JP2012020898A - Hydrogen generating apparatus and fuel cell system provided with the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hydrogen generating apparatus which keeps a hydro-desulfurizer at a suitable temperature, is additionally integrated with the hydro-desulfurizer, and is compact, and to provide a fuel cell system provided with the same.SOLUTION: The hydrogen generating apparatus includes: the hydro-desulfurizer 51 that has a first catalyst layer 11 composed to convert a sulfur compound contained in a raw material gas into a hydrogen sulfide and a second catalyst layer 12 composed to adsorb the hydrogen sulfide; a reformer 52 which generates a hydrogen-containing gas by reforming reaction using the raw material gas that has passed the hydro-desulfurizer 51; and a hydrogen-containing gas flow passage 54 which is provided to be adjacent to the reformer 52 through a partition 53 and through which the hydrogen-containing gas sent from the reformer 52 flows. The hydro-desulfurizer 51 is composed to heat the first catalyst layer 11 and the second catalyst layer 12 in this order by the hydrogen-containing gas flowing in the hydrogen-containing gas flow passage 54.

Description

  The present invention relates to a hydrogen generator that generates hydrogen by reacting a hydrocarbon-based fuel and water, and a fuel cell system including the hydrogen generator, and more particularly to a configuration of the hydrogen generator.

  A fuel cell system usually includes a hydrogen generator because hydrogen gas used as a fuel during power generation is not maintained as a general infrastructure. In the hydrogen generator, a steam reforming reaction is generally used. In this steam reforming reaction, for example, hydrogen as a main component is produced by reacting a raw city gas and steam with a Ni-based or Ru-based reforming catalyst at a high temperature of about 600 ° C. to 700 ° C. To produce a hydrogen-containing gas. As a method for obtaining thermal energy necessary for the steam reforming reaction, a method of burning fuel off-gas from the fuel cell with a burner is generally used.

  By the way, the source gas supplied to the hydrogen generator contains a sulfur compound. Specifically, in city gas and LP gas mainly composed of methane, sulfur compounds such as sulfides and mercaptans are added as an odorant for the purpose of leakage detection in addition to sulfur derived from raw materials. ing. And it is known that even if the sulfur contained in these sulfur compounds has a very low concentration, the activity of the Ni-based or Ru-based reforming catalyst frequently used in the steam reforming reaction is reduced. .

  For this reason, source gas, such as city gas and LP gas, is appropriately desulfurized before being supplied to the hydrogen generator. As a method of desulfurization treatment, a method of removing sulfur compounds by adsorption at room temperature is common, but in this room temperature desulfurization method, the amount of sulfur that can be adsorbed and removed is small, so the adsorbent must be replaced at regular intervals. There are problems such as an increase in cost and frequent maintenance.

  Thus, as a countermeasure for such a problem, a hydrodesulfurization type desulfurizer (hereinafter, hydrodesulfurizer) capable of increasing the desulfurization amount has been developed. In the hydrodesulfurization method, a sulfur compound contained in a raw material gas is reacted with hydrogen at about 300 ° C. to 350 ° C. using a hydrogenation catalyst to convert it into hydrogen sulfide, and then, 250 ° C. to 300 ° C. using an adsorption catalyst. Adsorb and remove hydrogen sulfide at about ℃. As described above, in the hydrodesulfurization method, it is necessary to raise the temperature of each catalyst in the hydrodesulfurizer to the above temperature in order to exert its function.

  Here, hydrogen generators that utilize the retained heat of the reformed gas to heat the hydrodesulfurizer have been proposed (see, for example, Patent Document 1 and Patent Document 2). In the fuel reformer disclosed in Patent Document 1, heat transfer is performed to transfer heat from the combustion exhaust gas to the desulfurization layer between the wall surface of the desulfurization layer of the desulfurizer and the wall surface between the flow of the combustion exhaust gas of the reformer. Means (heat pipe) are provided, and startability is improved by heat transfer from the combustion exhaust gas. Further, the fuel cell reformer disclosed in Patent Document 2 includes a reforming reaction cylinder that houses a desulfurization section between the reforming section and the transformation section, and the reforming section side of the reforming reaction cylinder. By providing the combustion means at the end of the apparatus, the configuration of the apparatus is simplified.

JP 2007-55868 A JP 2009-96706 A

  However, in the fuel reformer disclosed in Patent Document 1, since the desulfurizer and the reformer are provided separately, by providing a separate heat transfer means (heat pipe), Although startability has been improved by heat transfer, there has been a problem that the configuration becomes complicated and the manufacturing process cannot be complicated and the cost cannot be reduced. In addition, since a separate heat transfer means is provided, there is a problem that the cost of the hydrogen generator and hence the fuel cell system cannot be reduced. Further, in the fuel cell reforming apparatus disclosed in Patent Document 2, the desulfurization section has an inlet on the metamorphic section side, and the desulfurization section has an outlet on the reforming section. However, there was a problem that it was difficult to keep the desulfurization part at an appropriate temperature.

  The present invention has been made in view of the above problems, and improves the heat utilization of the reformer, and has a simpler configuration than that of the conventional hydrogen generator and an easy-to-maintain hydrodesulfurizer. It aims at providing a fuel cell system provided with the same.

  In order to solve the above conventional problems, a hydrogen generator according to the present invention adsorbs the hydrogen sulfide and a first catalyst layer configured to convert a sulfur compound contained in a raw material gas into hydrogen sulfide. A hydrodesulfurizer having a second catalyst layer, a reformer that generates a hydrogen-containing gas by a reforming reaction using a raw material gas that has passed through the hydrodesulfurizer, and a partition wall in the reformer And a hydrogen-containing gas flow path through which the hydrogen-containing gas sent from the reformer flows, and the hydrodesulfurizer includes the hydrogen-containing gas flow path. The first catalyst layer and the second catalyst layer are heated in this order by the hydrogen-containing gas flowing therethrough.

  With this configuration, the first catalyst layer of the hydrodesulfurizer can be kept at a high temperature and the second catalyst layer can be kept at a low temperature by heat transfer of the hydrogen-containing gas, and the heat utilization of the reformer can be improved. It becomes.

  In the hydrogen generator according to the present invention, the hydrodesulfurizer and the reformer may be disposed so as to sandwich the hydrogen-containing gas flow path.

  In the hydrogen generator according to the present invention, the first catalyst layer is a catalyst having a function of converting to hydrogen sulfide, and the second catalyst among the functions of converting to hydrogen sulfide and adsorbing hydrogen sulfide. The layer may be a catalyst having a function of adsorbing hydrogen sulfide.

  In the hydrogen generator according to the present invention, the first catalyst layer and the second catalyst layer have a catalyst species having a function of converting the sulfur compound into the hydrogen sulfide and a function of adsorbing the hydrogen sulfide. Due to heat transfer from the hydrogen-containing gas, the first catalyst layer has a first temperature at which the reaction for converting it to hydrogen sulfide becomes superior to the reaction for adsorbing hydrogen sulfide, and the second catalyst layer receives hydrogen sulfide. The adsorbing reaction may be configured to be a second temperature lower than the first temperature, which is superior to the reaction converting the sulfur compound into hydrogen sulfide.

