JP4762496B2 - Catalytic reactor - Google Patents

Description

  The present invention relates to a catalytic reaction apparatus filled with a plurality of types of catalysts for performing a plurality of catalytic reactions. More specifically, the present invention relates to a catalytic reaction apparatus in which a plurality of types of catalysts for performing a plurality of catalytic reactions are packed in an integral cylindrical container. Concerning structure. In particular, in a hydrogen production apparatus that supplies hydrogen to a fuel cell from a hydrocarbon-based fuel such as city gas or LPG, a plurality of catalysts having different characteristics are arranged in separate layers in a cylindrical container, The present invention relates to an integrally configured catalytic reaction apparatus.

  In a fuel processing apparatus for supplying hydrogen to a catalytic reactor, for example, a fuel cell such as a polymer electrolyte fuel cell (PEFC, hereinafter abbreviated as PEFC), a plurality of reforming catalysts, shift catalysts, CO removal catalysts, etc. A catalyst is used. Here, as the shift catalyst, a single shift catalyst may be used, a high temperature shift catalyst and a low temperature shift catalyst may be used in combination, and a desulfurizing agent may be used in addition to these catalysts. When the reactors filled with these catalysts and desulfurization agents are installed separately, piping and heat insulating materials for connecting the reactors are required, and the equipment configuration becomes complicated. Therefore, with the aim of simplifying and downsizing them, a fuel processing apparatus in which the respective reactors are integrated, that is, an integrated catalytic reaction apparatus has been developed. FIG. 1 is a view showing an example thereof, which is shown as a longitudinal sectional view (WO 02 / 098790A).

WO 02 / 098790A

  As shown in FIG. 1, the catalytic reaction apparatus is configured by arranging a plurality of cylindrical bodies having different diameters provided with the same central axis at intervals. In FIG. 1, the alternate long and short dash line indicates the central axis, and the arrow indicates the direction, that is, the axial direction. The first cylindrical body 1, the second cylindrical body 2, and the third cylindrical body 3, which are sequentially increased in diameter (diameter, hereinafter the same), are arranged with the same central axis and spaced from each other. A fourth cylinder 4 having a diameter larger than that of the third cylinder 3 is disposed on the third cylinder 3. Inside the first cylindrical body 1, a cylindrical heat transfer partition wall, that is, a radiation cylinder 5 having the same central axis as the diameter of the first cylindrical body 1 is arranged, and a burner 6 is arranged in the radiation cylinder 5. ing. That is, the burner 6 is disposed at the central shaft portion and is attached to the inside of the radiation tube 5 via the upper lid / burner mounting base 7.

  The radiation cylinder 5 is disposed with a gap between the lower end thereof and the bottom plate 8 of the first cylindrical body 1, and this gap and a gap between the radiation cylinder 5 and the first cylindrical body 1 connected to the clearance are provided. Form an exhaust passage 9 for combustion exhaust gas from the burner 6. The bottom plate 8 is formed in a disc shape with a diameter corresponding to the diameter of the first cylindrical body 1. The exhaust passage 9 is connected to the exhaust port 11 of the combustion exhaust gas through a gap between the upper cover of the exhaust passage 9 (the upper surface of the upper cover and burner mounting base 7) and the partition wall 10 (the upper cover of the preheating layer 14 described later) at the upper part. Combustion exhaust gas is discharged from here.

