JP6381458B2 - Method for removing finely divided catalyst for gas processing apparatus - Google Patents

Description

  In the present invention, a granular catalyst is accommodated in the catalyst accommodating space, and the target gas supplied to the catalyst accommodating space is subjected to a predetermined treatment in a state where the catalyst is heated to a predetermined treatment temperature. The present invention relates to a method for removing a segmented catalyst for a gas processing apparatus provided with a section.

  Such a gas processing device performs a predetermined process on a processing target gas supplied to a catalyst storage space with a granular catalyst. For example, the gas processing apparatus is modified for a raw fuel gas supplied to a catalyst storage space. There is a gas processing apparatus for generating a hydrogen-containing gas that performs a reforming process for reforming a reformed gas containing hydrogen gas as a main component by a catalyst for quality treatment.

  In such a gas treatment device, the compressive stress is repeatedly applied to the granular catalyst accommodated in the catalyst accommodating space due to the expansion and contraction of the member forming the catalyst accommodating space by the repeated starting and stopping of the device. The catalyst is crushed and subdivided. Then, when the subdivided catalyst in which the catalyst is subdivided accumulates in the gaps between the granular catalysts housed in the catalyst housing space, the flow of the processing object gas is hindered, and the processing object gas flowing through the catalyst housing space As a result, a region where the processing target gas is processed in the catalyst accommodating space is narrowed, and the processing capability of performing the predetermined processing on the processing target gas is reduced.

  Therefore, in the conventional gas processing apparatus, the processing target gas inlet is provided in the upper part of the catalyst housing space, and the processing target gas outlet is provided in the lower part, so that the processing target gas flows downward in the catalyst housing space. And an end plate having a discharge port for discharging the subdivided catalyst out of the processing target gas flow path and a guide portion for guiding the subdivided catalyst to the discharge port below the gas outlet for processing. And the processing target gas flow path is configured to flow the processing target gas toward the end plate and then turn the direction upward to flow the side of the processing unit ( For example, see Patent Document 1.)

  In other words, the finely divided catalyst collected in the gaps between the granular catalysts is placed on the flow of the gas to be treated and flows out of the catalyst accommodating space, and passes through the outlet of the end plate, thereby accommodating the finely divided catalyst in the catalyst. It was configured to discharge from space.

JP 2012-250873 A

However, in the conventional gas processing apparatus, as described below, since the fragmented catalyst accumulated in the catalyst housing space cannot be sufficiently removed from the catalyst housing space, the processing capacity of the operation time with the passage of time is reduced. There was a problem that the decrease was large.
In other words, since the finely divided catalyst is light in weight, it is easy to flow on the downstream side by placing it on the gas to be processed. However, since the relatively large finely divided catalyst is relatively heavy, it is placed on the gas to be processed on the downstream side. It is difficult to flow.
Further, when water is contained in the gas to be treated, the subdivided catalyst is likely to adhere to the surrounding catalyst, so that it is difficult to flow downstream on the gas to be treated.

  This invention is made | formed in view of this situation, The objective is to provide the fragmentation catalyst removal method for gas processing apparatuses which can suppress the fall of the processing capability accompanying progress of operation time.

In order to achieve the above object, the method for removing a segmented catalyst for a gas processing apparatus according to the present invention, in which a granular catalyst is stored in a catalyst storage space and the catalyst is heated to a predetermined processing temperature, A subdivided catalyst removal method for a gas processing apparatus provided with a processing unit for performing a predetermined process on a processing target gas supplied to the catalyst containing space, the characteristic configuration is:
The catalyst housing space is partitioned into an upper catalyst housing portion for accommodating the catalyst and a lower fragmented catalyst housing portion by a porous partition that allows passage of the finely divided catalyst into which the catalyst is finely divided. And providing a subdivided catalyst removal structure provided with a vibration means for vibrating the catalyst in the catalyst housing space,
When it is determined that it is time to remove the finely divided catalyst from the catalyst accommodating portion of the catalyst accommodating space, the excitation means is stopped in a state where the supply of the processing target gas to the catalyst accommodating space is stopped. The point is to execute the operation of removing the subdivided catalyst to be operated.

According to the above characteristic configuration, when it is determined that it is time to remove the subdivided catalyst, the subdivided catalyst removing operation is executed.
In the subdivided catalyst removal operation, the supply of the processing target gas to the catalyst containing space is stopped, and the vibration means is operated to vibrate the catalyst in the catalyst containing space, so that the subdivided catalyst is placed on the processing target gas. Thus, the finely divided catalyst accumulated in the gaps between the granular catalysts can be passed through the partitioning body and screened into the finely divided catalyst accommodating portion in a state where it is prevented from flowing to a process downstream of the processing unit. .
In other words, since the catalyst in the catalyst housing space is vibrated, not only the finely divided catalyst accumulated in the gaps between the granular catalysts, but also the relatively large fragmented catalyst is allowed to pass through the partitioning body to receive the fragmented catalyst containing portion. Can be eliminated.
Even if the gas to be treated contains moisture and the finely divided catalyst easily adheres to the surrounding catalyst, the finely divided catalyst that easily adheres to the surrounding catalyst is partitioned by vibrating the catalyst in the catalyst housing space. It can be passed through the body and screened into the segmented catalyst containing part.
Thereby, it is possible to sufficiently suppress the occurrence of a drift in the gas to be processed flowing through the catalyst housing space.
Therefore, it is possible to provide a method for removing a fragmented catalyst for a gas processing apparatus that can suppress a decrease in processing capacity with the passage of operating time.

  A further characteristic configuration of the method for removing a subdivided catalyst for a gas processing apparatus according to the present invention is that the subdivided catalyst removal timing is set when the pressure of the gas to be processed supplied to the catalyst containing space is equal to or higher than a predetermined set pressure. It is in the point to judge that it became.

According to the above characteristic configuration, when the pressure of the gas to be processed supplied to the catalyst housing space is equal to or higher than a predetermined set pressure, it is determined that it is time to remove the segmented catalyst.
That is, as the granular catalyst is further fragmented, the area where the finely divided catalyst is accumulated in the catalyst accommodating portion is expanded, and the pressure of the processing target gas supplied to the catalyst accommodating space increases. Therefore, based on the pressure of the gas to be treated supplied to the catalyst housing space, the timing at which the subdivided catalyst removal operation should be executed, that is, the subdivided catalyst removal timing is not too early and too late. It can be judged accurately without any problems.
Accordingly, since the subdivided catalyst removal operation can be executed at an appropriate timing without being too early and not too late, the process associated with the passage of the operation time is further suppressed while preventing the normal operation from being obstructed. A decrease in ability can be accurately suppressed.

A further characteristic configuration of the subdivided catalyst removal method for the gas processing apparatus according to the present invention is as the processing unit,
A catalyst for reforming treatment is accommodated in the catalyst accommodating space, and the raw material supplied to the catalyst accommodating space in a state where the temperature of the reforming catalyst is raised to a predetermined reforming treatment temperature. A processing unit for reforming processing for reforming the fuel gas into a reformed gas containing hydrogen gas as a main component;
A reforming treatment is accommodated in the catalyst housing space, and the reforming treatment is performed in the reforming treatment section in a state where the temperature of the transformation treatment catalyst is increased to a predetermined transformation treatment temperature. A modification processing unit for performing a modification process for transforming carbon monoxide gas into carbon dioxide gas with respect to the reformed gas,
The subdivided catalyst removal structure is provided for at least one of the reforming processing section and the modification processing section.