  In the hydrogen generator according to the present invention, the second catalyst layer includes a high temperature adsorption catalyst layer and a low temperature adsorption catalyst layer, and the high temperature adsorption catalyst layer and the low temperature adsorption catalyst layer are heated in this order by the hydrogen-containing gas. It may be arranged as described.

  In the hydrogen generator according to the present invention, the high-temperature adsorption catalyst layer is disposed adjacent to the first catalyst layer, and the low-temperature adsorption catalyst layer is disposed with a space between the high-temperature adsorption catalyst layer. May be.

  Further, the hydrogen generator according to the present invention includes a mixed gas passage through which a mixed gas of the raw material gas and water vapor before flowing into the reformer flows, and at least a part of the second catalyst layer is You may be comprised so that it may be heated with the said hydrogen containing gas which flows through the part adjacent to the said mixed gas flow path through the partition of a hydrogen containing gas flow path.

  Moreover, in the hydrogen generator according to the present invention, a heat transfer relaxation portion may be provided between the hydrodesulfurizer and the partition wall forming the hydrogen-containing gas flow path.

  Moreover, in the hydrogen generator according to the present invention, the heat transfer relaxation portion may be configured by either a heat insulating material or an air reservoir.

  The hydrogen generator according to the present invention further includes a shifter having a Cu—Zn-based catalyst for reducing carbon monoxide in the hydrogen-containing gas sent from the reformer by a shift reaction, and the second catalyst. The layer may include the Cu—Zn-based catalyst, and the hydrodesulfurizer may be configured such that the second catalyst layer is located in the vicinity of the shift converter.

  The hydrogen generator according to the present invention further includes a shifter having a Cu-Zn-based catalyst that reduces carbon monoxide in the hydrogen-containing gas sent from the reformer by a shift reaction, and the low-temperature adsorption catalyst. The layer may include the Cu—Zn-based catalyst, and the hydrodesulfurizer may be configured such that the low-temperature adsorption catalyst layer is positioned in the vicinity of the shift converter.

  The fuel cell system according to the present invention includes the hydrogen generation device and a fuel cell that generates power using a hydrogen-containing gas supplied from the hydrogen generation device.

  With this configuration, it is possible to easily keep the first catalyst layer of the hydrodesulfurizer at a high temperature and the second catalyst layer at a low temperature by heat transfer of the hydrogen-containing gas, and improve the heat utilization of the reformer. Is possible.

  According to the hydrogen generator of the present invention and the fuel cell system including the hydrogen generator, the heat utilization of the retained heat of the reformer is improved with respect to the heating of the hydrodesulfurizer, and the water can be easily and easily configured with a simpler configuration than before. It is possible to keep the addition desulfurizer at an appropriate temperature.

FIG. 1 is a block diagram schematically showing a schematic configuration of the hydrogen generator according to Embodiment 1 of the present invention. FIG. 2 is a block diagram schematically showing a schematic configuration of the hydrogen generator according to Embodiment 2 of the present invention. FIG. 3 is a block diagram schematically showing a schematic configuration of the hydrogen generator according to Embodiment 3 of the present invention. FIG. 4 is a block diagram schematically showing a schematic configuration of the hydrogen generator according to Embodiment 4 of the present invention. FIG. 5 is a schematic diagram showing a schematic configuration of a hydrogen generator according to Embodiment 5 of the present invention. FIG. 6 is a block diagram schematically showing a schematic configuration of the fuel cell system according to Embodiment 6 of the present invention.

  Hereinafter, embodiments of the present invention will be exemplified with reference to the drawings. In all the drawings, the same or corresponding parts are denoted by the same reference numerals, and redundant description is omitted. Further, in all the drawings, only components necessary for explaining the present invention are extracted and illustrated, and other components are not illustrated. Furthermore, the present invention is not limited to the following embodiment.

(Embodiment 1)
The hydrogen generator according to Embodiment 1 of the present invention includes a first catalyst layer configured to convert a sulfur compound contained in a raw material gas into hydrogen sulfide, and a second catalyst configured to adsorb hydrogen sulfide. A hydrodesulfurizer having a catalyst layer, a reformer that generates a hydrogen-containing gas by a reforming reaction using the raw material gas that has passed through the hydrodesulfurizer, and a reformer that is adjacent to the reformer via a partition wall. A hydrogen-containing gas flow path through which a hydrogen-containing gas sent from the reformer flows, and the hydrodesulfurizer includes a first catalyst layer formed by the hydrogen-containing gas flowing through the hydrogen-containing gas flow path. And the aspect comprised so that it may heat in order of a 2nd catalyst layer is illustrated.

[Configuration of hydrogen generator]
FIG. 1 is a block diagram schematically showing a schematic configuration of the hydrogen generator according to Embodiment 1 of the present invention.

  As shown in FIG. 1, the hydrogen generator 101 according to Embodiment 1 of the present invention includes a first catalyst layer 11 configured to convert a sulfur compound contained in a raw material gas into hydrogen sulfide, and hydrogen sulfide. A hydrodesulfurizer 51 having a second catalyst layer 12 configured to adsorb, a reformer 52 that generates a hydrogen-containing gas by a reforming reaction using a raw material gas that has passed through the hydrodesulfurizer 51, and And a hydrogen-containing gas flow path 54 disposed adjacent to the reformer 52 via a partition wall 53 (see FIG. 5). The hydrodesulfurizer 51 is configured to be heated in the order of the first catalyst layer 11 and the second catalyst layer 12 by the hydrogen-containing gas flowing through the hydrogen-containing gas passage 54.

  Here, as the source gas, in addition to the sulfur content derived from the source material, sulfur gas such as sulfides and mercaptans is added as an odorant for the purpose of leakage detection, and a city gas mainly composed of methane ( Natural gas) or LP gas can be used.

  Further, the hydrogen generator 101 has a housing 50. In the casing 50, a reformer 52, a hydrogen-containing gas flow channel 54, a combustor 55, and a mixed gas flow channel 56 are arranged. A hydrodesulfurizer 51 is disposed outside the casing 50.

  A raw material gas supply unit 102 is connected to the hydrodesulfurizer 51 through a raw material gas supply path 71. The upstream end of the source gas supply passage 71 is connected to a gas infrastructure such as city gas, and the downstream end thereof is connected to the mixed gas passage 56. Further, a hydrogen gas path 73 is connected midway upstream of the source gas supply unit 102 in the source gas supply path 71 so that hydrogen is supplied to the hydrodesulfurizer 51 together with the source gas. ing. That is, in the middle of the source gas supply path 71, the hydrogen gas path 73, the source gas supply unit 102, and the hydrodesulfurization unit 51 are arranged in this order.