Reference numeral 12 denotes a hydrocarbon-based source gas supply pipe. In the space between the first cylindrical body 1 and the second cylindrical body 2, a preheating layer 14 is formed in the upper part, and a reforming catalyst layer 16 is formed in the lower part. Is provided. The second cylindrical body 2 is configured such that a portion surrounding the reforming catalyst layer 16 and a portion surrounding the preheating layer 14 are configured separately, and an upper end portion surrounding the reforming catalyst layer 16 and a lower end portion surrounding the preheating layer 14 are formed. Although it joins by the junction part in between, you may comprise integrally, without providing a junction part. Moreover, although the catalyst of the reforming catalyst layer 16 is supported by a porous plate or the like at the lower part, the description thereof is omitted. A single round bar 15 is spirally arranged inside the preheating layer 14, thereby forming one continuous spiral gas passage inside the preheating layer 14. The raw material gas is supplied from the supply pipe 12, and water (water vapor) is mixed in the mixing unit 13, and then introduced into the reforming catalyst layer 16 through the preheating layer 14. In the reforming catalyst layer 16, the hydrocarbon-based raw material gas is reformed by steam while descending. When the hydrocarbon-based raw material gas is, for example, methane gas, it is reformed by the reaction of the following reaction formula (I). The reforming reaction in the reforming catalyst layer 16 is an endothermic reaction, and the reaction proceeds by absorbing the combustion heat generated in the burner 6. Specifically, when the combustion exhaust gas from the burner 6 flows through the exhaust passage 9 between the radiation cylinder 5 and the first cylindrical body 1, the heat of the combustion exhaust gas is absorbed by the reforming catalyst layer 16, A reforming reaction is performed.

  As the reforming catalyst of the reforming catalyst layer 16, a monolith type reforming catalyst is used in addition to a granular reforming catalyst, and a monolith type reforming catalyst (= honeycomb reforming catalyst) is preferably used. The reforming catalyst is used at a high temperature of about 700 ° C., for example, and when the catalytic reaction device (reformer) is used in a home cogeneration system (cogeneration system), for example, it is frequently started and stopped. There is a need. Therefore, when a reforming catalyst such as a granular material is used, there is a problem that the reforming catalyst filled in the reforming catalyst layer is crushed and pulverized due to repeated rise and fall of temperature, and the catalytic activity is lowered. . Therefore, by using a monolithic reforming catalyst as the reforming catalyst, those problems in the case of using a granular reforming catalyst can be solved. The monolithic reforming catalyst is a catalyst in which a fixed catalyst bed is integrated, and a metal catalyst, that is, a metal catalyst such as Ni or Ru, is formed on the inner surface of a ceramic or metal carrier having a number of parallel through holes, that is, cells. Is a catalyst on which is supported. Monolithic catalysts are often used mainly as exhaust gas purification catalysts for cars because they can withstand vibrations and high-temperature environments. However, by using a monolithic reforming catalyst as a reforming catalyst, The above problem can be solved.

  The lower end of the second cylindrical body 2 is spaced from the bottom plate 17 of the third cylindrical body 3, and the flow of the reformed gas is between the second cylindrical body 2 and the third cylindrical body 3. A path 18 is formed. The bottom plate 17 is configured in a disc shape with a diameter corresponding to the diameter of the third cylindrical body 3. The reformed gas is folded between the lower end of the second cylindrical body 2 and the bottom plate 17 of the third cylindrical body 3 and flows through the flow path 18 formed between the second cylindrical body 2 and the third cylindrical body 3. To do. A fourth cylindrical body 4 having a diameter larger than that of the third cylindrical body 3 is disposed on the third cylindrical body 3, and a CO shift catalyst layer 21 is provided between the second cylindrical body 2 and the fourth cylindrical body 4. It has been. A plate 19 (a portion corresponding to the diameter of the third cylinder 3 is occupied by the third cylinder 3 at the upper end of the third cylinder 3 and the lower end of the fourth cylinder 4. ) And a support plate 20 having a plurality of holes for gas circulation at intervals on the plate body 19 (the portion corresponding to the diameter of the second cylinder 2 is occupied by the second cylinder 2). , A donut-shaped support plate) is disposed. The CO shift catalyst layer 21 includes a support plate 20 and a support plate 22 having a plurality of holes for gas circulation (the portion corresponding to the diameter of the second cylindrical body 2 is occupied by the second cylindrical body 2, so a donut-shaped support plate And the upper cover of the CO shift catalyst layer 21). The support plates 20 and 22 may be formed of a mesh body made of metal or the like. In this case, the mesh body of the mesh body serves as a gas flow hole. The reformed gas that has flowed through the flow path 18 is supplied to the CO shift catalyst layer 21 through the holes of the support plate 20.