According to the above characteristic configuration, the reforming process is performed by reforming the raw fuel gas into a reformed gas containing hydrogen gas as a main component in the reforming process unit. , A reforming process is performed on the reformed gas that has been reformed in the reforming processing unit to convert carbon monoxide gas into carbon dioxide gas, so that the hydrogen rich with a low carbon monoxide gas concentration. Hydrogen-containing gas is produced.
And, since at least one of the reforming processing section and the modification processing section is provided with a subdivided catalyst removing structure and performing a subdivided catalyst removing operation, At least one of the catalyst fragmentation catalyst and the shift treatment catalyst fragmentation catalyst can be passed through the partition from the catalyst housing portion and screened into the fragmentation catalyst housing portion.
Accordingly, since it is possible to suppress a decrease in processing capacity with the passage of the operating time of at least one of the reforming process and the modification process, a gas processing apparatus for generating a hydrogen-containing gas having a low carbon monoxide gas concentration In this case, it is possible to suppress a decrease in the hydrogen-containing gas generation capacity with the elapse of the operation time.

A further characteristic configuration of the subdivided catalyst removal method for the gas processing apparatus according to the present invention is as the processing unit,
A catalyst for desulfurization treatment is accommodated in the catalyst accommodating space, and the catalyst for desulfurization treatment is supplied to the processing unit for reforming treatment in a state where the catalyst is heated to a predetermined treatment temperature for desulfurization treatment. A desulfurization treatment unit that desulfurizes the previous raw fuel gas;
A catalyst for selective removal treatment is accommodated in the catalyst accommodating space, and the catalyst for selective removal treatment is transformed to a predetermined treatment temperature for selective removal treatment in the state of the modification treatment section. A selective removal treatment processing unit for performing selective removal treatment for selectively removing carbon monoxide gas with respect to the treated reformed gas;
The subdivided catalyst removal structure is provided for at least one of the desulfurization treatment section and the selective removal treatment section.

According to the above characteristic configuration, in the desulfurization processing unit, the desulfurization process is performed on the raw fuel gas before being supplied to the reforming processing unit. It is possible to prevent the poisoning of the catalyst in each processing section (for processing, modification processing, selective removal processing, etc.).
Further, in the selective removal treatment processing section, selective removal treatment for selectively removing carbon monoxide gas is performed on the reformed gas that has been subjected to the modification treatment in the modification treatment processing section. A hydrogen-rich hydrogen-containing gas having a lower concentration can be generated.
In addition, since at least one of the processing unit for desulfurization processing and the processing unit for selective removal processing is provided with a subdivided catalyst removal structure and a subdivided catalyst removal operation is performed, a catalyst for desulfurization processing At least one of the subdivided catalyst and the catalyst for selective removal treatment can be passed through the partition from the catalyst housing portion and screened into the subdivided catalyst housing portion.
Therefore, since it is possible to suppress a decrease in processing capacity with the passage of the operating time of at least one of the desulfurization process and the selective removal process, a gas process for generating a hydrogen-containing gas having a lower carbon monoxide gas concentration. In the apparatus, it is possible to suppress a decrease in the hydrogen-containing gas generation capacity with the elapse of the operation time.

A further characteristic configuration of the method for removing a subdivided catalyst for a gas processing apparatus according to the present invention enables an auxiliary machine equipped with a prime mover to vibrate the catalyst of the processing unit provided with the subdivided catalyst removing structure. Provided,
The auxiliary machine is used as the vibration means.

According to the above characteristic configuration, when the auxiliary machine equipped with the prime mover is operated, the catalyst of the processing unit provided with the subdivided catalyst removal structure can be vibrated and subdivided in the gaps between the granular catalysts. The catalyst can be screened off from the catalyst housing part to the fragmented catalyst housing part.
That is, the gas processing apparatus is originally provided with an auxiliary machine provided with a prime mover.
Therefore, by using the auxiliary machine as a vibration means, it is not necessary to provide a dedicated vibration means, so that the processing capacity is reduced with the passage of operating time while reducing the size and cost of the gas processing apparatus. Can be suppressed.

A further characteristic configuration of the subdivided catalyst removal method for a gas treatment device according to the present invention is provided with a reforming burner for heating the reforming treatment catalyst to the reforming treatment temperature,
Blower means for supplying combustion air to the reforming burner is provided as the auxiliary machine,
The air blowing means is used as the vibration means.

According to the above characteristic configuration, when the blowing means for supplying combustion air to the reforming burner is provided so as to vibrate the catalyst of the processing unit provided with the subdivided catalyst removal structure, the blowing means is used as the vibrating means. Can be used.
That is, since the reforming reaction in the reforming process is an endothermic reaction, in order to raise the temperature of the reforming process catalyst to the reforming process temperature, the reforming burner and the reforming process are originally provided. Blowing means for supplying combustion air to the burner is provided.
And even if a ventilation means is operated while the gas processing apparatus is stopped, the air blown by the ventilation means is not supplied to the catalyst housing space. Therefore, by using the blowing means as the vibrating means, even if the blowing means used as the vibrating means is operated while the gas treatment apparatus is stopped, Since the processing to be performed is not adversely affected, it is possible to accurately suppress a decrease in processing capacity.
Accordingly, it is possible to accurately suppress a reduction in processing capacity with the passage of operation time while reducing the size and cost of the gas processing apparatus.

A further characteristic configuration of the fragmented catalyst removal method for a gas processing device according to the present invention is such that the catalyst accommodating space of each processing unit is formed in a separate flat container,
The plurality of containers that respectively form the catalyst housing spaces of the respective processing units are integrally assembled in a standing state with the container thickness direction oriented in the horizontal direction and arranged in a stacked state in the container thickness direction. The container laminate is configured,
The subdivided catalyst removal operation is performed in a state where the temperature of the catalyst of the processing unit provided with the subdivided catalyst removing structure is set to a predetermined set temperature lower than the processing temperature.

According to the above characteristic configuration, in a state where the catalyst in the plurality of containers assembled in the container stack is heated to the corresponding processing temperature, the temperature of each container is increased by heat transfer between adjacent containers. As a result, the volume of each container increases, so that the catalyst in each container sinks.
On the other hand, when the state in which the catalyst in each container is raised to the corresponding processing temperature is stopped, the volume in each container is reduced by the temperature and contraction of the entire container, so the catalyst in each container is reduced. Is lifted.

And if a vibration is applied in the state where the catalyst in each container sinks, the collapse of the catalyst is easily promoted. Therefore, if the catalyst removal operation is performed in a state where the temperature of the catalyst in the container of the processing section provided with the fragmentation catalyst removal structure is lowered to a set temperature lower than the treatment temperature, the progress of the catalyst collapse is sufficiently performed. The finely divided catalyst can be screened from the catalyst containing portion to the finely divided catalyst containing portion.
Therefore, it is possible to sufficiently prevent the crushing of the catalyst during the subdivided catalyst removal operation and improve the durability of the catalyst, so that it is possible to further suppress the decrease in the processing capacity with the lapse of the operation time. it can.

