JP2017105646A - Hydrogen generator and fuel cell system using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To reduce the loadage of a desulfurizing agent and to miniaturize and cost-reduce a hydrogen generator.SOLUTION: A hydrogenation desulfurizer 40 comprises: a desulfurizer filling part 41; and the second preheating flow passage 44 distributing raw material gas fed from a raw material gas feed passage 61 to a direction crossed to the progression direction of the raw material gas in the desulfurizer filling part 41 and further heating the raw material gas by heat transfer from a reformer so as to be fed to the desulfurizer filling part 41. The flow rate of the raw material gas flowing to the progressing direction of the raw material gas in the desulfurizer filling part 41 in the second preheating flow passage 44 is composed so as to be changed to a direction orthogonal to the progressing direction of the raw material gas in the desulfurizer filling part 41 and to be reduced in the vicinity of the connection part with the raw material gas feed passage 61.SELECTED DRAWING: Figure 2

Description

  The present invention relates to a hydrogen generator equipped with a desulfurizer and a fuel cell system using the same.

  The fuel cell system is mainly composed of a hydrogen generator that produces reformed gas containing hydrogen and a fuel cell that generates power using hydrogen generated by the hydrogen generator. The hydrogen generator is an apparatus that supplies hydrogen as a fuel to a fuel cell, and reforms a raw material gas to generate a hydrogen-containing gas.

  As the source gas, a hydrocarbon gas mainly composed of methane such as city gas, LP gas, and natural gas is used, but it often contains a sulfur compound as an odorous component. It is known that sulfur contained in the sulfur compound decreases the activity of reforming catalysts such as Ni-based and Ru-based used for the steam reforming reaction. In order to remove this sulfur component, the hydrogen generator generally includes a desulfurizer.

  An example of such a desulfurizer is a hydrodesulfurizer. Hydrodesulfurization is a desulfurization method in which a sulfur component is converted to hydrogen sulfide from a gas in which hydrogen is mixed with a raw material gas, and is adsorbed and removed by an adsorbent. CuZn-based, Ni-based, ZnO-based, etc. are used as the desulfurizing agent. It is done. The desulfurization agent used for hydrodesulfurization has a feature that it does not need to be replaced even for a long period of time because of its large sulfur component adsorption capacity.

  However, in hydrodesulfurization, it is necessary to heat the desulfurizing agent to a temperature suitable for desulfurization, for example, a high temperature of about 200 to 300 ° C. If the temperature of the desulfurizing agent is too high, the desulfurizing agent will be thermally deteriorated. Conversely, if the temperature is too low, the adsorption capacity of the sulfur component of the desulfurizing agent will decrease, so a large amount of desulfurizing agent will be required to be installed in the hydrodesulfurizer. Because.

  In order to reduce the size and cost of the hydrodesulfurizer, it is necessary to reduce the mounting amount of the desulfurizing agent. For that purpose, the entire temperature of the desulfurizing agent is almost uniform, for example, 250 to It is desirable to set it as 300 degreeC.

  As a hydrogen generator equipped with such a hydrodesulfurizer, for example, a hydrogen generator equipped with a hydrodesulfurizer on the outer periphery of a cylindrical reformer is known (see, for example, Patent Document 1). In this hydrogen generator, a combustor is disposed at the center in the radial direction, and a reformer and a hydrodesulfurizer are disposed in that order on the outer periphery.

  The reformer includes a reforming unit and a carbon monoxide reducing unit. The reformer is supplied with raw material gas and reformed water desulfurized by a hydrodesulfurizer, and generates reformed gas containing hydrogen by a reforming reaction in the reforming section.

  The reformed gas contains carbon monoxide as a by-product. Since carbon monoxide degrades battery performance, it is necessary to reduce carbon monoxide in hydrogen supplied to the fuel cell. The carbon monoxide reduction unit removes carbon monoxide contained in the reformed gas by a carbon monoxide shift reaction or a carbon monoxide selective oxidation reaction.

These reforming sections and carbon monoxide reduction sections have temperatures suitable for respective chemical reactions. The temperature suitable for the reforming reaction is, for example, 400 to 650 ° C., and the temperature suitable for the carbon monoxide shift reaction is, for example, 200. It is arrange | positioned around a combustor so that it may become -300 degreeC. The hydrodesulfurizer is disposed on the outer periphery of the reformer with a heat insulating material interposed therebetween so that the temperature is suitable for hydrodesulfurization.

  The reaction vessel of the hydrodesulfurizer has a concentric double cylindrical shape, and the desulfurizing agent is filled between partition plates arranged above and below the reaction vessel. An upper space is formed between the top plate and the desulfurizing agent on the upper side of the reaction vessel with the desulfurizing agent interposed therebetween, and a lower space is formed between the bottom plate and the desulfurizing agent on the lower side. The upper space is connected to a source gas discharge path for discharging the desulfurized source gas, and the lower space is connected to a source gas supply path for supplying a source gas added with hydrogen.

  The raw material gas to which hydrogen is added is introduced into the lower space of the desulfurizing agent from the raw material gas supply path, and is introduced into the inflow portion to the desulfurizing agent. In the course of the source gas rising in the desulfurizing agent, sulfur compounds in the source gas are removed by a desulfurization reaction with hydrogen. The raw material gas from which the sulfur compound has been removed reaches the upper space of the desulfurizing agent and is supplied to the reformer through the raw material gas discharge passage.

JP 2010-58995 A

  However, in the conventional hydrogen generator, the raw material gas flowing in the raw material gas supply path is supplied from the raw material gas supply path to the hydrodesulfurizer at a temperature close to the temperature of the external environment. In the vicinity of the connection with the supply path, the raw material gas flows at a temperature lower than a temperature suitable for hydrodesulfurization, for example, 250 to 300 ° C.