  As described above, the CO conversion catalyst layer 21 is provided between the second cylindrical body 2 and the fourth cylindrical body 4, and the cylindrical body 24 is arranged on the outer periphery of the fourth cylindrical body 4 with a space therebetween. The heat insulating material 23 is disposed between them. A heat transfer tube 26 connected to a water supply tube 25 is directly wound around the outer periphery of the cylindrical body 24 in a spiral shape. The heat transfer tube 26 acts as a cooling mechanism for indirectly cooling the CO shift catalyst layer 21. The heat insulating material 23 is wound to a thickness that can be uniformly maintained at an appropriate temperature without excessively reducing the temperature of the CO shift catalyst layer 12 by the cooling action of the heat transfer tube 26. As the heat insulating material 23, a material having good workability such as ceramic fiber is preferably used. Here, the heat transfer pipe 26 has a function as a boiler for the water supplied from the water supply pipe 25 and is a continuous single passage that continues from the water supply pipe 25, so that partial heat generation occurs in a plurality of passages. Stagnation does not occur.

In the CO conversion catalyst layer 21, a CO gas conversion reaction (water gas shift reaction) represented by the following reaction formula (II), that is, a shift reaction is performed, CO in the reformed gas is converted into carbon dioxide, and hydrogen is also added. Generate.

  The CO conversion catalyst may be a conventional catalyst (that is, a Cu / Zn-based low temperature CO conversion catalyst, etc.), but a catalyst that can be used continuously at least at 350 ° C. or higher (that is, a platinum-based or Fe / Cr-based high-temperature CO conversion catalyst). Etc.), the lengths of the reformed gas flow path 18 and the CO shift catalyst layer 21 (that is, the length between the support plate 20 and the support plate 22) can be shortened, and the respective layers can be reduced in size. As a result, the entire catalytic reaction device (reformer) can be reduced in size and weight. A platinum-based catalyst, that is, a catalyst containing platinum as a main component is configured by supporting platinum on a carrier such as alumina. Platinum-based catalysts are resistant to deterioration due to oxidation, etc., and can be used continuously even in a high temperature range of 350 ° C or higher, particularly in a high temperature range of 400 ° C or higher, and the reaction proceeds at a faster rate. Can be made.

In addition, if such a platinum-based catalyst is simply applied to the CO shift reaction, a side reaction called a methanation reaction represented by the following reaction formula (III) occurs at a high temperature range, thereby inhibiting the target CO shift reaction. May end up.

In this case, a catalyst containing platinum as a main component and a metal oxide such as CeO ₂ as an auxiliary component is used as the CO conversion catalyst. Thereby, the methanation reaction which generate | occur | produces in a high temperature range can fully be suppressed. Further, as the CO conversion catalyst, an Fe / Cr high-temperature CO conversion catalyst may be used, and furthermore, a high-temperature CO in which a base metal species such as Al, Cu, Fe, Cr, and Mo is supported on a support such as Zr. A shift catalyst or the like can also be used. The high temperature CO conversion catalyst may be used in combination with the low temperature CO conversion catalyst.

  A partition plate 27 having one communication hole 28 is provided above the support plate 22 at a predetermined interval, and CO removal air is supplied to the space between both plates through an air supply pipe 29. An annular passage 30 is provided above the partition plate 27. By using one communication hole 28 with a predetermined hole diameter, a predetermined passing speed is obtained when the reformed gas and the CO removal air pass through the communication hole 28, and the reforming gas is modified by turbulent flow during the passage. The quality gas and the air for removing CO can be mixed well. The CO removal catalyst layer 35 is disposed with a gap between the second cylinder 2, the cylinder 36 having a larger diameter, and the lower part and the upper part between the second cylinder 2 and the cylinder 36. A support plate 33 having a plurality of holes 34 (a portion corresponding to the diameter of the second cylindrical body 2 is occupied by the second cylindrical body 2), and a plurality of holes for gas circulation 38 and a support plate 37 (a portion corresponding to the diameter of the second cylindrical body 2 is occupied by the second cylindrical body 2), and is provided in a space between the support plate 37 and the support plate 37.