  The raw material gas supply unit 102 is configured to supply the raw material gas to the hydrodesulfurizer 51 while adjusting its flow rate. The source gas supply device 102 may be constituted by, for example, a single flow rate adjustment valve or a combination of a booster pump and a flow rate adjustment valve.

  Further, the first catalyst layer 11 of the hydrodesulfurizer 51 is disposed so as to be located upstream of the second catalyst layer 12 in the flow direction of the raw material gas in the hydrodesulfurizer 51. In the first embodiment, the first catalyst layer 11 is disposed so as to be positioned below the second catalyst layer 12.

  The hydrodesulfurizer 51 and the reformer 52 are disposed so as to sandwich the hydrogen-containing gas channel 54. As described above, the first catalyst layer 11 and the second catalyst layer 12 are heated in this order by the hydrogen-containing gas flowing through the hydrogen-containing gas channel 54. That is, the first catalyst layer 11 is disposed so as to be located upstream of the second catalyst layer 12 in the hydrogen-containing gas flow channel 54. For this reason, the 1st catalyst layer 11 becomes higher temperature than the 2nd catalyst layer 12, and in this Embodiment 1, the 1st catalyst layer 11 becomes 250-400 ° C, preferably 300-350 ° C. The 2nd catalyst layer 12 is constituted so that it may become 200-300 ° C, preferably 230-260 ° C.

  Any type of catalyst may be used as the catalyst contained in the first catalyst layer 11 as long as it has a function of converting a sulfur compound contained in the raw material gas into hydrogen sulfide. Examples of the catalyst included in the first catalyst layer 11 include a Co—Mo based catalyst and a Ni—Mo based catalyst. Moreover, the catalyst contained in the 1st catalyst layer 11 may use a single kind of catalyst, and may use a some kind of catalyst.

  Similarly, any type of catalyst may be used as the catalyst contained in the second catalyst layer 12 as long as it has a function of adsorbing hydrogen sulfide. Examples of the catalyst contained in the second catalyst layer 12 include zinc oxide (ZnO), Ni-based catalyst, Fe-based catalyst, Cu-Zn-based catalyst, Ni-Zn-based catalyst, and the like. Moreover, the catalyst contained in the 2nd catalyst layer 12 may use a single kind of catalyst, and may use a several kind of catalyst.

  Furthermore, the same catalyst species may be used for the catalyst contained in the first catalyst layer 11 and the catalyst contained in the second catalyst layer 12. Here, the catalyst type means not only a single type of catalyst but also an aspect constituted by a plurality of types of catalyst groups. Note that examples of the catalyst having both the function of converting a sulfur compound into hydrogen sulfide and the function of adsorbing hydrogen sulfide include a Cu-Zn-Ni-based catalyst and a Cu-Zn-Fe-based catalyst. These catalysts exhibit a function of converting a sulfur compound into hydrogen sulfide when the temperature is relatively high, and exhibit a function of adsorbing hydrogen sulfide when the temperature is relatively low.

  Of these catalysts, one catalyst may be used for the first catalyst layer 11 and the second catalyst layer 12, and both catalysts may be used for the first catalyst layer 11 and the second catalyst layer 12. The first catalyst layer 11 and the second catalyst layer 12 are made of a Co—Mo catalyst or Ni—Mo catalyst having a function of converting a sulfur compound into hydrogen sulfide, and zinc oxide having a function of adsorbing hydrogen sulfide ( (ZnO), Ni-based catalyst, and Fe-based catalyst may be included.

  In this case, as described above, due to heat transfer from the hydrogen-containing gas, the temperature of the first catalyst layer 11 becomes higher than that of the second catalyst layer 12, and the first catalyst layer 11 undergoes a reaction that converts it to hydrogen sulfide. The first temperature becomes superior to the reaction of adsorbing hydrogen sulfide, and the second catalyst layer 12 has a first temperature at which the reaction of adsorbing hydrogen sulfide is superior to the reaction of converting a sulfur compound into hydrogen sulfide. Lower than the second temperature. For this reason, in the 1st catalyst layer 11, a sulfur compound is converted into hydrogen sulfide, and in the 2nd catalyst layer 12, hydrogen sulfide is adsorbed.

  A reformer 52 is connected to the hydrodesulfurizer 51 via a raw material gas supply passage 71 (more precisely, the raw material gas supply passage 71 and the mixed gas passage 56). Thereby, the raw material gas desulfurized by the hydrodesulfurizer 51 is supplied to the reformer 52.

  A water supply device 103 is connected to the reformer 52 through a water supply channel 72 and a mixed gas channel 56. The water supply device 103 may be in any form as long as it can supply water while adjusting the flow rate and shut off the supply of water. For example, the water supply device 103 may be composed of a single flow rate adjustment valve. Moreover, you may be comprised by the combination of a pump and a flow regulating valve. The water supplied to the reformer 52 is heated by the heat transfer of the combustion exhaust gas generated by the combustor 55 described later and supplied as water vapor.

  In the present embodiment, the configuration including the mixed gas flow path 56 has been described. However, the raw material gas supply path 71 and the water supply path 72 do not merge and may be directly connected to the reformer 52. I do not care. In this case, at least a part of the water supply path 72 in the housing 50 is configured to be heated by the combustion exhaust gas path 75 and functions as an evaporator (not shown).

  The reformer 52 has a reforming catalyst. As the reforming catalyst, any substance may be used as long as it can catalyze a steam reforming reaction that generates a hydrogen-containing gas from a raw material and steam, for example, ruthenium on a catalyst carrier such as alumina. A ruthenium catalyst supporting (Ru) or a nickel catalyst supporting nickel (Ni) on the same catalyst carrier can be used. In the reformer 52, a hydrogen-containing gas is generated by a reforming reaction between the raw material gas desulfurized by the hydrodesulfurizer 51 and water (steam) supplied from the water supplier 103. The generated hydrogen-containing gas is supplied to a hydrogen-using device (for example, a fuel cell or a hydrogen storage tank) 100 via a hydrogen-containing gas channel 54 and a hydrogen-containing gas supply channel 76.

  The hydrogen-containing gas channel 54 is formed so as to be folded back in the first embodiment. More specifically, the hydrogen-containing gas passage 54 is formed so as to extend downward from the lower end of the reformer 52 and extend upward along the reformer 52 therefrom. Further, the hydrogen-containing gas flow channel 54 is configured to be adjacent to the mixed gas flow channel 56 via a partition wall constituting the hydrogen-containing gas flow channel 54 and to heat at least a part of the second catalyst layer 12. Portion 54a. In other words, at least a part of the second catalyst layer 12 is disposed so as to face the mixed gas flow path 56 with the portion 54a interposed therebetween. Thereby, it is possible to keep the second catalyst layer 12 at a more appropriate temperature.

  In the first embodiment, at least a part of the second catalyst layer 12 is heated by the hydrogen-containing gas flowing through the portion 54a of the hydrogen-containing gas channel 54. However, the present invention is not limited to this. Instead, the second catalyst layer 12 as a whole may be heated by the hydrogen-containing gas flowing through the portion 54a of the hydrogen-containing gas flow channel 54.

