

  As shown in FIG. 1, the seven containers B and the reformer M described above position the reformer M between the leftmost container B1 and the second container B2 from the left, Between the container B1 and the reformer M, between the reformer M and the second container B2 from the left, between the second container B2 from the left and the third container B3 from the left. In a state in which the heat insulating material 47 is disposed, the pressing means is pressed from both sides in the container arranging direction and arranged in close contact. Further, a cooling fan 48 is provided on the side of the rightmost container B7 constituting the selective oxidation unit 6 so as to ventilate the container B7.

  In arranging the seven containers B and the reformer M in the arrangement form as described above, the combustion amount of the reforming burner 3 is adjusted so as to maintain the reforming unit 2 at the reforming treatment temperature, In addition, the desulfurization unit 1 and the shift unit 5 are at the respective processing temperatures by adjusting the cooling capacity by adjusting the air flow rate of the cooling fan 48 so that the selective oxidation unit 6 is maintained at the selective oxidation treatment temperature. As described above, the heat transfer state between adjacent ones is set in advance.

  Next, the connection form of the flow path to each container B for supplying the fluid to each container B and discharging the fluid from each container B will be described with reference to FIG. In the internal space S in each container B, the fluid is supplied from the upper part and flows downward and discharged from the lower part, or the fluid is supplied from the lower part and flows upward. Since the fluid flows in the vertical direction so as to be discharged from the upper portion, each flow path is connected to the upper end portion or the lower end portion of the internal space S of each container B.

  The raw fuel gas supply path 35 is connected to the raw fuel flow section 13 before desulfurization, the desulfurization section 1 and the raw fuel flow section 11 after desulfurization, the raw fuel flow section 11 and reforming section 2 after desulfurization, The reforming section 2 and the upstream reformed gas flowing section 10 are connected to the upstream reformed gas flowing section 10 and the downstream reformed gas flowing section 12, respectively. The second stage transformation section 5, the third stage transformation section 5, the third stage transformation section 5, and the selective oxidation section 6 are respectively connected to the gas processing flow path 45. Further, the selective oxidation unit 6 and the fuel cell G are connected by a fuel gas supply path 32.

A raw material water preheating heat exchanger 49 is provided across the gas processing flow path 45 and the reforming water supply path 31 connecting the third stage shift section 5 and the selective oxidation section 6.
In addition, an ejector 29 for mixing water vapor into the desulfurized raw fuel gas is provided in the gas processing flow path 45 that connects the desulfurized portion 1 and the raw fuel flow-through portion 11 after desulfurization.

  The combustion part 4 and the heating exhaust gas flow part 7 are connected to the heating exhaust gas flow part 7 and the cooling exhaust gas flow part 9 via the combustion gas flow path 46, respectively, and discharged from the combustion part 4. The combustion gas to be discharged is configured to flow through the heating exhaust gas flow portion 7 and the cooling exhaust gas flow portion 9 in this order to be discharged.

  The reforming water supply path 31 is connected to the lower end of the evaporation processing unit 8, and the water vapor channel 50 that guides the water vapor generated in the evaporation processing unit 8 by heating by the heating exhaust gas flow unit 7 is provided in the ejector 29. It is connected.

  That is, the raw fuel gas supplied through the raw fuel gas supply path 35 is desulfurized in the desulfurization unit 1, and the steam generated in the evaporation processing unit 8 and supplied through the water vapor path 50 is supplied to the desulfurized raw fuel gas. The desulfurized raw fuel gas mixed with the ejector 29 and mixed with the water vapor is reformed in the reforming unit 2, and the reformed gas is supplied to the first, second, and third stage transformation units 5. Then, the reformed reformed gas is selectively oxidized in the selective oxidation unit 6 to generate a hydrogen-containing gas having a low carbon monoxide concentration, and the hydrogen-containing gas is used as a fuel gas to supply a fuel gas. The fuel cell G is supplied to the fuel cell G through 32.

Next, the control operation of the operation control unit C will be described.
As shown in FIG. 1, the operation control unit C manages time-series heat consumption data and time-series power consumption data, and sets the operation condition of the fuel cell G based on the management data. The learning unit Cp is provided, and the operation control unit C operates the hydrogen-containing gas generation device P to generate the hydrogen-containing gas so as to operate the fuel cell G under the operation conditions set by the learning unit Cp. Is configured to control.
Incidentally, the learning unit Cp sets the operation time zone of the fuel cell G as the operation condition of the fuel cell G, for example, by executing the power load follow-up operation for generating power following the power load. As a function for setting the operating condition of the fuel cell G based on the series heat consumption data and the time series power consumption data, a so-called learning function, various known methods can be used. The detailed explanation is omitted.