  Therefore, the vicinity of the connection with the feed gas supply path of the hydrodesulfurizer is cooled by the low temperature feed gas, and the connection with the feed gas supply path is close to the connection with the feed gas supply path of the hydrodesulfurizer. Compared to the part far from the part, the raw material gas flows into the desulfurizing agent filling part at a low temperature, and the temperature of the desulfurizing agent in the part near the connecting part with the raw material gas supply path of the hydrodesulfurizer becomes lower. The temperature becomes uneven.

  As a result, the entire desulfurization agent cannot be maintained at a temperature suitable for hydrodesulfurization, and there is a problem that the amount of the desulfurization agent cannot be reduced.

  The present invention solves the above-described conventional problems, and reduces the loading amount of the desulfurization agent by making the temperature of the entire desulfurization agent uniform and performing hydrodesulfurization at a temperature suitable for the conventional hydrogen generator. An object of the present invention is to provide a hydrogen generation apparatus and a fuel cell system using the same.

  In order to solve the above conventional problems, a hydrogen generator of the present invention is heated by heat transfer from a reformer that generates a hydrogen-containing gas from a raw material gas, and is supplied to the reformer. A hydrodesulfurizer for removing sulfur compounds in the raw material gas; and a raw material gas supply passage for supplying the raw material gas to the hydrodesulfurizer, wherein the hydrodesulfurizer is filled with a desulfurizing agent. And the raw material gas supplied from the raw material gas supply passage is distributed in a direction intersecting the traveling direction of the raw material gas in the desulfurizing agent filling section and supplied from the raw material gas supply passage. A preheating part that heats the raw material gas by heat transfer from the reformer and supplies the raw material gas to the desulfurizing agent filling part, and the flow rate of the raw material gas flowing in the preheating part is relative to the direction of the raw material gas in the desulfurizing agent filling part The material gas supply path In which the vicinity of the connecting portion is configured to be less.

As a result, in the preheating part of the hydrodesulfurizer, the flow length of the raw material gas is shorter in the vicinity of the connecting part of the raw material gas supply path than the opposite side of the connecting part of the raw material gas supply path. In the flow path near the connection part of the raw material gas supply path with a low flow rate, the temperature rise of the raw material gas per flow path length is larger than the flow path on the opposite side of the connection part with the high flow rate of the raw material gas supply path. The temperature difference after preheating of the raw material gas flowing in the vicinity of the connecting portion of the gas supply path and the opposite side can be reduced, and the entire desulfurizing agent filling portion can be set to a temperature suitable for hydrodesulfurization.

  The hydrogen generator of the present invention can reduce the mounting amount of the desulfurizing agent by setting the desulfurizing agent to a temperature suitable for hydrodesulfurization, so that the hydrogen generating device can be reduced in size and cost. .

Schematic longitudinal sectional view showing the configuration of the hydrogen generator in Embodiments 1 and 3 of the present invention The longitudinal cross-sectional view which shows the structure of the hydrodesulfurizer in Embodiment 1 of this invention. FIG. 2 is a cross-sectional view taken along line AA in FIG. Schematic perspective view showing the flow of the raw material gas in the hydrodesulfurizer in Embodiment 1 of the present invention Schematic longitudinal cross-sectional view which shows the structure of the fuel cell system in Embodiment 2 of this invention. The longitudinal cross-sectional view which shows the structure of the hydrodesulfurizer in Embodiment 2 of this invention. BB sectional drawing in FIG. 6 of the hydrodesulfurizer preheating part in Embodiment 2 of this invention The schematic perspective view which showed the flow of the raw material gas in the hydrodesulfurizer in Embodiment 2 of this invention The longitudinal cross-sectional view which shows the structure of the hydrodesulfurizer in Embodiment 3 of this invention. The top view which shows the distribution plate of the hydrodesulfurizer preheating part in Embodiment 3 of this invention The schematic perspective view which showed the flow of the raw material gas in the hydrodesulfurizer in Embodiment 3 of this invention

  The first invention is a reformer that generates a hydrogen-containing gas from a raw material gas, and hydrodesulfurization that is heated by heat transfer from the reformer and removes sulfur compounds in the raw material gas supplied to the reformer. And a raw material gas supply passage for supplying a raw material gas to the hydrodesulfurizer, and the hydrodesulfurizer is connected to a desulfurizing agent filling section filled with a desulfurizing agent and a raw material gas supply passage, and is supplied with a raw material gas. The raw material gas supplied from the passage is distributed in a direction crossing the traveling direction of the raw material gas in the desulfurization agent filling section, and the raw material gas supplied from the raw material gas supply passage is heated by heat transfer from the reformer. A flow rate of the raw material gas flowing in the preheating portion is changed in a direction orthogonal to the traveling direction of the raw material gas in the desulfurizing agent filling portion, Hydrogen configured to reduce the area near the connection It is formed apparatus.

  As a result, in the preheating section of the hydrodesulfurizer, the length of the flow path of the raw material gas flowing in the vicinity of the connection portion of the raw material gas supply path and the opposite side thereof is short in the vicinity of the connection section of the raw material gas supply path. However, the flow rate of the raw material gas in the preheating part near the connection of the raw material gas supply path is smaller than that on the opposite side of the connection part, so that the flow rate in the vicinity of the connection part of the raw material gas supply path is low. Is larger than the flow path on the opposite side of the connecting portion of the raw material gas supply path, so that the temperature difference after preheating of the raw material gas flowing near the connection of the raw material gas supply path and the opposite side can be reduced. . As a result, the temperature of the desulfurization agent filling part becomes a temperature suitable for hydrodesulfurization, and the amount of desulfurization agent mounted can be reduced.