  In the middle of the hydrogen-containing gas supply path 76, the upstream end of the hydrogen gas path 73 is connected. In the middle of the hydrogen gas path 73, a moisture remover (not shown) for removing water vapor in the hydrogen-containing gas generated by the reformer 52 may be provided. The moisture remover 104 may be in any form as long as it can remove water vapor in the hydrogen-containing gas flowing through the hydrogen gas path 73, for example, by adsorbing and removing water vapor with silica gel or the like. Alternatively, the water vapor may be condensed and removed.

  In addition, the hydrogen generator 101 has a combustor 55. The combustor 55 is supplied with combustion fuel (for example, raw material gas or hydrogen-containing gas discharged from the reformer 52) and combustion air, and these are combusted to generate combustion exhaust gas. The generated combustion exhaust gas heats the reformer 52 and the like, then flows through the combustion exhaust gas path 75 and is discharged out of the hydrogen generator 101.

  Furthermore, the hydrogen generator 101 has a controller 120. The controller 120 may be in any form as long as it is a device that controls each device that constitutes the hydrogen generator 101, and can be configured by, for example, a microprocessor, a CPU, or the like. Note that the controller 120 is not only configured as a single controller, but also configured as a controller group in which a plurality of controllers cooperate to execute control of the hydrogen generator 101. I do not care. The controller 120 may include not only a calculation processing unit exemplified by a microprocessor, a CPU, and the like, but also a storage unit including a memory and a timing unit.

[Operation of hydrogen generator]
Next, the operation of the hydrogen generator 101 according to Embodiment 1 (hydrogen generation operation of the hydrogen generator 101) will be described with reference to FIG. The following operation is performed under the control of the controller 120.

  First, combustion fuel and combustion air are supplied to the combustor 55, and these are combusted to generate combustion exhaust gas. The generated combustion exhaust gas heats the reformer 52 and the mixed gas flow path 56 while flowing through the combustion exhaust gas passage 75, and is discharged out of the hydrogen generator 101. The reformer 52 heated by the combustion exhaust gas heats the hydrogen-containing gas flow path 54 disposed adjacent to the partition wall 53 through the heat transfer. The heated hydrogen-containing gas channel 54 heats the first catalyst layer 11 and the second catalyst layer 12 of the hydrodesulfurizer 51 by the heat transfer.

  As described above, in the hydrogen generator 101 according to the first embodiment, the heat of the combustion exhaust gas generated by the combustor 55 is used to heat the reformer 52, the hydrogen-containing gas passage 54, and the hydrodesulfurizer 51. By using it to improve thermal efficiency. If the first catalyst layer 11 and the second catalyst layer 12 are not sufficiently heated when the hydrogen generator 101 is started up, for example, a heater such as an electric heater is provided around the hydrodesulfurizer 51 to heat the catalyst. The first catalyst layer 11 may be heated to a first temperature by a vessel, and the second catalyst layer 12 may be heated to a second temperature that is lower than the first temperature.

  Next, the raw material gas is supplied from the raw material gas supply device 102 to the hydrodesulfurizer 51 through the raw material gas supply path 71. At this time, the raw material gas is supplied to a room temperature adsorption desulfurizer provided in the bypass passage of the raw material gas supply passage 71 (not shown), and the sulfur compound is removed from the raw material gas. The raw material gas supplied to the hydrodesulfurizer 51 flows through the hydrodesulfurizer 51 in the order of the first catalyst layer 11 and the second catalyst layer 12. Then, while flowing through the first catalyst layer 11, the sulfur compound contained in the raw material gas is converted into hydrogen sulfide by reacting with hydrogen by the catalyst disposed in the first catalyst layer 11. The hydrogen sulfide converted in the first catalyst layer 11 is supplied to the second catalyst layer 12, adsorbed by the catalyst disposed in the second catalyst layer 12, and removed from the source gas. In this way, the sulfur compound in the raw material gas is desulfurized.

  The desulfurized source gas (hereinafter referred to as “desulfurized source gas”) is supplied to the mixed gas channel 56 through the source gas supply channel 71. Further, water is supplied to the mixed gas channel 56 from the water supplier 103 via the water supply channel 72. The desulfurized raw material gas and water supplied to the mixed gas flow path 56 are each heated by the combustion exhaust gas flowing through the combustion exhaust gas passage 75 and supplied to the reformer 52. In addition, the water supplied to the mixed gas flow path 56 is vaporized into steam by heat transfer of the combustion exhaust gas.

  The raw material gas after desulfurization and water vapor supplied to the reformer 52 undergo a reforming reaction to generate a hydrogen-containing gas. The generated hydrogen-containing gas flows through the hydrogen-containing gas channel 54. At this time, the first catalyst layer 11 is heated by heat transfer from the hydrogen-containing gas, and then the second catalyst layer 12 is heated. As a result, the first catalyst layer 11 of the hydrodesulfurizer 51 is easily maintained at a temperature higher than that of the second catalyst layer 12, the first catalyst layer 11 is maintained at the first temperature, and the second catalyst layer 12 is maintained. Can be easily maintained at a second temperature lower than the first temperature.

  The hydrogen-containing gas that has flowed through the hydrogen-containing gas flow path 54 flows through the hydrogen-containing gas supply path 76 and is supplied to the hydrogen-using device 100. Further, a part of the hydrogen-containing gas flowing through the hydrogen-containing gas supply path 76 flows through the hydrogen gas path 73 and is supplied from the source gas supply path 71 to the hydrodesulfurizer 51. The water-containing gas flowing through the hydrogen gas path 73 is removed from the water vapor by the moisture remover 104.

  As described above, in the hydrogen generator 101 according to Embodiment 1, the reformer 52 is heated by the heat of the combustion exhaust gas generated by the combustor 55, and the heat held by the reformer 52 is contained in hydrogen. Thermal efficiency can be improved by using it for heating the gas flow path 54 and thus the hydrodesulfurizer 51. Further, in the hydrogen generator 101 according to the first embodiment, the hydrogen-containing gas flowing through the hydrogen-containing gas channel 54 in the order of the first catalyst layer 11 and the second catalyst layer 12 of the hydrodesulfurizer 51 is used. The first catalyst layer 11 can be easily maintained at a higher temperature than the second catalyst layer 12, and the first catalyst layer 11 is maintained at the first temperature. It is possible to easily maintain the two catalyst layers 12 at the second temperature lower than the first temperature.

  Furthermore, in the hydrogen generator 101 according to the first embodiment, the raw material gas and water vapor that flow through the mixed gas flow channel 56 and the hydrogen-containing gas that flows through the portion 54a of the hydrogen-containing gas flow channel 54 are heat exchanged. As a result, the temperature of the hydrogen-containing gas flowing through the portion 54a of the hydrogen-containing gas flow path 54 decreases. For this reason, it becomes further easier to maintain the temperature of the second catalyst layer 12 at the second temperature without overheating the second catalyst layer 12 of the hydrodesulfurizer 51.