  A further characteristic configuration of the method for removing a fragmented catalyst for a gas processing apparatus according to the present invention is that the vibration means is provided so as to vibrate the container laminate.

According to the above characteristic configuration, when the vibration means is operated, the entire container stack can be vibrated, so that the catalyst inside all of the plurality of containers constituting the container stack can be vibrated.
That is, even if the subdivided catalyst removal structure is provided in the plurality of processing units, it is only necessary to provide one vibration unit in a state shared by the subdivided catalyst removal structures of the plurality of processing units.
Therefore, in the gas processing apparatus having a plurality of processing units, it is possible to suppress a reduction in processing capacity of the plurality of processing units with the passage of operating time while reducing the cost.

Longitudinal front view of hydrogen-containing gas generator Front view of hydrogen-containing gas generator Right side view of hydrogen-containing gas generator Perspective view of container constituting reforming unit Longitudinal right side view of the container constituting the reforming section Longitudinal front view of the container constituting the reforming section Front view of a hydrogen-containing gas generator according to another embodiment

Hereinafter, an embodiment in the case where the present invention is applied to a gas processing apparatus for generating a hydrogen-containing gas will be described with reference to the drawings.
As shown in FIGS. 1, 5, and 6, a gas processing device P for generating a hydrogen-containing gas (hereinafter sometimes referred to as a hydrogen-containing gas generating device) includes a granular catalyst 2 c ( 1c, 5c, 6c) is provided, and a processing unit D is provided that performs a predetermined process on the processing target gas supplied to the catalyst processing space R in a state where the catalyst is heated to a predetermined processing temperature. It has been.

  As shown in FIG. 1, in this embodiment, as the processing unit D, a hydrocarbon-based raw fuel gas (for example, a natural gas-based city gas such as 13A) supplied through the raw fuel gas supply path 20 is used. A desulfurization treatment section (hereinafter, may be referred to as a desulfurization section) 1 for performing a desulfurization process, and a raw fuel gas after desulfurization treatment supplied from the desulfurization section 1 (hereinafter referred to as a desulfurization raw fuel gas) 2), a reforming treatment processing section (hereinafter sometimes referred to as a reforming section) 2 for performing a reforming process for reforming a reformed gas containing hydrogen gas as a main component, A treatment section for modification treatment that performs a modification treatment for transforming carbon monoxide gas into carbon dioxide gas with respect to the reformed gas reformed in the mass portion 2 (hereinafter sometimes referred to as a modification portion) 5 And carbon monoxide gas with respect to the reformed gas transformed in the transformation section 5 A selective oxidation treatment processing section (an example of a selective removal processing section, which may be referred to as a selective oxidation section hereinafter) 6 that performs selective oxidation treatment (an example of a selective removal process) for selective oxidation. It is provided so as to generate a hydrogen-rich hydrogen-containing gas having a low carbon monoxide gas concentration (for example, 10 ppm or less).

  Further, in the hydrogen-containing gas generation device P, the reforming water supplied through the reforming water supply path 21 is heated to generate steam to generate steam, and the reforming catalyst 2c of the reforming unit 2 is reformed. A part of the reformed gas reformed in the reforming unit 2 (in this embodiment, the reformed gas reformed in the shift unit 5) provided with the reforming burner 3 that is heated to a temperature. A recycle gas passage 22 for mixing the raw gas into the raw fuel gas supplied through the raw fuel gas supply passage 20 as a recycle gas, a control unit C for controlling the operation of the hydrogen-containing gas generation device, and the like are provided.

The hydrogen-containing gas generated by the hydrogen-containing gas generator P is supplied to the fuel cell G through the fuel gas supply path 23 as fuel gas.
In the raw fuel gas supply path 20 for supplying the raw fuel gas to the desulfurization unit 1 of the hydrogen-containing gas generator P, the flow rate of the raw fuel gas supplied to the desulfurization unit 1 is adjusted in order to adjust the output power of the fuel cell G. A raw fuel gas flow rate adjusting valve 7 to be adjusted and a raw fuel gas supply pressure detector 19 for detecting the pressure of the raw fuel gas supplied through the raw fuel gas supply path 20 are provided.

  In this embodiment, the catalyst housing space R is separated from the upper catalyst housing portion Ra in which the catalyst is housed by a porous partition net 46 (an example of a partition body) through which the finely divided catalyst can be passed. A subdivided catalyst removal structure M is provided that is divided into a lower subdivided catalyst housing portion Rb and includes a vibrator 50 (an example of a vibrating means) that vibrates the catalyst in the catalyst housing space R. This subdivided catalyst removal structure M is provided in each processing part D of the desulfurization part 1, the reforming part 2, the shift part 5 and the selective oxidation part 6.

Next, based on FIG. 1, description will be added about each part of the hydrogen containing gas production | generation apparatus P. FIG.
Since the fuel cell G is well known and will not be described in detail and briefly described, for example, the fuel cell G is configured in a solid polymer type in which a plurality of cells having a solid polymer membrane as an electrolyte layer are provided in a stacked state, Fuel gas is supplied from the hydrogen-containing gas generating device P to the fuel electrode of each cell through the fuel gas supply path 23, and air is supplied to the oxygen electrode of each cell by the reaction air blower 31, so that the electrochemistry of hydrogen and oxygen is performed. It is comprised so that electric power generation may be performed by reaction. Further, the cooling water pump 32 is configured to cause the cooling water to flow through the fuel cell G, and to recover the heat generated from each cell.

A catalyst for desulfurization treatment (hereinafter sometimes referred to as a desulfurization catalyst) 1c is accommodated in the catalyst accommodation space R of the desulfurization section 1.
The desulfurization unit 1 recycles the desulfurization catalyst 1c in a state in which the desulfurization catalyst 1c is heated to a predetermined desulfurization treatment temperature (for example, in the range of 200 to 270 ° C., hereinafter sometimes referred to as a desulfurization treatment temperature). The sulfur compound in the raw fuel gas is hydrogenated by the hydrogen gas in the recycle gas mixed through the passage 22, and the hydride is adsorbed and desulfurized. The desulfurization 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.

A catalyst for reforming treatment (hereinafter sometimes referred to as a reforming catalyst) 2c is accommodated in the catalyst accommodating space R of the reforming unit 2, and steam generation is performed in the catalyst accommodating space R of the reforming unit 2. Desulfurized raw fuel gas is supplied in a state in which the water vapor generated in part J is mixed.
Then, the reforming unit 2 raises the temperature of the reforming catalyst 2c to a predetermined reforming processing temperature (for example, in the range of 600 to 700 ° C., hereinafter may be referred to as the reforming processing temperature). In the state, when the raw fuel gas is a natural gas mainly composed of methane gas, the methane gas is reacted with water vapor according to the following reaction formula to be reformed into a reformed gas containing hydrogen gas and carbon monoxide gas. To do. The reforming 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 catalyst housing space R of the shift section 5, a shift processing catalyst (hereinafter sometimes referred to as a shift catalyst) 5 c is stored.
Then, the shift section 5 raises the shift catalyst 5c to a predetermined shift processing temperature (for example, in the range of 150 to 250 ° C., hereinafter may be referred to as the shift processing temperature), and In this reaction formula, carbon monoxide gas in the reformed gas is reacted with water vapor to be transformed into carbon dioxide gas. The shift catalyst 5c 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 metamorphic reaction in the metamorphic part 5 is an exothermic reaction.