In particular, the second invention is characterized in that the preheating part of the hydrodesulfurization unit of the first invention, the preheating part first wall for transmitting the heat from the reformer to the raw material gas flowing into the preheating part, and the preheating part first wall, A preheating part in the vicinity of the connection part with the raw material gas supply path is configured so that the raw material gas flows between the opposing preheating part second wall and the preheating part second wall provided farther from the reformer. The distance between the first wall and the preheating part second wall is wider than the vicinity of the connection part with the raw material gas supply path in the part separated in the direction perpendicular to the direction of progress of the raw material gas in the desulfurizing agent filling part. Is.

  Thereby, the flow resistance which the raw material gas which flows between the preheating part 1st wall and the preheating part 2nd wall near the connection part of a raw material gas supply path receives is larger than the part away from the connection part of a raw material gas supply path. Therefore, the flow rate of the raw material gas flowing between the preheating part first wall and the preheating part second wall is small in the vicinity of the connecting part of the raw material gas supply path, and is increased on the opposite side of the connecting part of the raw material gas supply path. As a result, similar to the first invention, the temperature difference after preheating of the raw material gas flowing in the vicinity of the connecting portion of the raw material gas supply path and the opposite side can be reduced. A uniform temperature suitable for desulfurization is obtained, and the loading amount of the desulfurization agent can be reduced.

  In the third aspect of the invention, in particular, the reformer of the first or second aspect of the invention is cylindrical, and the desulfurization agent filling portion of the hydrodesulfurizer is an annular cylindrical shape disposed on the outer periphery of the reformer. The desulfurizing agent filling part and the preheating part are adjacent to each other in the axial direction, and the raw material gas supplied to the hydrodesulfurizer is configured to flow in the axial direction in the preheating part and the desulfurizing agent filling part.

  As a result, the temperature difference in the circumferential direction of the raw material gas that is preheated and supplied to the desulfurizing agent filling portion is reduced, the temperature of the desulfurizing agent filling portion becomes a temperature suitable for hydrodesulfurization, and the loading amount of the desulfurizing agent is reduced. be able to.

  In the fourth invention, in particular, the preheating part first wall and the preheating part second wall in the third invention are both cylindrical, and the central axis of the preheating part first wall and the central axis of the preheating part second wall are It is configured not to overlap.

  Thereby, the space | interval of the preheating part 1st wall and the preheating part 2nd wall of a hydrodesulfurizer is changed by simple structure, and the preheating part 1st wall and the preheating part 2nd wall near the connection part of a raw material gas supply path are made. The flow rate of the raw material gas flowing between them can be made smaller than that on the opposite side of the connecting portion of the raw material gas supply path, and the raw material gas flowing in the vicinity of the connecting portion of the raw material gas supply path and on the opposite side thereof, as in the third invention Since the temperature difference after preheating can be reduced, the temperature of the desulfurizing agent filling portion becomes a temperature suitable for hydrodesulfurization, and the amount of the desulfurizing agent mounted can be reduced.

  The fifth aspect of the invention is particularly a fuel cell system comprising the hydrogen generator of any one of the first to fourth aspects of the invention and a fuel cell that generates power using the hydrogen-containing gas supplied from the hydrogen generator. It is.

  Thereby, the hydrogen generator can be reduced in cost and size, and a low-cost and small fuel cell system can be realized.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings. Note that the present invention is not limited to the embodiments.

(Embodiment 1)
FIG. 1 is a schematic configuration diagram of a hydrogen generator in Embodiment 1 of the present invention. In FIG. 1, the hydrogen generator 10 includes a cylindrical combustor 20, a reformer 30, and a hydrodesulfurizer 40 as main components, respectively, and a raw material gas supply path 61, a water supply path 62, and a reformer. The gas path 64 and the combustible gas path 66 are connected.

The source gas supply path 61 is a path constituted by a pipe that supplies a source gas to which hydrogen has been added from a source gas source (not shown) to the hydrogen generator 10. The water supply path 62 is a path configured by a pipe that supplies water supplied from a water supply source (not shown) to the hydrogen generator 10, and is located upstream of the evaporation unit 31 of the reformer 30. Connected to the flow path.

  The combustible gas path 66 is a path configured by piping for supplying a combustible gas to be combusted from a combustible gas source (not shown) to the combustor 20.

  The combustor 20 includes a burner 21 and a combustion gas flow path 22. This is a device that heats the hydrodesulfurizer 40 via the reformer 30 and the reformer 30 by the heat generated by the combustion of the combustible gas and the combustion gas generated by the combustion. The combustor 20 is inserted into the central portion of the reformer 30, and the combustor 20 and the reformer 30 are integrated.

  The combustor 20 is configured to form a downward flame in the center, and burns supplied combustible gas to generate combustion gas. The combustion gas turns back from the downward direction to the upward direction inside the combustor 20, and is exhausted from the combustion gas discharge port (not shown) communicating with the outside (atmosphere) through the combustion gas flow path 22.

  The reformer 30 is a device that generates a reformed gas containing hydrogen from a raw material gas, and includes an evaporation unit 31, a reforming unit 32, and a carbon monoxide reducing unit 33. The reforming unit 32 is filled with a reforming catalyst and disposed on the outer periphery of the combustor 20.