The operation control unit C starts the desulfurization treatment catalyst 1c when an operation start command is issued before starting the supply of the raw fuel gas to the desulfurization unit 1 and starting the reforming process in the reforming unit 2. The temperature of the desulfurization section heater 21 is controlled to raise the temperature to the time desulfurization section temperature, and the temperature increase at startup is performed to adjust the combustion amount of the reforming burner 3 to raise the temperature of the reforming catalyst 2c to the temperature of the reforming section at startup. After performing the process, the normal operation of supplying the raw fuel gas to the desulfurization unit 1 to generate the hydrogen-containing gas is executed, and when the operation stop command is instructed, the supply of the raw fuel gas to the desulfurization unit 1 is stopped. The stop process which performs is performed, and the driving | operation of the hydrogen containing gas production | generation apparatus P is stopped.
In this embodiment, since the shift unit 5 and the selective oxidation unit 6 are provided, the operation control unit C in the start-up temperature rising process, the shift unit to raise the temperature of the shift process catalyst 5c to the start-up shift unit temperature. The selective oxidation unit heater 23 is controlled so as to control the heater 22 and raise the selective oxidation treatment catalyst 6c to the startup selective oxidation unit temperature (an example of the startup selective removal unit temperature).

Here, the reforming part temperature at start-up is set to the above reforming process temperature (for example, in the range of 600 to 700 ° C.) or a temperature slightly lower than the reforming process temperature.
Similarly, the start-up desulfurization section temperature is the above-mentioned desulfurization treatment temperature (for example, in the range of 200 to 300 ° C.) or a temperature slightly lower than the desulfurization treatment temperature. For example, the startup selective oxidation temperature is set to the above selective oxidation treatment temperature (for example, in the range of 80 to 150 ° C.) or to the selective oxidation at a temperature slightly lower than the transformation treatment temperature. The temperature is set to be slightly lower than the processing temperature.
That is, when the start-up temperature raising process is executed, a desulfurization process in the desulfurization unit 1, a reforming process in the reforming unit 2, a modification process in the shift unit 5 and a selective oxidation process in the selective oxidation unit 6 are possible, or Therefore, when the temperature increase process at startup is executed, it is possible to start normal operation for supplying the raw fuel gas to the desulfurization unit 1 to generate the hydrogen-containing gas.

In the present invention, in order to suppress the crushing of the desulfurization treatment catalyst 1c accommodated in the catalyst accommodation space R of the desulfurization section 1, as shown in FIG. Preheating means H for heating to the part preheating temperature is provided, and after the operation control part C operates the preheating means H to heat the desulfurization treatment catalyst 1c to the desulfurization part preheating temperature, the temperature raising process at the start-up Is configured to run.
In this first embodiment, a raw fuel gas heater 60 (raw material) that heats the raw fuel gas supplied to the desulfurization unit 1 to a raw fuel gas preheating temperature that is higher than the desulfurization unit preheating temperature and lower than the startup desulfurization unit temperature. An example of fuel gas heating means), and preheating control means 61 for supplying the raw fuel gas heated by the raw fuel gas heater 60 to the desulfurization section 1 until the desulfurization treatment catalyst 1c is heated to the desulfurization section preheating temperature. Is provided.
The preheating unit H includes a raw fuel gas heater 60 and a preheating control unit 61. The preliminary heating control means 61 is configured using the operation control unit C.
Here, as a desulfurization part preheating temperature, the temperature which can fully suppress the local curvature of the container B3 which comprises the desulfurization part 1 so that collapse of the desulfurization process catalyst 1c can fully be suppressed, for example, 100 degreeC or more ( In the first embodiment, the temperature is set to 100 ° C., and the raw fuel gas preheating temperature is set to, for example, a temperature of 200 ° C. or less (200 ° C. in the first embodiment).

The raw fuel gas heater 60 is composed of an electric heater and is provided so as to heat the raw fuel gas flowing through the raw fuel gas supply path 35.
The raw fuel gas supply path 35 is provided with a raw fuel gas preheating temperature sensor 62 that detects the temperature of the raw fuel gas heated by the raw fuel gas heater 60.