CO + H ₂ O → CO ₂ + H ₂

A catalyst for selective oxidation treatment (hereinafter sometimes referred to as a selective oxidation catalyst) 6c is accommodated in the catalyst accommodating space R of the selective oxidation unit 6.
In the selective oxidation unit 6, the selective oxidation catalyst 6 c is raised to a predetermined selective oxidation treatment temperature (for example, in the range of 80 to 100 ° C., hereinafter may be referred to as a selective oxidation treatment temperature). In this state, the carbon monoxide gas remaining in the reformed gas after the modification treatment is selectively oxidized. The selective oxidation 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 combustion section 4 is provided with a reforming burner 3 so as to burn gas fuel in the combustion space inside the combustion section 4, and the reforming of the reforming section 2 is adjusted by adjusting the combustion amount of the reforming burner 3. The catalyst 2c is configured to be heated to the reforming treatment temperature.
Off-gas discharged from the fuel electrode of the fuel cell G in a state where hydrogen remains is supplied to the reforming burner 3 as gas fuel through the off-gas passage 24, and a combustion air supply passage 25 is supplied by the combustion air blower 33. Combustion air is supplied through. In addition, when the reforming catalyst 2c of the reforming section 2 is heated to the reforming treatment temperature, city gas (13A, etc.) is supplied to the reforming burner 3 through the gas fuel supply path 26 as an insufficient amount that is insufficient with only off-gas. Is done. The gas fuel supply passage 26 is provided with a gas fuel flow rate adjustment valve 38 for adjusting the flow rate of the city gas. By controlling the gas fuel flow rate adjustment valve 38 and adjusting the flow rate of the city gas, a reforming burner is provided. 3 is adjusted.

  The water vapor generating part J is supplied through the reforming water supply path 21 by the heating exhaust gas flow part 8 for passing the combustion gas of the reforming burner 3 discharged from the combustion part 4 and the reforming water pump 34. And an evaporating unit 9 for evaporating the reforming water by heating with the heating exhaust gas flow unit 8.

  The hydrogen-containing gas generating device P is passed through the high-temperature reformed gas discharged from the reforming unit 2 to keep the reforming unit 2 warm, and is discharged from the reforming unit 2. The desulfurized raw fuel heat exchanger Ea that heats the desulfurized raw fuel gas desulfurized in the desulfurization unit 1 by the high-temperature reformed gas that has been desulfurized, and the modified after heat exchange in the raw fuel heat exchanger Ea after desulfurization The raw fuel gas to be desulfurized in the desulfurization section 1 is heated by the raw gas, the raw fuel heat exchanger Eb before desulfurization, and the combustion gas discharged from the heating exhaust gas flow section 8 is passed through the combustion gas. A cooling exhaust gas flow passage 11 for cooling the metamorphic portion 5 is provided.

  The desulfurized raw fuel heat exchanger Ea includes an upstream reformed gas flow section 12 through which the reformed gas discharged from the heat retaining flow section 10 flows, and a desulfurized raw fuel gas supplied to the reformed section 2. A heat exchanger Eb for raw fuel before desulfurization is configured to allow the reformed gas discharged from the upstream reformed gas flow portion 12 to be exchanged with the post-desulfurized raw fuel flow portion 13 through which heat is passed. A downstream side reformed gas flow part 14 to be passed and a raw fuel gas flow part 15 before desulfurization to flow the raw fuel gas supplied to the desulfurization part 1 are provided so as to be capable of heat exchange.

  Furthermore, the hydrogen-containing gas generator P includes a desulfurization section heater 35 that heats the desulfurization section 1 to the desulfurization processing temperature, and two shift section heaters 36 that heat the shift section 5 to the transformation process temperature at the time of startup. The cooling fan 37 that cools the oxidation unit 6, and the reforming gas discharged from the shift unit 5 and the reforming water supplied to the evaporation processing unit 9 of the steam generation unit J are heat-exchanged to provide reforming water. The raw material water preheating heat exchanger 16 is provided for preheating the water. Incidentally, the desulfurization part heater 35 and the transformation part heater 36 are constituted by electric heaters.

As shown in FIGS. 1-3, each part which comprises the hydrogen-containing gas production | generation apparatus P is comprised using the several flat container B which forms the internal space S inside.
Then, in a state where the plurality of containers B are arranged in a stacked state in the container thickness direction in a standing posture with the container thickness direction oriented in the horizontal direction, the pressing mechanism K (FIGS. 2 and 3) The container laminated body A is configured by being integrally assembled by being pressed in (see).

  Each container B is made of a heat-resistant metal having heat conductivity such as stainless steel, and the container B includes one that forms one internal space S and one that forms two internal spaces S. Incidentally, as shown in FIG. 4, the container B that forms two internal spaces S is welded and connected at the periphery with a flat partition member 42 positioned between a pair of dish-shaped container forming members 41. Then, two flat internal spaces S are defined in the interior, and illustration is omitted, but the container B forming one internal space S has a dish-shaped container forming member and a flat container forming member in the peripheral part. Are connected to each other by welding to form a flat inner space S.

  A nozzle-like gas inlet 43 and a gas outlet 44 are attached to each container B as necessary, and the partition member 42 of the container B having two internal spaces S is provided as necessary. A communication port 45 that communicates the space on both sides is provided.

In this embodiment, the hydrogen-containing gas generation device P is configured using nine containers B. In order to clarify the distinction of the nine containers B, for the sake of convenience, the reference numerals 1, 2, 3 indicating the arrangement order from the left in FIG. 1 and FIG. 9 is attached. Incidentally, the third container B3 from the left forms one internal space S, and the other eight containers B form two internal spaces S.
FIG. 4 shows the second container B2 from the left, and this container B2 constitutes the combustion section 4 and the reforming section 2 as will be described in detail later.

  As shown in FIG. 1, a heating exhaust gas flow section 8 is configured in a portion having the left internal space S in the leftmost container B <b> 1, and an evaporation processing section 9 is configured in a portion having the right internal space S. ing. That is, the water vapor generating part J is configured by the leftmost container B1.

  The left internal space S in the second container B2 from the left is the combustion space, the combustion section 4 is configured in the portion having the left internal space S, and the right internal space S is the catalyst housing space R. The reforming unit 2 is configured by a portion that accommodates 2c and has the right internal space S.

The third container B3 from the left constitutes the heat retaining flow-through portion 10.
The upstream reformed gas flow passage 12 is constituted by the portion having the left internal space S in the fourth container B4 from the left, and the raw fuel flow passage 13 after desulfurization is constituted by the portion having the right internal space S. Is configured. That is, the desulfurized raw fuel heat exchanger Ea is configured by the fourth container B4 from the left.

The desulfurization catalyst 1c is accommodated with the left inner space S in the fifth container B5 from the left as the catalyst accommodating space R, and the desulfurization part 1 is configured by the portion having the left inner space S. The part which has it comprises the raw fuel flow part 15 before desulfurization.
A desulfurization section heater 35 is provided on the left side of the fifth container B5 from the left, that is, in a state of being applied to the side surface on the desulfurization section 1 side.