  The evaporation unit 31 includes a flow path in which a rod material such as a round bar is formed in a spiral shape, and is disposed in the outer space of the combustor 20 above the reforming unit 32 on the upstream side of the reforming unit 32. . The carbon monoxide reduction unit 33 is filled with a carbon monoxide reduction catalyst, and is disposed on the outer periphery of the evaporation unit 31 on the downstream side of the reforming unit 32.

  The hydrodesulfurizer 40 is disposed on the outer periphery of the reformer 30 and the inner heat insulating material 35 disposed around the reformer 30. A detailed description of the hydrodesulfurizer 40 will be described later.

  Further, the outer heat insulating material 36 is arranged to cover the entire combustor 20, the reformer 30, and the hydrodesulfurizer 40, and is a heat insulating material that keeps the combustor 20, the reformer 30, and the hydrodesulfurizer 40 warm. .

  The desulfurization gas path 63 is a path for supplying a raw material gas (hereinafter, desulfurization gas) desulfurized by the hydrodesulfurizer 40 to the reformer 30, and connects between the hydrodesulfurizer 40 and the reformer 30. It is piping.

  The structural parts of the combustor 20, the reformer 30, and the hydrodesulfurizer 40 are made of a material having heat resistance and strength such as metal and ceramics. In the present embodiment, these are made of stainless steel, The heat insulating material 35 and the outer heat insulating material 36 are constituted by a heat insulating material obtained by solidifying ceramic powder.

  The reforming catalyst filled in the reforming section 32 is a catalyst containing Ru that generates hydrogen by reacting steam and hydrocarbons by a steam reforming reaction, and the carbon monoxide filling section 33 is filled with carbon monoxide. The reduction catalyst is a carbon monoxide conversion catalyst containing Cu—Zn that reduces carbon monoxide in the reformed gas by a shift reaction. The desulfurizing agent filled in the hydrodesulfurizer 40 is a desulfurizing agent mainly composed of Cu—Zn, Co—Mo, ZnO or the like.

  The operation and action of the hydrogen generator 10 configured as described above will be described below.

The raw material gas to which hydrogen is added is supplied to the hydrodesulfurizer 40 through the raw material gas supply path 61.
The hydrodesulfurizer 40 is disposed on the outer periphery of the reforming section 32 of the reformer 30 that is at a high temperature with the inner heat insulating material 35 interposed therebetween, and the desulfurizing agent filling section 41 is at a temperature suitable for hydrodesulfurization. It is kept in a certain range of 250 to 300 ° C. In the hydrodesulfurizer 40, the sulfur component is converted into hydrogen sulfide from the supplied raw material gas, and is removed by chemical adsorption to generate desulfurized gas.

  The desulfurization gas is supplied to the reformer 30 through the desulfurization gas path 63. The desulfurized gas flowing into the reformer 30 is mixed with the water supplied from the water supply path 62 and sent to the evaporation unit 31. The evaporating unit 31 is heated by the combustor 20, and the water sent to the evaporating unit 31 exchanges heat with the combustion gas flowing through the combustion gas flow path 22 to become steam. A mixed gas of desulfurized gas and water vapor is supplied to the reforming unit 32.

  In the reforming unit 32 heated to a high temperature by the combustor 20, a reformed gas containing hydrogen is generated from the supplied mixed gas of raw material gas and steam by a steam reforming reaction. The temperature of the reforming unit 32 is adjusted by the combustor 20 so that the temperature is 400 to 650 ° C. suitable for the reforming reaction.

  The reformed gas contains carbon dioxide and carbon monoxide generated as byproducts of the steam reforming reaction. In order to reduce the carbon monoxide contained in the reformed gas, the reformed gas is sent to the carbon monoxide reduction unit 33, where the carbon monoxide concentration is 1% by the carbon monoxide shift reaction. It is reduced to the following extent. The carbon monoxide reduction part 33 is arrange | positioned on the outer periphery of the evaporation part 31 so that it may be hold | maintained at the temperature suitable for a carbon monoxide conversion catalyst, 200-300 degreeC.

  The reformed gas having a reduced carbon monoxide concentration flows out of the reformer 30 through the reformed gas path 64 and is a hydrogen storage tank or the like (not shown) that stores hydrogen contained in the reforming gas. ).

  Next, the hydrodesulfurizer 40 will be described in detail with reference to FIG. FIG. 2 is a configuration diagram of the hydrodesulfurizer in Embodiment 1 of the present invention. In FIG. 2, the same components as those in FIG.

  In FIG. 2, the hydrodesulfurizer 40 is composed of hydrogenated inner cylinders 45, hydrogenated outer cylinders 46 arranged concentrically, and upper and lower surfaces covering the outer walls as outer walls. It arrange | positions at the outer periphery of the arrange | positioned inner heat insulating material 35. FIG. The desulfurization agent filling part 41 is an area filled with a desulfurization agent between the hydrogenated inner cylinder 45, the hydrogenated outer cylinder 46, the air-permeable partition plate 50a, and the partition plate 50b.

  The preheating unit includes a first preheating channel 43, a second preheating channel 44, and a third preheating channel 51.

  The first preheating channel 43 is constituted by a space below the cylindrical wall 47 between the hydrogenated inner cylinder 45 and the hydrogenated outer cylinder 46. The 2nd preheating flow path 44 is comprised from the space between the hydrogenated inner cylinder 45 which forms the preheating part 1st wall, and the cylindrical cylindrical wall 47 which forms the preheating part 2nd wall. The third preheating channel 51 is constituted by a space between the partition plate 50 b and the cylindrical wall 47 in the vertical direction between the hydrogenated inner cylinder 45 and the hydrogenated outer cylinder 46.