  A plurality of holes 32 that are equally provided in the circumferential direction are provided in the lower portion of the cylindrical body 36. The annular passage 30 is a passage formed by the cylindrical body 24, the partition plate 27, the partition plate 31, and the cylindrical body 36, and the plurality of holes 32 and the support plate 33 through the plurality of holes 34. The reformed gas, which is in communication with the CO removal catalyst layer 35 and mixed with CO removal air, is introduced into the CO removal catalyst layer 35 through the plurality of holes 32 and 34. The CO removal catalyst layer 35 communicates with a reformed gas take-out pipe 39 through a gap between a partition plate 37 having a plurality of holes 38 serving as an upper lid and the partition wall 10. Further, the CO removal catalyst layer 35 is surrounded by a cylindrical body 36, and a heat transfer tube 26 connected to the heat transfer tube 26 on the outer periphery of the cylindrical body 24 is directly spirally wound around the outer periphery of the cylindrical body 36.

The CO removal catalyst layer 35 is filled with a CO removal catalyst (= PROX catalyst), and a CO removal reaction is performed by the PROX catalyst to reduce the CO content in the reformed gas to ppm units. The CO removal catalyst is not particularly limited as long as it can selectively oxidize CO in the reformed gas. For example, a Ru-based metal catalyst is used. The metal catalyst is configured, for example, by supporting a metal catalyst such as Ru on a support such as alumina. In the CO removal catalyst layer 35, the CO removal reaction represented by the following reaction formula (IV) proceeds.

  The reformed gas from which CO has been removed in the CO removal catalyst layer 35 is discharged from a plurality of holes 38 provided in the partition plate 37 which is the upper lid, and reformed through the gap between the partition plate 37 and the partition wall 10. The gas is extracted from the gas extraction pipe 39. A heat insulating material 40 is disposed on the outer peripheral portion including the third cylindrical body 3, the cylindrical body 24, and the cylindrical body 36 to prevent heat from being dissipated to the outside. As the heat insulating material 40, for example, a heat insulating material having a high heat insulating effect such as microtherm, calcium silicate, alumina fiber or the like is used.

  FIG. 2 is an enlarged view centering on the portion of the CO removal catalyst layer 35 in FIG. As shown in FIG. 2, the reformed gas mixed with the CO removal air introduced from the plurality of holes 32 provided uniformly in the circumferential direction at the lower portion of the cylindrical body 36 passes through the CO removal catalyst layer 35. While rising, CO is oxidized and removed from the top. That is, the reformed gas mixed with the CO removal air passes through the doughnut-shaped CO removal catalyst layer 35 having a thickness from the lower side to the upper side, that is, the second cylindrical body 2 defining the CO removal catalyst layer 35 and It flows in the axial direction of the cylindrical body 36. The reformed gas take-out pipe 39 is connected to, for example, a fuel gas supply pipe to the PEFC. In this case, a reformed gas containing a predetermined concentration of hydrogen is supplied to the fuel electrode side of the PEFC, and electricity is generated using this as a fuel. Note that off-gas (anode off-gas) from the fuel electrode of PEFC may be used as fuel gas for combustion in the burner 6.

By the way, since each catalyst used in the catalytic reaction apparatus configured as described above is used in different characteristics and environments such as gas space velocity SV, gas linear velocity LV, and temperature conditions, restrictions on the apparatus design. There is. Among the catalytic reaction apparatuses, for example, the characteristics of each catalyst used in a hydrogen production apparatus for PEFC are as follows.
(1) Reforming catalyst: Since the reaction rate is high and the heat transfer rate-controlled reaction mode (because the heat transfer area is large), the reforming catalyst becomes longer in the gas flow axis direction. Moreover, since temperature is high, a heat insulating material becomes thick.
(2) Shift catalyst (CO shift catalyst): Since the reaction rate is slow, the amount of catalyst increases. Therefore, the gas space velocity SV is small and the reactor is large in the gas flow axis direction.
(3) CO removal catalyst: Since the gas linear velocity LV is large, it becomes longer in the gas flow axis direction. Further, since the temperature is low, the heat insulating material may be thin.