The portion having the left internal space S in the sixth container B6 from the left constitutes the downstream reformed gas flow section 14, and the shift catalyst 5c is accommodated with the right internal space S as the catalyst accommodating space R. The metamorphic portion 5 is constituted by the portion having the right internal space S.
The left inner space S in the seventh container B7 from the left is used as the catalyst housing space R to accommodate the shift catalyst 5c, and the shift section 5 is configured by the portion having the left inner space S. The cooling exhaust gas flow passage portion 11 is configured by the portion having the same.

The left and right internal spaces S in the eighth container B8 from the left are used as the catalyst housing space R to house the shift catalyst 5c, and the shift section 5 is configured by the eighth container B8 from the left.
That is, the metamorphic portion 5 composed of the sixth container B6 from the left, the metamorphic portion 5 composed of the seventh container B7 from the left, and the metamorphic portion composed of the eighth container B8 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.

  One of the two transformer heaters 36 is provided between the sixth container B6 and the seventh container B7 from the left, and the remaining one is the eighth container from the left. It is provided in a state of being applied to the right side surface in B8.

  The ninth portion from the left, that is, the portion having the left inner space S in the rightmost container B9 is used for heat transfer adjustment without being used for anything, and the selective oxidation catalyst 6c is used with the right inner space S as the catalyst housing space R. The selective oxidation unit 6 is configured by a portion having the right internal space S.

  Nine containers B are located between the leftmost container B1 and the second container B2 from the left, between the third container B3 from the left and the fourth container B4 from the left, and from the left. In a state where the heat insulating material 18 is disposed between the fourth container B4 and the fifth container B5 from the left, they are pressed by the pressing mechanism K from both sides in the container alignment direction, and are arranged in close contact. Further, a cooling fan 37 is provided on the side of the rightmost container B9 constituting the selective oxidation unit 6 so as to ventilate the container B9.

As shown in FIGS. 2 and 3, the pressing mechanism K includes a pair of holding plates 51 arranged to be respectively applied to the containers B at both ends of the container stack A in the container arrangement direction, and the pair of holding plates 51. And six sets of screw-type connecting means to be connected.
The screw type connecting means includes a bolt 52, a pair of nuts 53, and a pair of spring washers 54.
Each of the pair of holding plates 51 is formed in an L shape, and the pair of holding plates 51 are arranged in a line-symmetric form in a front view.
And the both ends of the volt | bolt 52 are tightened with the nut 53 via the spring washer 54 from the both sides in the state inserted in the holding | maintenance board 51, and the some container B in the direction orthogonal to a container arrangement direction It is configured to be pressed from both sides of the container arrangement direction in a state where relative movement is allowed. Further, the expansion and contraction of each container B in the container alignment direction is allowed by the expansion and contraction action of the spring washer 54.

In arranging the nine containers B 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, and the selective oxidation unit. By adjusting the cooling capacity by adjusting the air flow rate of the cooling fan 37 so as to maintain 6 at the selective oxidation treatment temperature, the desulfurization unit 1 and the transformation unit 5 are adjacent to each other at the treatment temperature. The heat transfer state between things is preset.
When the hydrogen-containing gas generator P is started, the desulfurization section heater 35 is heated to operate, the desulfurization section 1 is heated to the desulfurization processing temperature, and the two shift section heaters 36 are heated to operate. The shift section 5 is configured to be heated to the shift processing temperature.

  Although not shown, each of the desulfurization unit 1, the reforming unit 2, the shift unit 5 and the selective oxidation unit 6 is provided with a temperature sensor for detecting the temperature of each catalyst.

  As shown in FIGS. 2 and 3, when the pair of holding plates 51 are installed on the installation surface (not shown), the container laminate A is held in a state of being separated from the installation surface by the pair of holding plates 51.

  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 20 is connected to the raw fuel flow section 15 before desulfurization, the desulfurization section 1 and the raw fuel flow section 13 after desulfurization, the raw fuel flow section 13 and the reforming section 2 after desulfurization, The reforming section 2 and the heat retaining flow section 10 are composed of the heat retaining flow section 10 and the upstream reformed gas flowing section 12, and the upstream reformed gas flow section 12 and the downstream reforming section. The gas flow section 14 is the first stage transformation section 5 and the second stage transformation section 5 is the second stage transformation section 5 and the third stage transformation section 5 is the third stage transformation section. 5 and the selective oxidation unit 6 are connected to each other through a gas processing channel 27, and the selective oxidation unit 6 and a fuel gas supply unit of the fuel cell G are connected to each other through a fuel gas supply channel 23. .

A raw material water preheating heat exchanger 16 is provided across the gas processing flow path 27 and the reforming water supply path 21 that connect the third stage shift section 5 and the selective oxidation section 6.
Further, an ejector 17 for mixing water vapor into the desulfurized raw fuel gas is provided in the gas processing flow path 27 that connects the desulfurized section 1 and the raw fuel flow-through section 13 after desulfurization.

  Further, a selective oxidation air supply path 28 to which selective oxidation air is supplied from the combustion air blower 33 is connected to the gas processing flow path 27 that connects the third stage shift section 5 and the selective oxidation section 6. The reformed gas converted by the shift unit 54 is mixed with selective oxidation air and supplied to the selective oxidation unit 6.

  The combustion part 4 and the heating exhaust gas flow part 8 are connected to the heating exhaust gas flow part 8 and the cooling exhaust gas flow part 11 via the combustion gas flow path 29, 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 8 and the cooling exhaust gas flow portion 11 in this order to be discharged.

  The reforming water supply path 21 is connected to the lower end of the evaporation processing section 9, and a steam flow path 30 that guides the steam generated in the evaporation processing section 9 by heating by the heating exhaust gas flow section 8 is provided to the ejector 17. It is connected.

  That is, the raw fuel gas supplied through the raw fuel gas supply path 20 is desulfurized in the desulfurization unit 1, and the steam generated in the evaporation processing unit 9 and supplied through the water vapor path 30 is supplied to the desulfurized raw fuel gas. The desulfurized raw fuel gas mixed with the ejector 17 and mixed with the steam 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. 23 to supply to the fuel cell G.

Next, the subdivided catalyst removal structure M provided for each of the desulfurization unit 1, the reforming unit 2, the shift unit 5, and the selective oxidation unit 6 will be described.
Since the subdivided catalyst removal structure M provided in each of the desulfurization unit 1, the reforming unit 2, the shift unit 5 and the selective oxidation unit 6 has the same configuration, FIG. 5 and FIG. In the following, the subdivided catalyst removal structure M provided in the reforming unit 2 will be described with reference to FIGS. 5 and 6. FIG. 5 is a vertical right side view of a portion constituting the reforming unit 2 in the second container B2 from the left (hereinafter sometimes simply referred to as container B2), and FIG. FIG.

  As shown in FIG. 4, the container B2 communicates with the upper end portion of the left dish-shaped container forming member 41 to the upper end portion of the left inner space S (which becomes the combustion space of the combustion unit 4). A gas flow outlet 44 is attached to the upper end portion of the right dish-shaped container forming member 41 and communicates with the upper end portion of the right inner space S (which becomes the catalyst housing space R of the reforming unit 2). An inlet 43 is attached, and a gas outlet 44 is attached to a lower end portion of the right dish-shaped container forming member 41 so as to communicate with a lower end portion of the right inner space S.