  The raw material gas supply path 61 is connected to the first preheating flow path 43 from a hydrogenated outer cylinder 46 which is the outer peripheral side surface of the hydrodesulfurizer 40, and the desulfurized gas path 63 is connected to the hydrodesulfurizer 40 and the upper part of the partition plate 50a. Connected to space.

FIG. 3 is a cross-sectional view of the hydrodesulfurizer preheating portion in Embodiment 1 of the present invention, and represents a cross section AA of the hydrodesulfurizer 40 shown in FIG. In FIG. 3, the same components as those in FIG.

  As shown in FIG. 3, the cylindrical wall 47 is eccentric so that the central axes of the hydrogenated inner cylinder 45 and the hydrogenated outer cylinder 46 do not overlap, and the interval between the cylindrical wall 47 and the hydrogenated inner cylinder 45 is The connection side with the source gas supply path 61 is configured to be narrow.

  The operation and action of the hydrodesulfurizer 40 configured as described above will be described with reference to FIG. 4 is a diagram showing the flow of the raw material gas in the hydrodesulfurizer according to Embodiment 1 of the present invention. In FIG. 4, the same components as those in FIG. Description to be omitted is omitted.

  First, the raw material gas is supplied from the raw material gas supply passage 61 to the first preheating passage 43 of the hydrodesulfurizer 40. The temperature of the supplied raw material gas is the same temperature as the surrounding environment, and the first preheating flow The vicinity of the connection portion of the path 43 with the source gas supply path 61 is cooled by the source gas supplied from the source gas supply path 61 and becomes a lower temperature than the surroundings.

  Next, the source gas flows through the first preheating channel 43 and is distributed in the circumferential direction. The source gas supplied in the circumferential direction in the first preheating channel 43 flows into the second preheating channel 44 constituted by a space between the hydrogenated inner cylinder 45 and the cylindrical wall 47. Since the width of the second preheating channel 44 changes in the circumferential direction and the connection side with the source gas supply path 61 is narrow, the amount of source gas flowing through the second preheating channel 44 is the same as that of the source gas supply path 61. The connection side is reduced.

  The source gas is heated through the hydrogenated inner cylinder 45 by heat transfer from a high-temperature reformer (not shown) arranged inside the hydrogenated inner cylinder 45. The flow length of the raw material gas flowing into the second preheating flow passage 44 from the connecting portion with the raw material gas supply passage 61 in the first preheating passage 43 is short in the vicinity of the raw material gas supply passage 61, and from the raw material gas supply passage 61. It gets longer as you leave.

  Since the heating amount of the source gas flowing into the second preheating channel 44 increases as the distance from the source gas supply channel 61 increases, the temperature of the source gas flowing into the second preheating channel 44 is near the source gas supply channel 61. Is low and increases as the distance from the source gas supply path 61 increases.

  The raw material gas flowing into the second preheating channel 44 flows in the axial direction, and the hydrogenated inner cylinder 45 is transferred by heat from a high-temperature reformer (not shown) disposed inside the hydrogenated inner cylinder 45. Is heated through. The temperature rise of the source gas in the second preheating channel 44 increases in the vicinity of the connecting portion with the source gas supply channel 61 where the amount of source gas flowing is small.

  Thus, the source gas in the vicinity of the connection with the source gas supply path 61 flows into the second preheating channel 44 at a low temperature, but the second preheating on the opposite side of the source gas supply path 61 in the second preheating channel 44. Since the temperature rise is larger than that of the raw material gas that has passed through the flow path 44, the temperature difference in the circumferential direction of the raw material gas after passing through the second preheating flow path 44 is reduced, and a temperature suitable for hydrodesulfurization is 250 to 300 ° C. It can be.

  The source gas flowing through the second preheating channel 44 and flowing into the third preheating channel 51 is distributed in the circumferential direction in the third preheating channel 51 so that the axial flow rate component is uniform in the circumferential direction. Then, it flows into the desulfurizing agent filling part 41.

  In the desulfurization agent filling unit 41, the raw material gas heated to a temperature suitable for hydrodesulfurization flows through the inside of the desulfurization agent maintained at a temperature suitable for hydrodesulfurization, and is desulfurized. The desulfurized raw material gas (desulfurization gas) flows out from the hydrodesulfurizer 40 through the desulfurization gas path 63 and is supplied to a reformer (not shown).

  As described above, in the present embodiment, the source gas is configured by changing the channel width of the second preheating channel 44 in the circumferential direction and narrowing the connection side with the source gas supply channel 61. By reducing the flow rate of the raw material gas flowing in the vicinity of the connection portion with the supply path 61, the temperature difference after preheating of the raw material gas flowing in the vicinity of the connection portion of the raw material gas supply path 61 and the opposite side thereof can be reduced. it can. Thereby, since the temperature of the desulfurizing agent is maintained at a uniform temperature suitable for hydrodesulfurization, the amount of the desulfurizing agent mounted can be reduced, and the hydrogen generator 10 can be reduced in cost and size.

  In addition, in this embodiment, although the hydrogen generator 10 is formed in the cylindrical shape, it is not limited to it. Further, the reformer 30 and the hydrodesulfurizer 40 may have any shape that can effectively cause the reforming reaction, the carbon monoxide shift reaction, and the hydrodesulfurization. Examples of such a shape include a cylindrical shape and a rectangular tube shape.

(Embodiment 2)
FIG. 5 is a schematic configuration diagram of a fuel cell system according to Embodiment 2 of the present invention. In FIG. 5, the same components as those in FIG.

  The hydrogen generator 10 shown in FIG. 1 and the hydrogen generator 10b in Embodiment 2 of the present invention shown in FIG. 5 have the same configuration except for the configuration of the hydrodesulfurizer 40b, and redundant description thereof is omitted. . Detailed description of the hydrodesulfurizer 40b will be described later.