  In the conventional catalytic reaction apparatus as described above, since each catalyst is sequentially partitioned and installed along the gas flow axis direction, that is, the gas flows in the same direction as the axial direction of the cylindrical container. Since it is divided and installed sequentially, it becomes a shape as shown in FIGS. Among these, especially the section filled with the CO removal catalyst is smaller in the radial direction than the section filled with the CO shift catalyst, and therefore, the outer shape of the catalyst reaction apparatus in which these are integrally arranged is a complicated stepwise shape. It becomes a structure. For this reason, the number of parts is large, and it takes time for heat insulating material and piping construction. Therefore, there are problems that the manufacturing cost is high and the gas flow cannot be downsized in the axial direction.

  Therefore, in the present invention, the purpose is to solve the above-mentioned problems in the conventional catalytic reaction apparatus, and each catalyst, particularly the CO removal catalyst layer is specially and specifically arranged without impairing the characteristics of each catalyst. Accordingly, it is an object of the present invention to provide a catalytic reaction apparatus in which the number of parts is reduced, the labor for heat insulation and piping work is reduced, the production cost is reduced, and the catalytic reaction apparatus is downsized.

  The present invention provides a catalyst reactor in which a plurality of types of catalyst layers for sequentially performing a plurality of gas phase catalytic reactions in a cylindrical container are divided into separate layers, and the cylindrical reactor is integrally formed. A space defined by a catalyst layer A through which gas flows in the axial direction of the container and partition walls before and after the axial direction of the cylindrical container so that gas flows in a direction perpendicular to the axial direction of the cylindrical container and radially. The catalyst layer B is disposed in the catalyst layer B, and the reaction gas having passed through the catalyst layer A is introduced into the catalyst layer B.

  In this catalytic reaction apparatus, at least one of the partition walls before and after partitioning so that the gas flows in a direction perpendicular to the axial direction of the cylindrical container and tilted with respect to the direction in which the gas flows. By providing the above, the cross section of the flow path can be narrowed toward the outer peripheral side corresponding to the inclination. Further, the present catalytic reactor has a structure in which a gas leak due to sedimentation of the catalyst in the catalyst layer B does not occur by inclining the rear partition among the partition walls before and after the catalyst layer B in the cylindrical container. be able to. In addition, a cooling mechanism through which a cooling medium flows can be provided between the front and rear partition walls so that the reaction heat of the catalyst layer B can be removed. Further, a plurality of cooling fins for removing reaction heat of the catalyst layer B can be disposed between the partition walls before and after partitioning the catalyst layer B, and the plurality of fins partition the catalyst layer B. It is fixed to at least one of the front and rear partition walls.

In the catalyst reaction apparatus of the present invention, in the conventional catalyst reaction apparatus as described above, the catalysts respectively installed along the gas flow axis direction are configured as follows (1) to (4), The external shape of the catalytic reactor is simplified (ie, straightened), and the miniaturization thereof (ie, downsizing by shortening the length in the gas flow axis direction) is achieved.
(1) A CO removal catalyst is disposed at a portion where gas is circulated perpendicularly (that is, perpendicularly) to the gas flow axis direction and radially.
(2) A gas flow is formed vertically and radially with respect to the gas flow axis direction, and at least one of the partition walls before and after partitioning the catalyst is against the gas flow (that is, the gas flows). Be inclined).
(3) A cooling mechanism through which a cooling medium flows is attached to at least one of the front and rear partition walls to remove reaction heat of the catalyst.
(4) A cooling fin for removing reaction heat of the catalyst is fixed between at least one of the partition walls between the front and rear partition walls.