Further, a recycle path 63 is provided in which the raw fuel gas heated by the raw fuel gas heater 60 is taken out after passing through the selective oxidation unit 6 and is supplied to the reforming burner 3 as combustion fuel.
The recycle path 63 is connected to the fuel gas supply path 32 via the preheating gas switching three-way valve 64, and is connected to the combustion gas fuel supply path 38 via the mixer 43. The preheating gas switching three-way valve 64 is in a normal flow path state in which the upstream side of the preheating gas switching three-way valve 64 in the fuel gas supply passage 32 and the downstream side of the preheating gas switching three-way valve 64 are in communication with each other. In addition, the fuel gas supply path 32 is configured to be selectively switchable to a recycle flow path state in which the upstream side of the preheating gas switching three-way valve 64 and the recycle path 62 are in communication with each other.
That is, the raw fuel gas heated to the raw fuel gas preheating temperature by the raw fuel gas heater 60 is taken out after passing through the desulfurization section 1, the reforming section 2, the three-stage shift section 5 and the selective oxidation section 6 in this order. Thus, the reformer burner 3 is configured to be supplied as a combustion fuel.

  Further, in the first embodiment, when the operation start command is issued, when the temperature of the desulfurization treatment catalyst 1c is equal to or higher than the preheating avoidance temperature set to a predetermined temperature that is slightly lower than the desulfurization section preheating temperature. The start-up temperature raising process is executed without operating the preheating means H. Incidentally, the preheating avoidance temperature is set to a temperature lower by about 5 ° C., for example, than the desulfurization part preheating temperature.

The preheating means H is actuated, and the preheating treatment time, which is the time required for the treatment for heating the desulfurization treatment catalyst 1c to the desulfurization section preheating temperature (hereinafter sometimes referred to as preheating treatment), and preheating The startup temperature increase process time, which is the time required for the startup temperature increase process after the process is executed, is known in advance. Therefore, during the execution of the learning operation in which the fuel cell G is operated under the operation condition set in the learning unit Cp, at least the preliminary heating is performed from the start of the operation time zone of the fuel cell G set in the learning unit Cp. An operation start command is instructed based on reaching a time point that is the sum of the processing time and the temperature increase processing time at startup, and an operation stop command is issued based on reaching the end point of the operation time zone. It is configured to be commanded.
Although not shown, an operation switch for instructing an operation start command and an operation stop command to the operation control unit C by manual operation is also provided. That is, it is possible to pause the learning operation by using this operation switch and to issue an operation start command by human operation.

The control operation of the operation control unit C will be described.
As shown in the flowchart of FIG. 4, when the operation start command is instructed, the operation control unit C reads the detected temperature of the desulfurization unit temperature sensor 24 and the detected temperature is lower than a predetermined preheating avoidance temperature. After starting the preheating process, perform the start-up temperature rise process. If the detected temperature is equal to or higher than the preheat avoidance temperature, immediately execute the start-up temperature rise process without executing the preheat process. (Steps # 1 to # 4).
When the temperature raising process at start-up is completed, normal operation is executed until an operation stop command is issued. When the operation stop command is issued, stop operation is executed to stop the operation (steps # 5 to 7). .

  In the preheating process, the operation control unit C switches the preheating gas switching three-way valve 64 to the recycle flow path state, and then operates the raw fuel gas pump 34 and the combustion air blower 41 to burn the reforming burner 3. At the same time, the raw fuel gas heater 60 is operated, and the raw fuel gas flow rate adjusting valve 36 is controlled so that the flow rate of the raw fuel gas is adjusted to a predetermined preheating flow rate, and the raw fuel gas preheating temperature sensor 62 is controlled. The heating amount (supply power) of the raw fuel gas heater 60 is adjusted so that the detected temperature becomes the raw fuel gas preheating temperature.

  Further, when the temperature detected by the reforming unit temperature sensor 27 approaches the carbon deposition preventing temperature (for example, 300 ° C.) during the preheating process, the operation control unit C prevents the detected temperature from becoming higher than the carbon deposition preventing temperature. In addition, the raw fuel gas flow rate adjustment valve 36 is controlled so that the flow rate of the raw fuel gas is less than the preheating flow rate.

  Then, when the temperature detected by the desulfurization section temperature sensor 24 reaches the desulfurization section preheating temperature, the operation control section C stops the raw fuel gas pump 34 and the raw fuel gas heater 60, and passes the preheating gas switching three-way valve 63 through the normal flow path. Switch to the state, finish the preheating process, and execute the temperature raising process at startup.