  5, the fuel cell system 100 includes a hydrogen generator 10b and a fuel cell 101. The hydrogen generator 10b and the fuel cell 101 are connected by a reformed gas path 64b, and the fuel cell 101 and the combustor 20 are off-gas. Connected by a route 67. The fuel cell 101 is a polymer electrolyte fuel cell that generates power using a gas containing hydrogen.

  About the fuel cell system 100 comprised as mentioned above, the operation | movement and an effect | action are demonstrated using FIG.

  From the source gas supply path 61, a source gas to which hydrogen has been added is supplied from a source gas source (not shown) to the hydrogen generator 10b, and is supplied from the water supply path 62 from a water supply source (not shown). Water is supplied to the hydrogen generator 10b.

  The hydrogen generator 10b generates reformed gas from the supplied raw material gas and water, and the reformed gas is supplied to the fuel cell 101 through the reformed gas path 64b. The fuel cell 101 generates power using hydrogen in the supplied reformed gas as fuel. Off-gas containing hydrogen that has not been used for power generation by the fuel cell 101 is supplied to the combustor 20 from the off-gas path 67 and used as combustible gas in the combustor 20.

  Next, the hydrodesulfurizer 40b in Embodiment 2 of this invention is demonstrated in detail using FIG. FIG. 6 is a configuration diagram of a hydrodesulfurizer according to Embodiment 2 of the present invention. In FIG. 6, the same components as those in FIG.

  In FIG. 6, the hydrodesulfurizer 40b has a central axis that is eccentric to the hydrogenated inner cylinder 45, the hydrogenated outer cylinder 46b, the hydrogenated inner cylinder 45, and the hydrogenated outer cylinder 46b arranged concentrically. The cylindrical wall 47b, which is arranged so that the connection side with the source gas supply path 61 is narrowed, is configured as an inner and outer wall, and is arranged on the outer periphery of the reformer 30 and the inner heat insulating material 35 arranged around it. The

  The desulfurization agent filling portion 41 is an area filled with a desulfurization agent between the hydrogenated inner cylinder 45, the hydrogenated outer cylinder 46b, the air-permeable partition plate 50a, and the partition plate 50b.

  The preheating part is composed of a first preheating channel 43b and a second preheating channel 44b. The 1st preheating flow path 43b is comprised from the space between the hydrogenated inner cylinder 45 which forms the preheating part 1st wall, and the cylindrical cylindrical wall 47b which forms the preheating part 2nd wall. The second preheating channel 44b is located downstream of the first preheating channel 43b, and the vertical direction is a space between the cylindrical wall 47b and the partition plate 50b between the hydrogenated inner cylinder 45 and the hydrogenated outer cylinder 46b. Consists of The source gas supply channel 61 is connected to the first preheating channel 43b from the side surface of the cylindrical wall 47b.

  FIG. 7 is a cross-sectional view of the hydrodesulfurizer preheating portion in Embodiment 2 of the present invention, and represents a BB cross section of the hydrodesulfurizer 40b shown in FIG. In FIG. 7, the same components as those in FIG.

  As shown in FIG. 7, the cylindrical wall 47 b is eccentric so that the central axis with respect to the hydrogenated inner cylinder 45 does not overlap, and the interval between the cylindrical wall 47 b and the hydrogenated inner cylinder 45 is the same as the source gas supply path 61. The connection side is configured to be narrow.

  The operation and action of the hydrodesulfurizer 40b configured as described above will be described with reference to FIG.

  FIG. 8 is a perspective view showing the flow of the raw material gas in the hydrodesulfurizer in Embodiment 2 of the present invention. In FIG. 8, the same components as those in FIG. A duplicate description is omitted.

  First, the raw material gas is supplied from the raw material gas supply passage 61 to the first preheating passage 43b of the hydrodesulfurizer 40b. The temperature of the supplied source gas is the same as that of the surrounding environment, and the vicinity of the connection portion of the first preheating channel 43b with the source gas supply channel 61 is cooled by the source gas supplied from the source gas supply channel 61. , It becomes cooler than the surroundings.

  Next, the raw material gas flows through the first preheating channel 43 b and is distributed in the circumferential direction, and at the same time, is heated by a high-temperature reformer (not shown) disposed inside the hydrogenated inner cylinder 45. The

  In the first preheating channel 43b, the length of the source gas flowing into the second preheating channel 44b from the connecting part with the source gas supply path 61 is short in the vicinity of the connecting part with the source gas supply path 61. As the distance from the connecting portion with the supply path 61 increases, the heating amount to the source gas in the first preheating channel 43b is small in the vicinity of the connecting portion with the source gas supplying path 61, and the amount of heating to the source gas supplying path 61 is small. Increasing away from the connection.

  Since the flow path width of the first preheating flow path 43b changes in the circumferential direction and the vicinity of the connecting portion with the raw material gas supply path 61 is narrow, the amount of the raw material gas flowing from the first preheating flow path 43b to the second preheating flow path 44b Is less in the vicinity of the connection portion with the source gas supply path 61 and increases as the distance from the connection portion with the source gas supply path 61 increases.

  The source gas flowing from the first preheating channel 43b to the second preheating channel 44b has a small heating amount in the vicinity of the source gas supply channel 61, but also has a small flow rate, and as the distance from the connection with the source gas supply channel 61 increases. Since the heating amount increases but the flow rate also increases, the temperature of the raw material gas flowing from the first preheating channel 43b to the second preheating channel 44b is equalized in the circumferential direction, and is a temperature suitable for hydrodesulfurization. It can be set to some 250-300 degreeC.