(Embodiment 2)
In the hydrogen generator according to Embodiment 2 of the present invention, the second catalyst layer has a high temperature adsorption catalyst layer and a low temperature adsorption catalyst layer, and the high temperature adsorption catalyst layer and the low temperature adsorption catalyst layer are heated in this order by the hydrogen-containing gas. This is an example of the arrangement as described above.

  FIG. 2 is a block diagram schematically showing a schematic configuration of the hydrogen generator according to Embodiment 2 of the present invention.

  As shown in FIG. 2, the hydrogen generator 101 according to the second embodiment of the present invention has the same basic configuration as the hydrogen generator 101 according to the first embodiment, but the second catalyst layer 12 has a high temperature. The difference is that the adsorption catalyst layer 12A and the low-temperature adsorption catalyst layer 12B are provided. Specifically, the high temperature adsorption catalyst layer 12A is disposed upstream of the low temperature adsorption catalyst layer 12B in the flow direction of the raw material gas in the hydrodesulfurizer 51. In the second embodiment, the high temperature adsorption catalyst layer 12A is arranged to be positioned below the low temperature adsorption catalyst layer 12B.

  The high temperature adsorption catalyst layer 12A and the low temperature adsorption catalyst layer 12B are heated in this order by the hydrogen containing gas flowing through the hydrogen containing gas flow path 54. That is, the high-temperature adsorption catalyst layer 12A is disposed so as to be located on the upstream side of the hydrogen-containing gas flow channel 54 with respect to the low-temperature adsorption catalyst layer 12B. Thereby, the high temperature adsorption catalyst layer 12A can be kept at a higher temperature than the low temperature adsorption catalyst layer 12B. In addition, as a catalyst contained in the high temperature adsorption catalyst layer 12A, a zinc oxide (ZnO) catalyst, a Ni-based catalyst, or a Fe-based catalyst can be used. Moreover, as a catalyst contained in the low temperature adsorption catalyst layer 12B, a Cu—Zn catalyst or a Ni—Zn catalyst can be used.

  In the second embodiment, the high temperature adsorption catalyst layer 12A and the first catalyst layer 11 are disposed adjacent to each other. For this reason, since the heat held by the first catalyst layer 11 is directly transmitted to the high temperature adsorption catalyst layer 12A, the temperature of the high temperature adsorption catalyst layer 12A and the temperature of the first catalyst layer 11 can be made comparable.

  On the other hand, the high temperature adsorption catalyst layer 12A and the low temperature adsorption catalyst layer 12B are disposed with a space in between. Here, the space is sandwiched between the high-temperature adsorption catalyst layer 12A and the low-temperature adsorption catalyst layer 12B, ie, a state in which an object such as a heat conduction medium is not disposed, that is, the high-temperature adsorption catalyst layer 12A and the low-temperature adsorption catalyst. A space between the layer 12B means a gap. For this reason, since heat is transferred from the high temperature adsorption catalyst layer 12A to the low temperature adsorption catalyst layer 12B through the space, the low temperature adsorption catalyst layer 12B has a lower temperature than the high temperature adsorption catalyst layer 12A.

  Thus, in the second embodiment, the temperature of the high temperature adsorption catalyst layer 12A is 250 to 400 ° C., preferably 300 to 350 ° C., and the low temperature adsorption catalyst layer 12B is 200 to 200 ° C. It is configured to be 300 ° C, preferably 230 to 260 ° C.

  Even the hydrogen generator 101 according to the second embodiment configured as described above has the same effects as the hydrogen generator 101 according to the first embodiment.

(Embodiment 3)
The hydrogen generator according to Embodiment 3 of the present invention exemplifies a mode in which a heat transfer relaxation portion is provided between a hydrodesulfurizer and a partition wall that forms a hydrogen-containing gas flow path.

  FIG. 3 is a block diagram schematically showing a schematic configuration of the hydrogen generator according to Embodiment 3 of the present invention.

  As shown in FIG. 3, the hydrogen generator 101 according to the third embodiment has the same basic configuration as the hydrogen generator 101 according to the first embodiment, but the hydrodesulfurizer 51 and the hydrogen-containing gas flow are the same. The difference is that a heat transfer relaxation portion 57 is provided between the partition wall 53 (see FIG. 5) forming the path 54. As the heat transfer relaxation part 57, for example, a heat insulating material may be disposed between the hydrodesulfurizer 51 and the partition wall 53. Examples of the heat insulating material include a heat insulating material including silica, titania, alumina, or a mixture thereof, a heat insulating material including glass wool, and the like. Further, the heat transfer relaxation portion 57 may be an air reservoir portion in which a space (gap) is formed between the hydrodesulfurizer 51 and the partition wall 53 so that air is accumulated.

  Even the hydrogen generator 101 according to the third embodiment configured as described above has the same effects as the hydrogen generator 101 according to the first embodiment.

  Further, in the hydrogen generator 101 according to the third embodiment, by providing the heat transfer relaxation unit 57, when the temperature of the hydrogen-containing gas flowing through the hydrogen-containing gas channel 54 becomes too high, The amount of heat transferred to the first catalyst layer 11 and the second catalyst layer 12 of the hydrodesulfurization unit 51 is relaxed by the heat transfer relaxation unit 57, and the temperatures of the first catalyst layer 11 and the second catalyst layer 12 are kept at appropriate temperatures. be able to.

(Embodiment 4)
The hydrogen generator according to Embodiment 4 of the present invention includes a shifter, and the hydrodesulfurizer exemplifies an aspect in which the second catalyst layer is configured in the vicinity of the shifter. .

  FIG. 4 is a block diagram schematically showing a schematic configuration of the hydrogen generator according to Embodiment 4 of the present invention.

  As shown in FIG. 4, the hydrogen generator 101 according to the fourth embodiment has the same basic configuration as the hydrogen generator 101 according to the first embodiment, but includes a transformer 58 and a hydrodesulfurizer. The difference is that 51 second catalyst layers 12 are arranged in the vicinity of the transformer 58. Specifically, the transformer 58 is provided in the middle of the hydrogen-containing gas flow channel 54 and is disposed so as to be positioned in the vicinity of the mixed gas flow channel 56. The transformer 58 also has a Cu—Zn-based catalyst that reduces carbon monoxide in the hydrogen-containing gas by a shift reaction. Similarly, the second catalyst layer 12 of the hydrodesulfurizer 51 has a Cu—Zn-based catalyst in the fourth embodiment.

  And since the 2nd catalyst layer 12 is arrange | positioned so that it may be located in the vicinity of the transformer 58, the 2nd catalyst layer 12 and the transformer 58 are the same temperature range ( For example, each difference can be ± 10 ° C.).