  In the start-up temperature raising process, the operation control unit C operates the combustion gas fuel pump 39 and the combustion air blower 41 to burn the reforming burner 3 and the temperature detected by the reforming unit temperature sensor 27 is high. The combustion gas fuel flow rate adjusting valve 44 is controlled so as to adjust the combustion amount of the reforming burner 3 so as to be the reforming section temperature at the start, and the temperature detected by the desulfurization section temperature sensor 24 is the start desulfurization section. The heating amount (supply power) of the desulfurization unit heater 21 is adjusted so that the temperature becomes the temperature, and the heating amount (supply) of the transformation unit heater 22 is set so that the detection temperature of the transformation unit temperature sensor 25 becomes the startup transformation unit temperature. Power) and the heating amount (supplied power) of the selective oxidation unit heater 23 is adjusted so that the temperature detected by the selective oxidation unit temperature sensor 26 becomes the selective oxidation unit temperature at startup. Although the flow rate of the combustion air to the reforming burner 3 is adjusted so as to match the combustion amount of the reforming burner 3, such a method for adjusting the combustion air flow rate is well known. Since there is, explanation is omitted.

  In the operation control unit C, the temperature detected by the reforming unit temperature sensor 27 becomes the reforming unit temperature at startup, the temperature detected by the desulfurization unit temperature sensor 24 becomes the startup desulfurization unit temperature, and the transformation unit temperature sensor When the detected temperature 25 becomes the start-time metamorphic portion temperature and the detection temperature of the selective oxidation portion temperature sensor 26 becomes the start-time selective oxidation portion temperature, the desulfurization portion heater 21, the shift portion heater 22, and the selective oxidation portion heater 23 are turned on. Stop and end the temperature increase process at startup.

When the start-up temperature raising process is completed, the operation control unit C operates the raw fuel gas pump 34, the reforming water pump 30, and the cooling fan 48 to start normal operation.
In this normal operation, the operation control unit C is configured to adjust the combustion amount of the reforming burner 3 so as to maintain the temperature detected by the reforming unit temperature sensor 27 at the reforming processing temperature. 44, and the air flow rate of the cooling fan 48 is adjusted so that the temperature detected by the selective oxidation unit temperature sensor 26 is maintained at the selective oxidation temperature, and the output of the fuel cell G follows the power load. The raw fuel gas flow rate adjustment valve 36 is controlled so as to adjust the flow rate of the raw fuel gas supplied to the desulfurization unit 1 in order to adjust the electric power within the output power adjustment range. The flow rate of the reforming water supplied to the evaporation processing unit 8 is adjusted so as to correspond to the flow rate of the raw fuel gas supplied to the desulfurization unit 1. Since various known methods can be used as the adjustment method, description thereof is omitted.

  In the stop process, the operation control unit C extinguishes the reforming burner 3, stops the cooling fan 48, stops supplying raw fuel gas by stopping the raw fuel gas pump 34, and reforming water by stopping the reforming water pump 30. Each process such as supply stop is performed according to a predetermined procedure, and the normal operation is terminated.

In the hydrogen-containing gas generation device P of the first embodiment, in the preheating process, the raw fuel gas heated to the raw fuel gas preheating temperature by the raw fuel gas heater 60 is converted into the desulfurization unit 1, the reforming unit 2, and the third stage. After passing through the transformation section 4 and the selective oxidation section 6 in this order, the reforming section 4 and the selective oxidation section 6 are supplied to the reforming burner 3 through the recycling path 63 and burned by the reforming burner 3.
The desulfurization treatment catalyst 1c accommodated in the catalyst accommodation space R of the desulfurization section 1 and the shift treatment catalyst accommodated in the catalyst accommodation space R of the shift section 5 by the flow of the raw fuel gas heated by the raw fuel gas heater 60 5c, the selective oxidation catalyst 6c accommodated in the catalyst accommodating space R of the selective oxidation unit 6 is heated uniformly over a wide range, so that the vessel B (B3) constituting the desulfurization unit 1 and the transformation unit 5 are configured. For each of the containers B (B4, 5, 6) and the containers B (B7) constituting the selective oxidation unit 6, thermal expansion can be spread over a wide range and evenly.