<1. Mode of making gas flow radial>
FIG. 3 is a diagram for explaining a mode in which the gas flow is made radial. This catalyst reaction apparatus is cylindrical, FIG. 3 (a) is a longitudinal cross-sectional view, FIG.3 (b) is XX sectional drawing in Fig.3 (a). In FIG. 3, 41 is a cylindrical body, and 42 is an upper lid. Reference numeral 45 denotes a CO removal catalyst layer. The CO removal catalyst layer 45 includes a small-diameter porous cylinder 44, a large-diameter porous cylinder 46, a lower partition wall 43, and an upper partition wall 47 disposed in the cylinder body 41. It is arranged in a donut-shaped space having a thickness divided by The cylindrical body 41 and the large-diameter porous cylindrical body 46 are arranged at an interval, and the gap 48 therebetween forms a flow path for the processed gas. Here, the lower partition wall 43 corresponds to a front partition wall in the gas flow axis direction, and the upper partition wall 47 corresponds to a rear partition wall in the gas flow axis direction. The CO removal catalyst may be granular, granular, pellet, cylindrical, etc., and may be a honeycomb type catalyst. Hereinafter, a granular catalyst, a granular catalyst, a pellet catalyst, a cylindrical catalyst, and the like are referred to as a granular catalyst or a granular catalyst.

  During operation of the catalytic reaction apparatus configured as described above, a gas to be treated introduced from the lower part of the apparatus, for example, a reformed gas mixed with CO removal air, is introduced from the lower part of the small-diameter porous cylindrical body 44. The CO component flows into the CO removal catalyst layer 45 through the pores, and the CO component is oxidized and burned and removed while flowing in the direction of the large-diameter porous cylindrical body 46. Here, the reformed gas flows in the CO removal catalyst layer 45 in the lateral direction, that is, perpendicular to the axial direction of the cylindrical container, as shown by arrows (← ---- →) in FIG. And, it flows radially through the CO removal catalyst layer 45 as indicated by arrows (--- →) in FIG. The treated gas passes through the gap 49 between the upper lid 42 and the partition wall 47 from the gap 48 between the cylinder 41 and the large diameter porous cylinder 46 through the hole of the large diameter porous cylinder 46, The discharge pipe 50 is discharged. Since the reaction rate of the oxidation reaction of CO in the CO removal catalyst layer 45 is fast, it is necessary to increase the linear velocity LV, but the reformed gas circulates in the CO removal catalyst layer 45 in a radial manner as in this embodiment. Thus, even if the reactor is not enlarged in the gas flow axis direction (longitudinal direction) (that is, the interval between the lower partition wall 43 and the upper partition wall 47 is not increased in FIG. 3A), The linear velocity LV can be increased.

<2. A mode in which gas flow is made radial and the partition wall is inclined>
In the cylindrical catalyst reaction apparatus, it is one of the important characteristic points in the present invention that the upper partition wall and / or the lower partition wall forming the catalyst layer are inclined toward the outer periphery. FIG. 4 is a view for explaining a mode in which the gas flow is made radial and the partition wall is inclined, and is shown as a longitudinal sectional view. As shown as 47 'in FIG. 4, the partition corresponding to the upper partition 47 in FIG. 3 is inclined, and the upper partition is formed in an inverted mortar shape. Here, the lower partition wall 43 corresponds to a front partition wall in the gas flow axis direction, and the upper partition wall 47 'corresponds to a rear partition wall in the gas flow axis direction. The configuration other than the upper partition wall 47 'configured in an inverted mortar shape and the configuration related thereto is the same as that shown in FIG. A gas to be treated introduced from the lower part of the apparatus, for example, reformed gas mixed with CO removal air, is introduced from the lower part of the small-diameter porous cylindrical body 44 and flows into the CO removal catalyst layer 45 through the holes. While flowing in the direction of the large-diameter porous cylinder 46, the CO component is oxidized and burned and removed.