A gas processing flow path 27 for receiving the desulfurized raw fuel gas sent from the raw fuel flow section 13 after desulfurization into the reforming section 2 is formed in the gas inlet 43 at the upper end portion of the right dish-shaped container forming member 41 in the container B2. A gas processing flow path 27 that sends the reformed gas that is connected and reformed in the reforming section 2 to the heat retaining flow-through section 10 has a gas flow in the lower end portion of the right dish-shaped container forming member 41 in the container B2. Connected to outlet 44.
A combustion gas passage 29 for sending the combustion gas of the reforming burner 3 from the combustion section 4 to the heating exhaust gas flow section 8 is a gas outlet at the upper end portion of the left dish-shaped container forming member 41 in the container B2. 44.

In the catalyst storage space R for the reforming unit 2 constituted by the internal space S on the right side of the container B2, a partition net is provided at a position near the lower part of the middle part in the vertical direction and above the connection part of the gas outlet 44. 46 is provided so as to partition the catalyst housing space R up and down, and the catalyst housing space R is partitioned into an upper catalyst housing portion Ra and a lower segmented catalyst housing portion Rb.
The partition net 46 does not pass a normal granular catalyst (reformed catalyst 2c in the case of the reforming unit 2) that has not been subdivided, and does not pass through the subdivided catalyst (reformed catalyst 2c in the case of the reforming unit 2). A catalyst that can pass through the catalyst 2s) is used, and, for example, a mesh made of SUS having a mesh opening (size of a gap between the lines) of 0.4 mm is used.

  Then, the reforming catalyst 2c is accommodated in the catalyst accommodating portion Ra of the catalyst accommodating space R constituted by the left inner space S of the container B2 in a state where it is received by the partition net 46.

  Although detailed explanation and illustration are omitted, as shown in FIG. 1, the catalyst storage space R for the desulfurization section 1 constituted by the left inner space S of the fifth container B5 from the left, six from the left The metamorphic section 5 is composed of an inner space S on the right side of the container B6 of the eye, an inner space S on the left side of the seventh container B7 from the left, and an inner space S on the left and right of the eighth container B7 from the left. Similarly, a partition net 46 is provided in each of the catalyst housing space R and the catalyst housing space R for the selective oxidation unit 6 constituted by the left inner space S of the rightmost container B9. Each catalyst housing space R is partitioned into an upper catalyst housing portion Ra and a lower fragmented catalyst housing portion Rb.

  The desulfurization catalyst 1c, the shift catalyst 5c, and the selective oxidation catalyst 6c are received by the partition net 46 in the catalyst storage portions Ra of the catalyst storage spaces R for the desulfurization unit 1, the shift unit 5, and the selective oxidation unit 6, respectively. Is accommodated in a state where

As shown in FIG. 2, the vibrator 50 vibrates the container laminate A by being held by the container laminate A while being spaced from the installation surface and being applied to the lower end surface of the container laminate A. Is provided.
Since the vibrator 50 is well known, a detailed description and illustration thereof will be omitted. Briefly, the vibrator 50 is attached with a weight with its center of gravity biased to the rotation shaft of the motor, and is rotated by rotating the rotation shaft. It is the structure which produces.

  When the vibrator 50 is operated, the container stack A is vibrated and the entire container stack A vibrates, so that the desulfurization catalyst 1c in the catalyst storage space R of the desulfurization unit 1 and the catalyst storage of the reforming unit 2 are accommodated. The reforming catalyst 2c in the space R, the shift catalyst 5c in the catalyst storage space R of the shift converter 5, and the selective oxidation catalyst 6c in the catalyst storage space R of the selective oxidation section 6 can be vibrated.

  That is, in this embodiment, the subdivided catalyst removal structure M is provided in a state where the vibrator 50 is shared with respect to each of the desulfurization unit 1, the reforming unit 2, the shift unit 5, and the selective oxidation unit 6.

Next, the control operation of the control unit C will be described.
When the operation start is commanded, the control unit C controls the gas fuel flow rate adjustment valve 38 to adjust the combustion amount of the reforming burner 3 so as to maintain the reforming unit 2 at the reforming processing temperature. In order to maintain the selective oxidation unit 6 at the selective oxidation treatment temperature, the air flow rate of the cooling fan 37 is adjusted, and the output power of the fuel cell C is adjusted within the output power adjustment range following the power load. Then, a normal operation for controlling the raw fuel gas flow rate adjustment valve 7 is executed so as to adjust the flow rate of the raw fuel gas supplied to the desulfurization unit 1 within the normal flow rate adjustment range.
When the operation stop is instructed, the control unit C extinguishes the reforming burner 3, stops the cooling fan 37, closes the raw fuel gas flow rate adjustment valve 7, and starts from the raw fuel gas supply path 20. The normal operation is terminated by stopping the supply of the raw fuel gas.

Next, a method for removing a fragmented catalyst from the hydrogen-containing gas generator will be described.
When it is determined that it is time to remove the fragmented catalyst from the catalyst housing portion Ra of the catalyst housing space R, the raw fuel gas flow rate adjustment valve 7 is closed to stop the supply of the processing target gas to the catalyst housing space R In this state, the subdivided catalyst removing operation for operating the vibrator 50 is executed.
When the normal operation is finished and the raw fuel gas flow rate adjustment valve 7 is closed, the supply of the raw fuel gas as the processing target gas to the catalyst housing space R of the desulfurization unit 1 is stopped, and the catalyst housing of the reforming unit 2 is accommodated. The supply of the desulfurized raw fuel gas as the processing target gas to the space R is stopped, the supply of the reformed gas as the processing target gas to the catalyst housing space R of the shift unit 5 is stopped, and the selective oxidation unit 6 The supply of the reformed gas after the modification process as the process target gas to the catalyst housing space R is stopped.
Therefore, the subdivided catalyst removal operation is executed when the normal operation is stopped.

In this embodiment, when the pressure of the gas to be processed supplied to the catalyst housing space R becomes equal to or higher than a predetermined set pressure that is higher than normal and the state continues for a set time for timing determination, the subdivided catalyst removal timing is reached. It is determined that Incidentally, as the set pressure, for example, a pressure that is about 30% higher than the preset normal pressure is set.
That is, when the pressure of the raw fuel gas detected by the raw fuel gas supply pressure detector 19 becomes equal to or higher than the set pressure and the state continues for the set time for timing determination, it is determined that the subdivided catalyst removal timing has come.

In this embodiment, the subdivided catalyst removal operation (subdivided catalyst removal method) is configured to be executed by the control unit C, and the control operation will be described below.
The control unit C monitors the pressure of the raw fuel gas detected by the raw fuel gas supply pressure detector 19 during normal operation, and the detected pressure becomes equal to or higher than the set pressure, and the state is set for timing determination. If the time continues, then, when the normal operation is terminated based on the operation stop command, the temperature of the reforming unit 2 decreases to the set temperature for starting the subdivided catalyst removal operation (for example, 60 ° C.). Then, the vibrator 50 is activated to start the subdivided catalyst removal operation. After the start, when the set time for the subdivided catalyst removal operation elapses, the vibrator 50 is stopped and the subdivided catalyst removal operation is ended. Incidentally, the set time for the subdivided catalyst removal operation is set to a time during which the subdivided catalyst can be sufficiently removed from the catalyst housing portion Ra by executing the subdivided catalyst removal operation.