In such a state that the thermal expansion of each container B is spread over a wide range and evenly, the desulfurization section heater 21, the shift section heater 22, and the selective oxidation section heater 23 are operated to start the desulfurization treatment catalyst 1c. The temperature of the desulfurization section 1 is raised, the shift catalyst 5c is heated to the start-up shift section temperature, and the selective oxidation catalyst 6c is raised to the start-up selective oxidation section temperature. B3) Even if each of the containers B (B4, 5, 6) constituting the metamorphic section 5 and the containers B (B7) constituting the selective oxidation section 6 are locally heated, the containers B , Local warping can be effectively suppressed.
Therefore, the reforming process and the selective removal process are performed on the reformed gas generated in the reforming unit 2 to reduce the carbon monoxide gas, so that a hydrogen-containing gas having a much lower carbon monoxide concentration is generated. Is done. In such a hydrogen-containing gas generator that can generate a hydrogen-containing gas having a lower carbon monoxide concentration, the desulfurization treatment catalyst 1c, the shift treatment catalyst 5c, and the selective oxidation treatment catalyst 6c are prevented from being collapsed at the time of startup. And since the fall of a desulfurization process capability, a shift process capability, and a selective removal process capability can be suppressed, the production capability fall of the hydrogen containing gas accompanying progress of operation time can be suppressed.

Further, during the preheating process, since the temperature of the reforming catalyst 2c is controlled so as not to be higher than the carbon deposition preventing temperature, dry raw fuel gas not containing water vapor is converted into the reforming catalyst 1c. Even if it is made to flow through, deposition of carbon can be prevented.
In addition, when the temperature of the desulfurization treatment catalyst 1c is equal to or higher than the preheating avoidance temperature, such as when the elapsed time after the shutdown of the hydrogen-containing gas generation device P is short, the preheating treatment is not performed and the start-up temperature raising processing is immediately performed. Even so, the local warping of the container B constituting each of the desulfurization unit 1, the transformation unit 5, and the selective oxidation unit 6 is sufficiently suppressed. In such a case, since the preheating process is avoided, it is possible to avoid the preheating process being performed unnecessarily and the start-up time being lengthened.

[Second Embodiment]
Hereinafter, the second embodiment of the present invention will be described. This second embodiment will explain another embodiment of the preheating means H, and the configuration other than the preheating means H will be described in the first embodiment. It is the same. Therefore, in order to avoid redundant description, the same constituent elements as those in the first embodiment and the constituent elements having the same functions are denoted by the same reference numerals, and the description thereof is omitted, and the preheating means H will be mainly described.

In the second embodiment, the operation control unit C desulfurizes the desulfurization treatment catalyst 1c during the operation stop in which the supply of the raw fuel gas to the desulfurization unit 1 is stopped and the reforming process in the reforming unit 2 is stopped. As shown in FIG. 5, the preheating means H includes a desulfurization section heater 21 and an operation control section C. The standby heating process is performed to control the desulfurization section heater 21 so as to maintain the partial preheating temperature. And is configured.
In addition, since the shift unit 5 and the selective oxidation unit 6 are provided, the operation control unit C may maintain the shift process catalyst 5c at the shift unit preheating temperature lower than the start-up shift unit temperature in the standby heating process. And the selective oxidation unit heater 23 is controlled so as to maintain the selective removal treatment catalyst 6c at a selective oxidation unit preheating temperature lower than the selective removal unit temperature at startup. Yes.
That is, the preheating means H is configured to include a shift heater 22 and a selective oxidation heater 23 in addition to the desulfurization heater 21 and the operation controller C.

  Here, the desulfurization part preheating temperature is set, for example, to the same temperature as the desulfurization part preheating temperature in the first embodiment, and the transformation part preheating temperature is set to a predetermined temperature of, for example, 100 ° C. or more, The selective oxidation part preheating temperature is set to a predetermined temperature of, for example, 50 ° C. or higher.

As shown in FIG. 5, in the second embodiment, an operation reservation unit 65 that manually sets the operation start date and time for starting the operation of the fuel cell G is provided.
Then, the operation control unit C executes stop processing such as supply stop of the raw fuel gas by stopping the raw fuel gas pump 34, and the operation set by the operation reservation unit 65 from the operation stop time when the normal operation is finished. When the operation stop period until the start date and time is longer than a predetermined setting period set in advance, the standby heating process is stopped. Here, the setting period is set to about one week, for example.