The source gas flowing through the first preheating channel 43b and flowing into the second preheating channel 44b is distributed in the circumferential direction so that the axial flow rate component is uniform in the circumferential direction in the second preheating channel 44b. Then, it flows into the desulfurizing agent filling part 41.

  In the desulfurization agent filling unit 41, the raw material gas heated to a temperature suitable for hydrodesulfurization flows through the inside of the desulfurization agent maintained at a temperature suitable for hydrodesulfurization, and is desulfurized. The desulfurized raw material gas (desulfurization gas) flows out from the hydrodesulfurizer 40b through the desulfurization gas path 63 and is supplied to a reformer (not shown).

  As described above, in the present embodiment, the source gas is configured by changing the channel width of the first preheating channel 43b in the circumferential direction and narrowing the vicinity of the connection portion with the source gas supply channel 61. By reducing the flow rate of the raw material gas flowing in the vicinity of the connection portion with the supply passage 61, the temperature difference after preheating of the raw material gas flowing on the connection side with the raw material gas supply passage 61 and the opposite side thereof can be reduced. it can.

  As a result, since the temperature of the entire desulfurization agent filling unit 41 can be set to a temperature suitable for hydrodesulfurization, the amount of desulfurization agent can be reduced, and the hydrogen generator 10b can be reduced in cost and size. Can do.

  The fuel cell 101 used in the fuel cell system 100 according to the present embodiment may be any fuel cell that generates power using a gas containing hydrogen, such as a solid oxide fuel cell, a solid oxide fuel cell, or the like. But you can.

(Embodiment 3)
The schematic configuration of the hydrogen generator of Embodiment 3 of the present invention is the same as that of Embodiment 1, and the schematic configuration of the hydrogen generator of Embodiment 3 is shown in FIG.

  FIG. 9 is a configuration diagram of the hydrodesulfurizer according to the third embodiment of the present invention. In FIG. 9, the same components as those of the hydrodesulfurizer in the first embodiment shown in FIG.

  The difference from Embodiment 1 is that the preheating part of the hydrodesulfurizer 40c is comprised from the 1st preheating flow path 43c and the 2nd preheating flow path 44c, as shown in FIG.

  The first preheating flow path 43c and the second preheating flow path 44c are both formed of a space between the hydrogenated inner cylinder 45 and the hydrogenated outer cylinder 46, and are located between the first preheating flow path 43c and the second preheating flow path 44c. A distribution plate 48 provided with a distribution hole 49 is arranged. The source gas supply path 61 is connected to the first preheating channel 43 c from the side surface of the hydrogenated outer cylinder 46.

  FIG. 10 is a diagram illustrating a distribution plate of the hydrodesulfurizer preheating unit in the third embodiment of the present invention. In the distribution plate 48 shown in FIG. 10, a plurality of distribution holes 49 through which the raw material gas passes are arranged in the circumferential direction, and the diameter of the distribution holes 49 is a connecting portion with the raw material gas supply path 61 on the right side in the drawing. The side is configured to be smaller than the opposite side.

  The operation and action of the hydrodesulfurizer 40c configured as described above will be described with reference to FIG.

  FIG. 11 is a diagram illustrating the flow of the raw material gas in the hydrodesulfurizer according to the third embodiment of the present invention. In FIG. 11, the same components as those in FIG. 9 described above are denoted by the same reference numerals, and redundant description thereof is omitted.

First, the raw material gas is supplied from the raw material gas supply passage 61 to the first preheating passage 43c of the hydrodesulfurizer 40c. The temperature of the supplied raw material gas is the same temperature as the surrounding environment, and the first preheating channel 43
The vicinity of the connecting portion of c with the source gas supply path 61 is cooled by the source gas supplied from the source gas supply path 61 and becomes a lower temperature than the surroundings.

  Next, the source gas flows through the first preheating channel 43c and is distributed in the circumferential direction, and at the same time, is heated by a high-temperature reformer (not shown) disposed inside the hydrogenated inner cylinder 45. The

  The source gas flows from the first preheating channel 43 c into the second preheating channel 44 c through the plurality of distribution holes 49 on the distribution plate 48, and the size of the distribution hole 49 is a connecting portion with the source gas supply channel 61. Since the side is smaller than the opposite side, the amount of the raw material gas flowing from the first preheating passage 43c to the second preheating passage 44c is smaller on the connecting portion side with the raw material gas supply passage 61 than on the opposite side.

  The source gas flowing into the second preheating channel 44c is distributed in the circumferential direction so that the axial flow rate component is uniform in the circumferential direction in the second preheating channel 44c, and flows into the desulfurizing agent filling unit 41. The source gas in the second preheating channel 44 c is heated by a high-temperature reformer (not shown) disposed inside the hydrogenated inner cylinder 45.

  The channel length of the source gas flowing from the first preheating channel 43c through the second preheating channel 44c and flowing into the desulfurizing agent filling unit 41 from the connecting portion with the source gas supply channel 61 is the source gas Since the vicinity of the connection portion with the supply path 61 is short and becomes longer as the distance from the connection portion with the source gas supply path 61 increases, the amount of heating of the source gas in the first preheating channel 43c to the second preheating channel 44c is The vicinity of the connection portion with the source gas supply path 61 is small and increases as the distance from the connection portion with the source gas supply path 61 increases.

  The source gas flowing from the first preheating channel 43 c into the second preheating channel 44 c has a small heating amount in the vicinity of the source gas supply channel 61, but the flow rate is small, and as the distance from the connecting portion with the source gas supply channel 61 increases. Since the heating amount increases but the flow rate also increases, the temperature of the raw material gas flowing from the first preheating channel 43c to the second preheating channel 44c is equalized in the circumferential direction, and is a temperature suitable for hydrodesulfurization. It can be set to some 250-300 degreeC.