  When the subdivided catalyst removal operation is executed, the reforming catalyst 2c of the catalyst housing portion Ra in the catalyst housing space R of the reforming portion 2 is vibrated as shown in FIGS. 5 (b) and 6 (b). Therefore, the subdivided catalyst 2s of the reforming catalyst 2c mixed in the reforming catalyst 2c passes through the partition net 46 and is screened to the subdivided catalyst housing portion Rb.

Although illustration is omitted, since the desulfurization catalyst 1c of the catalyst housing portion Ra in the catalyst housing space R of the desulfurization section 1 is also vibrated, the subdivided catalyst 1s of the desulfurization catalyst 1c mixed in the desulfurization catalyst 1c is also separated by a partition network. After passing through 46, the finely divided catalyst containing portion Rb is screened off.
Further, since the shift catalyst 5c in the catalyst housing portion Ra in the catalyst housing space R of the shift section 5 is also vibrated, the subdivided catalyst 5s of the shift catalyst 5c mixed in the shift catalyst 5c also passes through the partition net 46. Then, it is screened out into the segmented catalyst housing portion Rb.
Further, since the selective oxidation catalyst 6c of the catalyst housing portion Ra in the catalyst housing space R of the selective oxidation unit 6 is also vibrated, the subdivided catalyst 6s of the selective oxidation catalyst 6c mixed in the selective oxidation catalyst 6c is also separated from the partition network. After passing through 46, the finely divided catalyst containing portion Rb is screened off.

Accordingly, since it is possible to prevent the raw fuel gas flowing through the catalyst housing space R of the desulfurization section 1 from drifting, it is possible to suppress a decrease in the desulfurization processing capacity with the passage of time.
Moreover, since it is possible to prevent a drift in the desulfurization raw fuel gas flowing through the catalyst housing space R of the reforming unit 2, it is possible to suppress a decrease in reforming treatment capacity over time.
Moreover, since the uneven flow of the reformed gas flowing through the catalyst housing space R of the shift section 5 can be suppressed, it is possible to suppress a decrease in shift processing capacity with time.
Furthermore, since the uneven flow of the reformed gas after the shift treatment flowing through the catalyst housing space R of the selective oxidation unit 6 can be suppressed, it is possible to suppress a decrease in the selective oxidation treatment capability with time.
In short, in the hydrogen-containing gas generation device P that generates a hydrogen-rich hydrogen-containing gas with a low carbon monoxide gas concentration, it is possible to suppress a decrease in the hydrogen-containing gas generation capability with time.

[Another embodiment]
(A) In the hydrogen-containing gas generating device P described above, as an auxiliary machine H equipped with a prime mover (electric motor or the like), a reaction air blower 31, a cooling water pump 32, a combustion air blower 33, a reforming water pump 34, etc. Is provided. And among these, even if it operates while the hydrogen-containing gas generating device P is stopped, the one that does not adversely affect the hydrogen-containing gas generating device P is provided so that the container stack A can be vibrated. The auxiliary machine H can be used as a vibration means.
For example, even if the combustion air blower 33 (an example of a blowing unit) for supplying combustion air to the reforming burner 3 or the cooling water pump 32 is operated while the hydrogen-containing gas generator P is stopped, the hydrogen-containing gas This is an auxiliary machine H that does not adversely affect the generator P.
Therefore, as shown in FIG. 7, instead of the vibrator 50, the combustion air blower 33 is held on the container laminated body A in a state of being spaced from the installation surface and applied to the lower end surface of the container laminated body A. Thus, when the container stack A is provided so as to be vibrated, the combustion air blower 33 can be used as the vibration means.
Although illustration is omitted, if the cooling water pump 32 is provided so as to vibrate the container stack A as in the case of the combustion air blower 33, the cooling water pump 32 can be used as the vibration means. it can.

(B) In the above embodiment, each of the desulfurization unit 1, the reforming unit 2, the transformation unit 5 and the selective oxidation unit 6 is configured using a separate flat container B, and the plurality of containers B are described above. The container laminate A was constructed by assembling integrally as described above. Then, an oscillating means (vibrator 50 in the above embodiment) is provided so as to vibrate the container laminate A, so that the desulfurization unit 1, the reforming unit 2, the transformation unit 5 and the selective oxidation unit 6 are all subdivided. The case of providing the catalyst for removing catalyst M was illustrated.
Instead of this, even when the vibrating means is provided so as to vibrate the container laminate A, the partition net 46 is provided in a part of the desulfurization unit 1, the reforming unit 2, the transformation unit 5, and the selective oxidation unit 6. Accordingly, the subdivided catalyst removal structure M may be provided in a part of the desulfurization unit 1, the reforming unit 2, the conversion unit 5, and the selective oxidation unit 6.

  Further, the desulfurization unit 1, the reforming unit 2, the shift unit 5 and the selective oxidation unit 6 may be provided separately, and the subdivided catalyst removal structure M may be provided in all or part of them.

(C) The specific configuration of the reforming unit 2 and the combustion unit 4 that heats the reforming unit 2 is limited to the configuration using each of the different flat containers B as in the above embodiment. Is not to be done.
For example, an inner cylinder is provided inside the outer cylinder, the inner cylinder is used as a combustion space to form a combustion portion using the inner cylinder, and a space between the inner cylinder and the outer cylinder is defined as a catalyst housing space R. A configuration in which the reforming portion 2 is formed using the outer cylinder and the outer cylinder may be used.
In this case, in the state where the reforming burner 3 is burned and the reforming catalyst 2c in the catalyst housing space R is heated to the reforming treatment temperature, the inner cylinder expands more than the outer cylinder. The volume of the storage space R decreases, and the reforming catalyst 2 in the catalyst storage space R is lifted.
Conversely, when the reforming burner 3 is extinguished and the state in which the temperature of the reforming catalyst 2c in the catalyst housing space R is raised to the reforming temperature is stopped, the inner cylinder contracts more greatly than the outer cylinder. As the volume of the storage space R increases, the reforming catalyst 2 in the catalyst storage space R sinks.
Therefore, in this case, it is preferable to execute the subdivided catalyst removal operation in a state where the reforming burner 3 is combusted and the reforming catalyst 2c in the catalyst housing space R is heated to the reforming treatment temperature.

(D) In the above embodiment, when it is determined that the timing for removing the subdivided catalyst is reached during execution of the normal operation, the subdivided catalyst removal operation is executed when the normal operation is terminated next based on the operation stop command. However, if it is determined that the timing for removing the subdivided catalyst is reached during execution of the normal operation, the normal operation may be forcibly terminated and the subdivided catalyst removal operation may be executed.
In the above embodiment, the subdivided catalyst removal operation is automatically executed by the control unit C. However, the subdivided catalyst removal operation may be executed manually.

(E) The condition for determining that it is the timing for removing the subdivided catalyst is the condition exemplified in the above embodiment, that is, the pressure of the gas to be treated supplied to the catalyst housing space R is equal to or higher than the set pressure, Moreover, the condition is not limited to the condition that the set time for timing determination continues.
For example, a condition in which the pressure of the processing target gas supplied to the catalyst housing space R is equal to or higher than a set pressure, a condition in which the cumulative execution time of normal operation reaches a predetermined set time, and the raw fuel gas to the desulfurization unit 1 in normal operation Various conditions can be applied, such as a condition that the cumulative flow rate reaches a predetermined set flow rate, and a condition that the cumulative power generation amount of the fuel cell G reaches a predetermined set power generation amount.