  That is, since the time when the operation of the fuel cell G is started corresponds to the time when the supply of the raw fuel gas to the desulfurization unit 1 is started and the reforming process is started, the operation control unit C is operated by the desulfurization unit 1. The operation stop period from when the supply of raw fuel gas to the desulfurization unit 1 is stopped after the stop of the supply of raw fuel gas to the desulfurization unit 1 until the reforming process is started is a predetermined set period. If it is longer than that, the standby heating process is stopped.

The control operation of the standby heating process by the operation control unit C will be described.
After executing the stop process, the operation control unit C performs a standby heating process. In the standby heating process, the operation temperature of the desulfurization unit temperature sensor 24, the shift unit temperature sensor 25, and the selective oxidation unit temperature sensor 26 is detected. The desulfurization section heater 21 is controlled so that the temperature detected by the desulfurization section temperature sensor 24 is maintained at the desulfurization section preheating temperature, and the detection temperature of the shift section temperature sensor 25 is maintained at the shift section preheating temperature. The shift converter heater 22 is controlled, and the selective oxidation section heater 23 is controlled so as to maintain the temperature detected by the selective oxidation section temperature sensor 26 at the selective oxidation section preheating temperature.
Further, the operation control unit C stops the standby heating process when the operation stop period from the operation stop time to the operation start date and time set by the operation reservation unit 65 is longer than the set period.

As a control mode for controlling the desulfurization section heater 21 so as to maintain the desulfurization treatment catalyst 1c at the desulfurization section preheating temperature, for example, the detection temperature of the desulfurization section temperature sensor 24 is a predetermined control range with respect to the desulfurization section preheating temperature. When the temperature decreases by Δt (for example, 1 to 2 ° C.), the desulfurization section heater 21 is operated, and when the detected temperature of the desulfurization section temperature sensor 24 becomes higher than the desulfurization section preheating temperature by the control width Δt, A form can be adopted.
A control mode for controlling the shift heater 22 so as to maintain the shift catalyst 5c at the shift preheating temperature, and a selective oxidation heater 23 to maintain the selective oxidation catalyst 6c at the selective oxidation preheat temperature. As the control mode to be controlled, a control mode similar to the control mode of the desulfurization section heater 21 described above can be adopted.

  In the hydrogen-containing gas generation device P of the second embodiment, the standby heating process is executed during the operation stop, and the temperature of the desulfurization treatment catalyst 1c accommodated in the catalyst accommodation space R of the desulfurization part 1 is set as the desulfurization part preliminary. The temperature of the shift treatment catalyst 5c that is maintained at the heating temperature and is accommodated in the catalyst housing space R of the shift section 5 is maintained at the shift section preheating temperature and is selected in the catalyst storage space R of the selective oxidation section 6 The temperature of the oxidation catalyst 6c is maintained at the selective oxidation part preheating temperature. Then, even when the operation is stopped, the container B (B3) constituting the desulfurization unit 1, the container B (B4, 5, 6) constituting the transformation unit 5, and the container B (B7) constituting the selective oxidation unit 6 respectively. Is maintained in a state where the thermal expansion is evenly distributed over the whole.

  In the start-up temperature raising process, the container B (B3) constituting the desulfurization unit 1, the container B (B4, 5, 6) constituting the transformation unit 5, and the container B (B7 constituting the selective oxidation unit 6). ) In a state where the respective thermal expansions are evenly distributed over the entire area, the desulfurization section heater 21, the shift section heater 22, and the selective oxidation section heater 23 are operated to raise the temperature of the desulfurization treatment catalyst 1c to the desulfurization section temperature at startup, Since the temperature of the shift treatment catalyst 5c is raised to the start-up shift portion temperature and the selective oxidation treatment catalyst 6c is raised to the start-up selective oxidation portion temperature, each container B is heated locally. About the container B, a local curvature can be suppressed effectively.

  In addition, when the operation stop period from the operation stop time to the operation start date and time set in the operation reservation unit 65 is longer than a predetermined setting period (for example, one week), the standby heating process is stopped. Excessive energy consumption can be prevented.

[Another embodiment]
(A) In the first embodiment, the recycle path 63 is provided so that the raw fuel gas heated by the raw fuel gas heater 60 is taken out after passing through the selective oxidation unit 6. It may be provided so as to be taken out before being supplied to the selective oxidation unit 6 after passing through the (third stage transformation unit 5). In this case, the recycle path 63 is connected to the gas processing flow path 45 that connects the third stage shift section 5 and the selective oxidation section 6 via a flow path switching mechanism such as a three-way valve.