  Furthermore, since the transformer 58 is disposed so as to be positioned in the vicinity of the mixed gas flow path 56, heat exchange with the raw material gas and water vapor flowing through the mixed gas flow path 56 can be performed. Therefore, in the fourth embodiment, the ratio (S / C) of the steam and the raw material gas supplied to the reformer 52 is changed, or the supply amount of combustion air supplied to the combustor 55 is changed. By doing so, the temperature of the transformer 58 can be controlled. Thereby, the temperature of the transformer 58 and by extension, the second catalyst layer 12 can be controlled. Note that the second catalyst layer 12 and the transformer 58 are controlled to have a second temperature, that is, 200 to 300 ° C., preferably 230 to 260 ° C.

  The hydrogen generator 101 according to the fourth embodiment configured as described above has the same operational effects as the hydrogen generator 101 according to the first embodiment. In the hydrogen generator 101 according to the fourth embodiment, the temperature of the second catalyst layer 12 of the hydrodesulfurizer 51 can also be controlled by controlling the temperature of the transformer 58, and the second catalyst layer 12 can be more stably maintained at the second temperature.

(Embodiment 5)
The hydrogen generator according to Embodiment 5 of the present invention includes a shifter, and the hydrodesulfurizer is illustrated as an example in which the low-temperature adsorption catalyst layer of the second catalyst layer is positioned in the vicinity of the shifter. To do.

  FIG. 5 is a schematic diagram showing a schematic configuration of a hydrogen generator according to Embodiment 5 of the present invention. In FIG. 5, the configuration inside the housing of the hydrogen generator is schematically shown, and the vertical direction in the housing is represented as the vertical direction in the drawing. Hereinafter, a specific configuration inside the housing 50 in the hydrogen generator 101 according to Embodiment 5 of the present invention will be described with reference to FIG. 5, and the other configurations will be described with respect to the hydrogen generator according to Embodiment 1. Since it is the same as 101, detailed description thereof is omitted.

  As shown in FIG. 5, the housing 50 is formed in a stepped cylindrical shape. In addition, the casing 50 includes an outer cylinder 61, an inner cylinder 62, and a radiation cylinder 63 that share the central axis C of the casing 50. A combustor 55 is disposed inside the radiation tube 63. A cylindrical space formed between the inner cylinder 62 and the radiation cylinder 63 constitutes the combustion exhaust gas flow path 75a. As a result, the combustion exhaust gas generated in the combustor 55 flows through the combustion exhaust gas passage 75a, and in the meantime, the raw material gas and water vapor flowing through the mixed gas passage 56 are heated. Further, the combustion exhaust gas flowing through the combustion exhaust gas passage 75 a is discharged out of the hydrogen generator 101 from the combustion exhaust gas path 75.

  The upper part of the cylindrical space formed between the outer cylinder 61 and the inner cylinder 62 constitutes a mixed gas flow path 56, and a raw material gas supply path 71 and a water supply path 72 are provided in the mixed gas flow path 56. It is connected. In addition, a reforming catalyst is filled in a lower portion of a cylindrical space formed between the outer cylinder 61 and the inner cylinder 62 to constitute a reformer 52. Further, a gap is provided between the lower end of the outer cylinder 61 and the bottom surface of the housing 50, and the lower end of the reformer 52 in the cylindrical space formed between the outer cylinder 61 and the inner cylinder 62. The space between the casing 50 and the bottom surface of the casing 50 and the cylindrical space between the casing 50 and the outer cylinder 61 constitute a hydrogen-containing gas flow path 54. That is, a part of the wall constituting the outer cylinder 61 constitutes the partition wall 53. Further, in the cylindrical space between the casing 50 and the outer cylinder 61, a transformer 58 and a CO remover 59 are provided in a portion constituted by the stepped portion of the casing 50.

  The transformer 58 has a Cu—Zn-based catalyst that reduces carbon monoxide in the hydrogen-containing gas by a shift reaction. The CO remover 59 has a Ru-based catalyst that reduces carbon monoxide in the hydrogen-containing gas by a selective oxidation reaction. A space is provided between the transformer 58 and the CO remover 59, and an air supply unit 105 for supplying oxygen (air) used for the selective oxidation reaction is connected to the space through the air supply path 77. Connected through. As a result, the air supplied from the air supplier 105 via the air supply path 77 is mixed with the hydrogen-containing gas and supplied to the CO remover 59.

  In the fifth embodiment, the CO remover 59 has reduced carbon monoxide by the selective oxidation reaction, but is not limited to this, and has reduced carbon monoxide in the hydrogen-containing gas by the methanation reaction. May be. In this case, oxygen is unnecessary, and thus the air supply unit 105 and the air supply path 77 need not be provided. Further, a form in which the CO remover 59 (including the air supply path 77 and the air supply unit 105) is not provided may be employed.

  A hydrodesulfurizer 51 is provided at a lower portion of the stepped portion of the housing 50 via a heat transfer relaxation portion 57. The hydrodesulfurizer 51 has a first catalyst layer 11 and a second catalyst layer 12, and the second catalyst layer 12 has a high temperature adsorption catalyst layer 12A and a low temperature adsorption catalyst layer 12B. The first catalyst layer 11 and the high temperature adsorption catalyst layer 12A are arranged so as to be adjacent to each other, and the low temperature adsorption catalyst layer 12B is provided in the vicinity of the transformer 58. Further, the high temperature adsorption catalyst layer 12A and the low temperature adsorption catalyst layer 12B are disposed with a space in between. Thereby, the temperature of the high temperature adsorption catalyst layer 12 </ b> A and the temperature of the first catalyst layer 11 can be made comparable. In addition, the temperature of the low temperature adsorption catalyst layer 12B and the temperature of the transformer 58 can be made approximately the same.

  In addition, as a catalyst contained in the high temperature adsorption catalyst layer 12A, a zinc oxide (ZnO) catalyst, a Ni-based catalyst, or a Fe-based catalyst can be used. Moreover, as a catalyst contained in the low temperature adsorption catalyst layer 12B, a Cu—Zn catalyst or a Ni—Zn catalyst can be used.

  Even the hydrogen generator 101 according to the fifth embodiment configured as described above has the same effects as the hydrogen generator 101 according to the first embodiment. Further, in the hydrogen generator 101 according to the fifth embodiment, since the heat transfer relaxation portion 57 is provided, the same operational effects as those of the second embodiment are obtained. In the hydrogen generator 101 according to the fifth embodiment, the first catalyst layer 11 and the high temperature adsorption catalyst layer 12A are disposed adjacent to each other, and the high temperature adsorption catalyst layer 12A and the low temperature adsorption catalyst layer 12B sandwich the space. Therefore, the same effects as those of the third embodiment are obtained.

  Further, in the hydrogen generator 101 according to the fifth embodiment, since the low temperature adsorption catalyst layer 12B is arranged in the vicinity of the transformer 58, the temperature of the transformer 58 is controlled, so that the low temperature adsorption catalyst layer 12B is controlled. The temperature of the catalyst layer 12B can also be controlled, and the low temperature adsorption catalyst layer 12B can be more stably maintained at the second temperature.