(F) The supply / discharge mode of the gas to be processed with respect to the processing unit D (in the above embodiment, the desulfurization unit 1, the reforming unit 2, the shift unit 5 and the selective oxidation unit 6) provided with the subdivided catalyst removal structure M is as follows: It is not limited to the supply / discharge form illustrated in the above embodiment.
For example, the supply / discharge mode of the desulfurization raw fuel gas that is the processing target gas to the reforming unit 2 is a mode of supplying from above and discharging from below, but conversely, supplying from below It is good also as a form discharged | emitted from upper direction, and good also as a form supplied from one side of both right and left sides, and discharged | emitted from the other side.

(G) As a specific example of the processing section for selective removal processing, in the above embodiment, the selective oxidation section 6 (that is, for selective oxidation processing) that selectively oxidizes and removes carbon monoxide gas in the reformed gas. However, instead of this, a selective methanation treatment in which the selective methanation catalyst is accommodated in the catalyst accommodating space R and the carbon monoxide gas in the reformed gas is selectively methanated and removed. A processing unit may be provided.

(H) The gas processing apparatus to which the subdivided catalyst removal method according to the present invention is applicable is not limited to the gas processing apparatus for generating a hydrogen-containing gas exemplified in the above embodiment.
For example, even when applied to a gas processing apparatus for generating a hydrogen-containing gas, the present invention is limited to a configuration in which all of the desulfurization unit 1, the reforming unit 2, the shift unit 5 and the selective oxidation unit 6 are provided as in the above embodiment. However, the present invention can be applied to at least the modified portion 2 provided.
In addition, the use of the gas treatment apparatus for generating the hydrogen-containing gas is not limited to the fuel cell exemplified in the above embodiment, but the hydrogen-containing gas for various uses such as for a hydrogen purification (concentration) apparatus. It can be applied to a gas processing apparatus for generation.
Further, the present invention can be applied to gas treatment apparatuses used for various purposes such as treatment of combustion exhaust gas and deodorization treatment of odorous exhaust gas.

  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 method for removing a segmented catalyst for a gas processing apparatus that can suppress a decrease in processing capacity with the passage of operating time.

1 Desulfurization section (treatment section for desulfurization treatment)
1c Desulfurization catalyst (catalyst for desulfurization treatment)
1s Subdivided catalyst 2 Reforming part (Processing part for reforming treatment)
2c reforming catalyst (catalyst for reforming treatment)
2s Subdivided catalyst 3 Reforming burner 5 Metamorphic section (processing section for metamorphic treatment)
5c shift catalyst (catalyst for shift treatment)
5s Subdivided catalyst 6 Selective oxidation part (Processing part for selective removal treatment)
6c selective oxidation catalyst (catalyst for selective removal treatment)
6s Subdivided catalyst 33 Combustion air blower (air blowing means)
46 Partition net (partition body)
50 Vibrator (vibration means)
A Container laminated body B Container D Processing part H Auxiliary machine M Subdivision catalyst removal structure R Catalyst accommodation space Ra Catalyst accommodation part Rb Subdivision catalyst accommodation part

Claims (8)

A processing unit is provided that performs a predetermined process on the processing target gas supplied to the catalyst storage space in a state where a granular catalyst is stored in the catalyst storage space and the catalyst is heated to a predetermined processing temperature. A subdivided catalyst removal method for a gas processing apparatus, comprising:
The catalyst housing space is partitioned into an upper catalyst housing portion for accommodating the catalyst and a lower fragmented catalyst housing portion by a porous partition that allows passage of the finely divided catalyst into which the catalyst is finely divided. And providing a subdivided catalyst removal structure provided with a vibration means for vibrating the catalyst in the catalyst housing space,
When it is determined that it is time to remove the finely divided catalyst from the catalyst accommodating portion of the catalyst accommodating space, the excitation means is stopped in a state where the supply of the processing target gas to the catalyst accommodating space is stopped. A subdivided catalyst removal method for a gas processing apparatus that executes a subdivided catalyst removal operation to be operated.   The subdivided catalyst removal method for a gas processing apparatus according to claim 1, wherein when the pressure of the processing target gas supplied to the catalyst containing space is equal to or higher than a predetermined set pressure, it is determined that the subdivided catalyst removal timing has come. As the processing unit,
A catalyst for reforming treatment is accommodated in the catalyst accommodating space, and the raw material supplied to the catalyst accommodating space in a state where the temperature of the reforming catalyst is raised to a predetermined reforming treatment temperature. A processing unit for reforming processing for reforming the fuel gas into a reformed gas containing hydrogen gas as a main component;
A reforming treatment is accommodated in the catalyst housing space, and the reforming treatment is performed in the reforming treatment section in a state where the temperature of the transformation treatment catalyst is increased to a predetermined transformation treatment temperature. A modification processing unit for performing a modification process for transforming carbon monoxide gas into carbon dioxide gas with respect to the reformed gas,
The subdivided catalyst for a gas processing apparatus according to claim 1 or 2, wherein the subdivided catalyst removing structure is provided for at least one of the reforming processing unit and the shift processing unit. Removal method. As the processing unit,
A catalyst for desulfurization treatment is accommodated in the catalyst accommodating space, and the catalyst for desulfurization treatment is supplied to the processing unit for reforming treatment in a state where the catalyst is heated to a predetermined treatment temperature for desulfurization treatment. A desulfurization treatment unit that desulfurizes the previous raw fuel gas;
A catalyst for selective removal treatment is accommodated in the catalyst accommodating space, and the catalyst for selective removal treatment is transformed to a predetermined treatment temperature for selective removal treatment in the state of the modification treatment section. A selective removal treatment processing unit for performing selective removal treatment for selectively removing carbon monoxide gas with respect to the treated reformed gas;
The subdivided catalyst removal method for a gas processing device according to claim 3, wherein the subdivided catalyst removal structure is provided for at least one of the desulfurization treatment section and the selective removal treatment section. . An auxiliary machine equipped with a prime mover is provided so as to vibrate the catalyst of the processing unit provided with the subdivided catalyst removal structure,
The subdivided catalyst removal method for a gas processing apparatus according to claim 3 or 4, wherein the auxiliary machine is used as the vibration means. A reforming burner is provided for heating the reforming catalyst to the reforming treatment temperature;
Blower means for supplying combustion air to the reforming burner is provided as the auxiliary machine,
The method for removing a fragmented catalyst for a gas processing apparatus according to claim 5, wherein the blowing means is used as the vibration means. The catalyst housing space of each processing unit is formed in a separate flat container,
The plurality of containers that respectively form the catalyst housing spaces of the respective processing units are integrally assembled in a standing state with the container thickness direction oriented in the horizontal direction and arranged in a stacked state in the container thickness direction. The container laminate is configured,
The subdivided catalyst removal operation is performed in a state where the temperature of the catalyst of the processing unit provided with the subdivided catalyst removing structure is set to a predetermined set temperature lower than the processing temperature or less. A method for removing a fragmented catalyst for a gas treatment device according to item 1.   The subdivided catalyst removal method for a gas processing apparatus according to claim 7, wherein the vibration means is provided so as to vibrate the container stack.

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