(B) A specific example of the raw fuel gas heating means is not limited to the configuration in which the electric heater is a heat source, such as the raw fuel gas heater 60 illustrated in the first embodiment. For example, a gas burner is used as the heat source. The configuration described above can be applied.

(C) In said 2nd Embodiment, you may provide the manual operation type | mold standby heating process stop switch which instruct | indicates execution stop of standby heating process. In this case, the operation control unit C is configured not to execute the standby heating process when the standby heating process execution switch is instructed by the standby heating process stop switch.

(D) In the second embodiment, when the reforming process is performed and the normal operation is performed, the standby heating is performed during the operation stop after the reforming process is stopped based on the operation stop command. Although the process is configured to be executed, the standby heating process may be performed even when the hydrogen-containing gas generation device P is installed and the operation is stopped before the reforming process is performed for the first time. good.
In this case, the standby heat treatment is continued until the thermal expansion of the container B constituting each of the desulfurization unit 1, the transformation unit 5 and the selective oxidation unit 6 reaches the whole.
Further, the operation control unit C is configured such that when the operation start command is instructed for the first time by the operation switch, the standby heating process is immediately executed and then the startup temperature raising process is executed.

(E) As a specific example of the selective removal processing unit, in each of the first and second embodiments, the selective oxidation unit 6 that selectively oxidizes and removes the carbon monoxide gas in the reformed gas is provided. However, instead of this, a selective methanation treatment unit that accommodates the selective methanation catalyst in the catalyst housing space R and selectively methanates and removes the carbon monoxide gas in the reformed gas may be provided.

(F) The specific configuration of the reformer M is not limited to the configuration described in each of the first and second embodiments. For example, the reformer M may be configured by using a flat container B having two flat internal spaces S similar to those in the above embodiments. That is, the flat reforming portion 2 is configured using a portion having one internal space S in the flat container B, and the flat combustion portion 7 is configured using a portion having the other internal space S. It will be.

(G) The use of the hydrogen-containing gas generation device according to the present invention is not limited to the fuel cell exemplified in the first and second embodiments, but for a hydrogen purification (concentration) device, etc. The present invention can be applied to a hydrogen-containing gas generator for various uses.

  Note that the configuration disclosed in the above embodiment (including another embodiment, the same applies hereinafter) can be applied in combination with the configuration disclosed in the other embodiment as long as no contradiction occurs. The embodiments disclosed in this specification are exemplifications, and the embodiments of the present invention are not limited thereto, and can be appropriately modified without departing from the object of the present invention.

  As described above, it is possible to provide a hydrogen-containing gas generation device that can suppress a decrease in the hydrogen-containing gas generation capability with the passage of operating time.

DESCRIPTION OF SYMBOLS 1 Desulfurization part 1c Desulfurization process catalyst 2 Reforming part 2c Reforming process catalyst 3 Reforming burner 5 Transformation part 5c Transformation process catalyst 6 Selective oxidation part (selective removal part)
6c Selective oxidation catalyst (selective removal catalyst)
21 Desulfurization section heater (desulfurization section heating means)
22 Transformer heater (transformer heating means)
23 Selective oxidation unit heater (selective removal unit heating means)
60 Raw fuel gas heater (raw fuel gas heating means)
61 Preheating control means 63 Recycling path B Container C Operation control part (operation control means)
H Preheating means R Catalyst accommodating space

Claims (8)