  In the fifth embodiment, as the hydrogen supplied to the hydrodesulfurizer 51, the hydrogen-containing gas in which carbon monoxide is reduced by the CO remover 59 is used. However, the present invention is not limited to this. Alternatively, a form in which the hydrogen-containing gas with reduced carbon monoxide is supplied by the transformer 58 may be employed. Specifically, the upstream end of the hydrogen gas path 73 may be connected to the space between the transformer 58 and the CO remover 59. As a result, the hydrogen-containing gas whose carbon monoxide has been reduced by the converter 58 is supplied to the first catalyst layer 11 of the hydrodesulfurizer 51 via the hydrogen gas path 73 and the raw material gas supply path 71.

(Embodiment 6)
The fuel cell system according to Embodiment 6 of the present invention exemplifies an aspect including the hydrogen generator according to Embodiment 5 and a fuel cell that generates power using the hydrogen-containing gas supplied from the hydrogen generator. Is.

[Configuration of fuel cell system]
FIG. 6 is a block diagram schematically showing a schematic configuration of the fuel cell system according to Embodiment 6 of the present invention.

  As shown in FIG. 6, the fuel cell system 200 according to Embodiment 6 of the present invention includes the fuel cell 100 according to Embodiment 1, a hydrogen generator 101, an oxidant gas supplier 106, and a controller 120. ing. Note that the controller 120 is configured to control not only each device configuring the hydrogen generator 101 but also each device configuring the fuel cell system 200.

  The fuel cell 100 has an anode 100A and a cathode 100B. Further, the fuel cell 100 is provided with an anode gas channel 10A for supplying a hydrogen-containing gas to the anode 100A and an oxidant gas channel 10B for supplying an oxidant gas to the cathode 100B. Since the configuration of the fuel cell 100 is the same as that of a general fuel cell, detailed description thereof is omitted. Further, as the fuel cell 100, each fuel cell such as a polymer electrolyte fuel cell or a phosphoric acid fuel cell can be used.

  The hydrogen generator 101 is connected to the inlet of the anode gas passage 10A of the fuel cell 100 via a hydrogen-containing gas supply passage 76, and the hydrogen-containing gas discharge passage 78 is connected to the outlet of the anode gas passage 10A. Is connected to the combustor 55 of the hydrogen generator 101. An oxidant gas supply device 106 is connected to the inlet of the oxidant gas flow path 10B via an oxidant gas supply path 79, and an oxidant gas discharge is connected to the outlet of the oxidant gas flow path 10B. A path 80 is connected.

  The oxidant gas supply unit 106 may be in any form as long as it can supply the oxidant gas flow path 10B of the fuel cell 100 with the flow rate of the oxidant gas (air) adjusted. Fans such as a sirocco fan can be used.

[Operation of fuel cell system]
Next, the operation of the fuel cell system 200 according to Embodiment 6 will be described with reference to FIG. The following operation is performed by the controller 120 controlling each device constituting the fuel cell system 200.

  First, for example, when the start-up time of the fuel cell system 200 is reached in advance, or when the user operates a remote controller (not shown) to instruct start-up processing of the fuel cell system 200, the combustion fuel is supplied to the combustor 55. And combustion air are supplied, and these are combusted to generate combustion exhaust gas. The generated combustion exhaust gas heats the reformer 52 and the mixed gas flow path 56 while flowing through the combustion exhaust gas passage 75, and is discharged out of the hydrogen generator 101. The reformer 52 heated by the combustion exhaust gas heats the hydrogen-containing gas flow path 54 disposed adjacent to the partition wall 53 through the heat transfer. The heated hydrogen-containing gas channel 54 heats the first catalyst layer 11 and the second catalyst layer 12 of the hydrodesulfurizer 51 by the heat transfer. The combustion fuel and combustion air supplied to the combustor 55 are controlled so that the fuel cell 100 has a combustion air ratio of 1.7 under power generation conditions corresponding to 1 kW.

  Next, the raw material gas supply unit 102 is operated to supply the raw material gas to the hydrodesulfurizer 51. In the hydrodesulfurizer 51, the sulfur compound in the raw material gas is converted into hydrogen sulfide in the first catalyst layer 11, and the converted hydrogen sulfide is adsorbed on the catalyst contained in the second catalyst layer 12 and desulfurized. The raw material gas after desulfurization (hereinafter referred to as post-desulfurized raw material gas) is supplied to the mixed gas passage 56 via the raw material gas supply passage 71. Further, water is supplied to the mixed gas channel 56 from the water supplier 103 via the water supply channel 72. The water supplied to the mixed gas flow path 56 is vaporized to become steam, and is supplied to the reformer 52 together with the heated raw material gas. The ratio (S / C) between the number of moles of water molecules contained in the water vapor supplied to the reformer 52 and the number of moles of carbon element contained in the raw material gas is controlled to be 3.0. Has been.

  In the reformer 52, a hydrogen-containing gas is generated by a reforming reaction between the raw material gas after desulfurization and water vapor. The generated hydrogen-containing gas flows through the hydrogen-containing gas channel 54. While flowing through the hydrogen-containing gas channel 54, the heat of the hydrogen-containing gas is transferred to the hydrodesulfurizer 51 through the partition wall 53, and the first catalyst layer 11 and the second catalyst of the hydrodesulfurizer 51. Layer 12 is maintained at an appropriate temperature. Carbon monoxide contained in the hydrogen-containing gas is reduced by the transformer 58 and the CO remover 59. A hydrogen-containing gas with reduced carbon monoxide (hereinafter referred to as fuel gas) is supplied to the hydrogen-containing gas supply path 76.

  The fuel gas supplied to the hydrogen-containing gas supply path 76 flows through the hydrogen-containing gas supply path 76 and is supplied to the anode gas flow path 10 </ b> A of the fuel cell 100. A part of the fuel gas flowing through the hydrogen-containing gas supply path 76 flows through the hydrogen gas path 73 and is supplied from the source gas supply path 71 to the hydrodesulfurizer 51. The fuel gas supplied to the hydrodesulfurizer 51 is controlled to be about 2 to 10% (converted with the amount of hydrogen gas) of the raw material gas, and is 3% in the sixth embodiment. So that it is controlled. The above operating conditions (the fuel cell 100 is a power generation condition equivalent to 1 kW, the combustion air ratio is 1.7, the S / C is 3.0, and the amount of hydrogen gas relative to the raw material gas supplied to the hydrodesulfurizer 51 When the fuel cell system 200 is operated at 3%), the first catalyst layer 11 is about 340 ° C., and the second catalyst layer 12 is about 250 to 330 ° C.

  Further, an oxidant gas (air) is supplied to the oxidant gas flow path 10B of the fuel cell 100 from the oxidant gas supply device 106 via the oxidant gas supply path 79.