  In the desulfurization agent filling unit 41, the raw material gas heated to a temperature suitable for hydrodesulfurization flows through the inside of the desulfurization agent maintained at a temperature suitable for hydrodesulfurization, and is desulfurized. The desulfurized source gas (desulfurization gas) flows out from the hydrodesulfurizer 40c through the desulfurization gas path 63 and is supplied to a reformer (not shown).

  As described above, in the present embodiment, the amount of the raw material gas flowing through the preheating portion including the first preheating passage 43c and the second preheating passage 44c is changed in the circumferential direction, and the raw material gas supply passage 61 and The flow rate of the raw material gas flowing in the vicinity of the connecting portion can be reduced, and the difference in temperature after preheating of the raw material gas flowing on the connecting portion side to the raw material gas supply path 61 and the opposite side can be reduced. As a result, since the temperature of the entire desulfurization agent filling unit 41 can be set to a temperature suitable for hydrodesulfurization, the amount of the desulfurization agent can be reduced, and the hydrogen generator 10 can be reduced in cost and size. Can do.

  In the present embodiment, the distribution plate 48 of the hydrodesulfurizer 40c is provided with a plurality of distribution holes 49 in the circumferential direction, and the diameter of the distribution holes 49 is opposite to the connection portion side with the source gas supply path 61. However, the amount of the raw material gas to be passed from the first preheating passage 43c to the second preheating passage 44c is reduced on the connecting portion side with the raw material gas supply passage 61 compared to the opposite side. Any configuration can be used.

As such a configuration, the diameter of the distribution holes 49 may be constant, and the number of the distribution holes 49 may be arranged so that the number of the connection portions with the source gas supply path 61 is smaller than that on the opposite side. The size of the hole 49 is made smaller on the side connected to the source gas supply path 61 than on the opposite side, and the number of the distribution holes 49 is made smaller on the side connected to the source gas supply path 61 than on the opposite side. May be.

  In the hydrogen generator of the present invention, since the desulfurizing agent is set to a temperature suitable for hydrodesulfurization, the amount of the desulfurizing agent can be reduced, and the hydrogen generator can be reduced in size and cost. The present invention can be applied to a domestic fuel cell system provided with a desulfurizer in the generation device.

DESCRIPTION OF SYMBOLS 10,10b Hydrogen generator 20 Combustor 21 Burner 22 Combustion gas flow path 30 Reformer 31 Evaporating part 32 Reforming part 33 Carbon monoxide reduction part 35 Inner heat insulating material 36 Outer heat insulating material 40, 40b, 40c Hydrodesulfurizer 41 Desulfurizing agent filling portion 43, 43b, 43c First preheating flow path 44, 44b, 44c Second preheating flow path 45 Hydrogenated inner cylinder 46, 46b Hydrogenated outer cylinder 47, 47b Cylindrical wall 48 Distribution plate 49 Distribution hole 50a 50b Partition plate 51 Third preheating flow path 61 Raw material gas supply path 62 Water supply path 63 Desulfurization gas path 64, 64b Reformed gas path 66 Combustible gas path 67 Off-gas path 100 Fuel cell system 101 Fuel cell

Claims (5)

  A reformer that generates a hydrogen-containing gas from a raw material gas; a hydrodesulfurizer that removes sulfur compounds in the raw material gas that is heated by heat transfer from the reformer and is supplied to the reformer; and the water A raw material gas supply path for supplying a raw material gas to the hydrodesulfurizer, wherein the hydrodesulfurizer is connected to a desulfurizing agent filling section filled with a desulfurizing agent and the raw material gas supply path, and the raw gas supply The raw material gas supplied from the passage is distributed in a direction intersecting the traveling direction of the raw material gas in the desulfurizing agent filling section, and the raw material gas supplied from the raw material gas supply passage is transferred from the reformer. And a preheating part that is heated by and supplied to the desulfurization agent filling part, and the flow rate of the raw material gas flowing in the preheating part changes in a direction orthogonal to the advancing direction of the raw material gas in the desulfurization agent filling part. , Contact with the source gas supply path Configuration hydrogen generator as part vicinity is reduced.   The preheating unit is opposed to the preheating unit first wall, which transmits heat from the reformer to the raw material gas flowing in the preheating unit, and the preheating unit first wall, and is more reformed than the preheating unit first wall. The preheating unit first wall and the preheating unit second wall in the vicinity of the connection portion with the source gas supply path are configured so that the source gas flows between the preheating unit second wall provided away from the vessel. The interval between the portion and the portion separated in the direction perpendicular to the traveling direction of the raw material gas in the desulfurizing agent filling portion is wider than the vicinity of the connecting portion with the raw material gas supply path. The hydrogen generator described.   The reformer has a cylindrical shape, the hydrodesulfurizer has an annular cylindrical shape disposed on the outer periphery of the reformer, and the desulfurizing agent filling unit and the preheating unit are adjacent in the axial direction. The hydrogen generating apparatus according to claim 1, wherein the raw material gas supplied to the hydrodesulfurizer flows in the axial direction in the preheating unit and the desulfurization agent filling unit.   The preheating part first wall and the preheating part second wall are both cylindrical, and the central axis of the preheating part first wall and the central axis of the preheating part second wall do not overlap. Hydrogen generator.   5. A fuel cell system comprising: the hydrogen generator according to claim 1; and a fuel cell that generates electric power using a hydrogen-containing gas supplied from the hydrogen generator.

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