A desulfurization treatment catalyst is housed in the catalyst housing space inside the container, and a container-shaped desulfurization section that performs desulfurization treatment on the supplied raw fuel gas, and a part of the desulfurization section is heated from the outside, thereby A desulfurization part heating means for heating the desulfurization process catalyst and a reforming process catalyst are accommodated and connected to the desulfurization part so as to receive gas, and the raw fuel gas after the desulfurization process supplied from the desulfurization part is reformed And a reforming section for generating a reformed gas containing hydrogen gas as a main component, and an operation control means for controlling the operation.
Before the operation control means starts supplying the raw fuel gas to the desulfurization section and starts the reforming process in the reforming section, the operation control means should raise the temperature of the desulfurization treatment catalyst to the desulfurization section temperature at start-up. A hydrogen-containing gas generation device configured to perform a startup temperature increase process for controlling the desulfurization unit heating means,
Preheating means for heating the desulfurization treatment catalyst to a desulfurization part preheating temperature lower than the desulfurization part temperature at the start-up is provided,
The operation control means operates the preheating means to heat the desulfurization treatment catalyst to the desulfurization part preheating temperature, and then performs the start-up temperature raising process. apparatus.   The preheating means heats the raw fuel gas supplied to the desulfurization section to a raw fuel gas preheating temperature lower than the start-up desulfurization section temperature, and the desulfurization treatment catalyst serves as the desulfurization section. The hydrogen-containing component according to claim 1, further comprising a preheating control unit that supplies the raw fuel gas heated by the raw fuel gas heating unit to the desulfurization unit until the raw fuel gas is heated to a preheating temperature. Gas generator. A conversion treatment catalyst is accommodated in the catalyst accommodating space inside the container and is connected to the reforming unit so as to receive gas, and carbon monoxide is converted into carbon dioxide with respect to the reformed gas supplied from the reforming unit. A container-shaped metamorphic section for performing a metamorphic process, a metamorphic section heating means for heating the metamorphic catalyst by heating a part of the metamorphic section from the outside, and a selective removal process in a catalyst housing space inside the container A container-shaped container that is connected to the shift section so as to receive a gas and is capable of receiving gas, and that performs a selective removal process for selectively removing carbon monoxide from the reformed reformed gas supplied from the shift section. A selective removal unit, and a selective removal unit heating means for heating the selective removal treatment catalyst by heating a part of the selective removal unit from the outside,
The operation control means is
In the start-up temperature increase process, the shift unit heating means is controlled to increase the temperature of the shift process catalyst to the start-up shift unit temperature, and the selective removal process catalyst is heated to the start-up selective removal unit temperature. Therefore, the hydrogen-containing gas generating device according to claim 2, which is configured to control the selective removing unit heating means. A reforming burner for heating the reforming catalyst to a reforming section temperature at start-up;
4. A recycling path is provided in which the raw fuel gas heated by the raw fuel gas heating means is taken out after passing through at least the shift section and is supplied to the reforming burner as combustion fuel. 2. A hydrogen-containing gas generating device according to 1. The operation control means maintains the desulfurization treatment catalyst at the preheating temperature of the desulfurization unit during an operation stop where the supply of the raw fuel gas to the desulfurization unit is stopped and the reforming process in the reforming unit is stopped. Configured to perform standby heating processing to control the desulfurization unit heating means,
The hydrogen-containing gas generating apparatus according to claim 1, wherein the preheating unit includes the desulfurization unit heating unit and the operation control unit.   From the time when the operation control means stops the supply of the raw fuel gas to the desulfurization section, the supply of the raw fuel gas to the desulfurization section is started and the reforming process is started. The hydrogen-containing gas generation device according to claim 5, configured to stop the execution of the standby heating process when the operation stop period is longer than a predetermined set period. A conversion treatment catalyst is accommodated in the catalyst accommodating space inside the container and is connected to the reforming unit so as to receive gas, and carbon monoxide is converted into carbon dioxide with respect to the reformed gas supplied from the reforming unit. A container-shaped metamorphic section for performing a metamorphic process, a metamorphic section heating means for heating the metamorphic catalyst by heating a part of the metamorphic section from the outside, and a selective removal process in a catalyst housing space inside the container A container-shaped container that is connected to the shift section so as to receive a gas and is capable of receiving gas, and that performs a selective removal process for selectively removing carbon monoxide from the reformed reformed gas supplied from the shift section. A selective removal unit, and a selective removal unit heating means for heating the selective removal treatment catalyst by heating a part of the selective removal unit from the outside,
The operation control means is
In the start-up temperature increase process, the shift unit heating means is controlled to increase the temperature of the shift process catalyst to the start-up shift unit temperature, and the selective removal process catalyst is heated to the start-up selective removal unit temperature. And configured to control the selective removing unit heating means, and
In the standby heating process, the shift unit heating unit is controlled to maintain the shift process catalyst at a shift unit preheating temperature lower than the start-up shift unit temperature, and the selective removal process catalyst is selected at the start-up time. The hydrogen-containing gas generation device according to claim 5 or 6, wherein the selective removal unit heating means is controlled to maintain the selective removal unit preheating temperature lower than the removal unit temperature. The catalyst accommodating spaces of the desulfurization unit, the transformation unit, and the selective removal unit are formed in separate flat containers,
The plurality of containers that respectively form the catalyst housing spaces of the desulfurization unit, the shift conversion unit, and the selective removal unit are arranged in a stacked state in the container thickness direction. 2. The hydrogen-containing gas generator according to item 1.

Images