  The fuel gas supplied to the anode gas flow path 10A is supplied to the anode 100A while flowing through the anode gas flow path 10A, and the oxidant gas supplied to the oxidant gas flow path 10B is the oxidant gas flow path. It is supplied to the cathode 100B while flowing through 10B. In the fuel cell 100, electricity is generated by the electrochemical reaction between the fuel gas supplied to the anode 100A and the oxidant gas supplied to the cathode 100B.

  Unused fuel gas at the anode 100 </ b> A flows through the hydrogen-containing gas discharge path 78 as off-fuel gas and is supplied to the combustor 55. The off-fuel gas supplied to the combustor 55 is used as a combustion fuel. On the other hand, unused oxidant gas at the cathode 100B flows through the oxidant gas discharge path 80 as off-oxidant gas and is discharged out of the fuel cell system 200.

  Since the fuel cell system 200 according to the sixth embodiment configured as described above includes the hydrogen generator 101 according to the fifth embodiment, the same operational effects as the hydrogen generator 101 according to the fifth embodiment. Play.

  In the fuel cell system 200 according to the sixth embodiment, the hydrogen generator according to the fifth embodiment is provided. However, the present invention is not limited to this, and any of the hydrogen generators according to the first to fourth embodiments. Such a hydrogen generation apparatus may be provided.

  From the foregoing description, many modifications and other embodiments of the present invention are obvious to one skilled in the art. Accordingly, the foregoing description is to be construed as illustrative only and is provided for the purpose of teaching those skilled in the art the best mode of carrying out the invention. The details of the structure and / or function may be substantially changed without departing from the scope of the invention. Moreover, various inventions can be formed by appropriately combining a plurality of constituent elements disclosed in the embodiment.

  The hydrogen generator according to the present invention and the fuel cell system including the hydrogen generator improve the heat utilization of the reformer, and can easily keep the hydrodesulfurizer at an appropriate temperature with a simpler configuration than the conventional one. Useful in the field of fuel cells.

DESCRIPTION OF SYMBOLS 10A Anode gas flow path 10B Oxidant gas flow path 11 1st catalyst layer 12 2nd catalyst layer 12A High temperature adsorption catalyst layer 12B Low temperature adsorption catalyst layer 50 Case 51 Hydrodesulfurizer 52 Reformer 53 Partition wall 54 Hydrogen containing gas flow Path 54a Portion 55 Combustor 56 Mixed gas flow path 57 Heat transfer relaxation part 58 Transformer 59 CO remover 61 Outer cylinder 62 Inner cylinder 63 Radiation cylinder 71 Raw material gas supply path 72 Water supply path 73 Hydrogen gas path 75 Combustion exhaust gas path 75a Combustion exhaust gas flow path 76 Hydrogen-containing gas supply path 77 Air supply path 78 Hydrogen-containing gas discharge path 79 Oxidant gas supply path 80 Oxidant gas discharge path 100 Hydrogen utilization equipment (fuel cell)
DESCRIPTION OF SYMBOLS 100A Anode 100B Cathode 101 Hydrogen generator 102 Raw material gas supply device 103 Water supply device 105 Air supply device 106 Oxidant gas supply device 120 Controller 200 Fuel cell system

Claims (12)

A hydrodesulfurizer having a first catalyst layer configured to convert a sulfur compound contained in a raw material gas into hydrogen sulfide, and a second catalyst layer configured to adsorb the hydrogen sulfide;
A reformer that generates a hydrogen-containing gas by a reforming reaction using the raw material gas that has passed through the hydrodesulfurizer;
A hydrogen-containing gas flow path that is disposed adjacent to the reformer via a partition wall, and through which the hydrogen-containing gas sent from the reformer flows,
The hydrodesulfurizer is configured to be configured to be heated in order of the first catalyst layer and the second catalyst layer by the hydrogen-containing gas flowing through the hydrogen-containing gas flow path.   The hydrogen generation apparatus according to claim 1, wherein the hydrodesulfurizer and the reformer are disposed so as to sandwich the hydrogen-containing gas flow path.   Of the function of converting to hydrogen sulfide and the function of adsorbing hydrogen sulfide, the first catalyst layer is a catalyst having a function of converting to hydrogen sulfide, and the second catalyst layer has the function of adsorbing hydrogen sulfide. The hydrogen generator according to claim 1, which is a catalyst. The first catalyst layer and the second catalyst layer have a catalyst species having a function of converting the sulfur compound into the hydrogen sulfide and a function of adsorbing the hydrogen sulfide,
Due to heat transfer from the hydrogen-containing gas, the first catalyst layer has a first temperature at which the reaction for converting it to hydrogen sulfide becomes superior to the reaction for adsorbing hydrogen sulfide, and the second catalyst layer receives hydrogen sulfide. The hydrogen generator according to claim 1, wherein the adsorbing reaction is configured to be a second temperature lower than the first temperature, which is superior to a reaction of converting a sulfur compound into hydrogen sulfide.   The second catalyst layer includes a high-temperature adsorption catalyst layer and a low-temperature adsorption catalyst layer, and is disposed so as to be heated in order of the high-temperature adsorption catalyst layer and the low-temperature adsorption catalyst layer by the hydrogen-containing gas. Item 2. The hydrogen generator according to Item 1.   The hydrogen generating apparatus according to claim 5, wherein the high temperature adsorption catalyst layer is disposed adjacent to the first catalyst layer, and the low temperature adsorption catalyst layer is disposed across the high temperature adsorption catalyst layer and a space. A mixed gas flow path through which a mixed gas of raw material gas and water vapor before flowing into the reformer flows,
At least a part of the second catalyst layer is configured to be heated by the hydrogen-containing gas flowing through a portion adjacent to the mixed gas flow path via a partition wall of the hydrogen-containing gas flow path. The hydrogen generator according to claim 1.   The hydrogen generator according to claim 1, wherein a heat transfer relaxation part is provided between the hydrodesulfurizer and a partition wall forming the hydrogen-containing gas flow path.   The hydrogen generation apparatus according to claim 8, wherein the heat transfer relaxation part is configured by one of a heat insulating material and an air reservoir. A transformer having a Cu-Zn-based catalyst that reduces carbon monoxide in the hydrogen-containing gas sent from the reformer by a shift reaction;
The second catalyst layer has the Cu-Zn-based catalyst,
The hydrogen generation apparatus according to claim 1, wherein the hydrodesulfurizer is configured such that the second catalyst layer is positioned in the vicinity of the transformer. A transformer having a Cu-Zn-based catalyst that reduces carbon monoxide in the hydrogen-containing gas sent from the reformer by a shift reaction;
The said low temperature adsorption catalyst layer has the said Cu-Zn type catalyst, and the said hydrodesulfurizer is comprised so that the said low temperature adsorption catalyst layer may be located in the vicinity of the said converter. The hydrogen generator described. The hydrogen generator according to any one of claims 1 to 11,
A fuel cell system comprising: a fuel cell that generates power using a hydrogen-containing gas supplied from the hydrogen generator.

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