  Here, the reformed gas flows in the CO removal catalyst layer 45 in the lateral direction, that is, perpendicular to the axial direction of the cylindrical vessel, as indicated by arrows (← --- →) in FIG. As in the case of FIG. 3, it flows radially through the CO removal catalyst layer 45 (see FIG. 3B). At this time, since the upper partition wall 47 'is inclined toward the outer peripheral side, the flow passage cross section can be narrowed toward the outer peripheral side corresponding to the inclination, and the reformed gas The flow rate is faster. In this way, the upper partition wall defining the CO removal catalyst layer is inclined, and the degree of the inclination is adjusted so that each of the gas inlet portion and the outlet portion to the catalyst (and the intermediate portion thereof) is also provided. A catalytic reaction apparatus designed for an optimum gas linear velocity LV and gas space velocity SV can be obtained. For example, it is possible to design a reaction by slowing the gas flow rate at the inlet. Further, among the upper and lower partition walls forming the catalyst layer, in particular, the upper partition wall is inclined so that when the catalyst is a granular catalyst, a gas leak due to sedimentation or the like can be prevented.

  Figs. 5 to 8 integrate the reactors for hydrocarbon fuel (raw gas) reforming reaction, shift reaction, and CO removal reaction, with a basic structure that makes the gas flow radiate and the partition wall inclined. It is a figure explaining the aspect of the made fuel processing apparatus, ie, an integrated catalyst reaction apparatus. 5-6, the same code | symbol is used about the same member as FIGS. 1-2 except the part to which the CO removal catalyst layer 54 relates. The present catalytic reactor is configured by arranging a plurality of cylindrical bodies having different diameters provided with the same central axis at intervals. 5-6, the dashed-dotted line shows the central axis, and the arrow has shown the direction, ie, the axial direction. The same applies to FIGS. 9 to 10 described later. As shown in FIGS. 5 to 6, the CO removal catalyst layer 54 is arranged in an inverted mortar shape. Reference numeral 51 denotes a lower partition wall having a plurality of holes 52. FIG. 7 is a plan view showing the lower partition wall 51 taken out. The lower partition wall 51 has a donut shape and is provided with a plurality of holes 52 on the annular surface of the central edge thereof. 53 is a gap formed between the partition plate 27 and the lower partition wall 51. Reference numeral 55 denotes an inverted mortar-shaped upper partition wall having a plurality of holes 56 at its skirt, and is inclined downward from the central portion to the outside. 8 is a view showing the upper partition wall 55 taken out, FIG. 8A is a plan view (viewed from above), and FIG. 8B is a cross-sectional view taken along line YY in FIG. 8A. is there. 5 to 6, the lower partition wall 51 corresponds to a front partition wall in the gas flow axis direction, and the upper partition wall 55 corresponds to a rear partition wall in the gas flow axis direction. Is the same.

  57 is a cylindrical body having a plurality of communication holes spaced from the second cylindrical body 2, and 58 is a cylinder having a plurality of communication holes spaced from the cylindrical body 24. is there. The CO removal catalyst layer 54 is formed by filling a space defined by the lower partition 51, the upper partition 55, the cylindrical body 57, and the cylindrical body 58 with a CO removal catalyst. Here, it is one of the basic structures in this embodiment that the upper partition wall 55 is inclined downward toward the outer periphery. In this way, the upper partition wall that partitions the CO removal catalyst layer is inclined, and the degree of the inclination is adjusted, so that each of the gas inlet portion and the outlet portion to the catalyst (and the intermediate portion thereof) is also provided. It is possible to obtain a catalytic reaction apparatus designed for the optimum gas linear velocity LV and gas space velocity SV. For example, it is possible to design a reaction by slowing the gas flow rate at the inlet. Further, by providing the upper surface partition wall of the catalyst filling portion with an inclination, a structure in which gas leakage due to sedimentation of the catalyst does not occur can be achieved.

  In the conventional catalytic reactor in which a plurality of types of catalyst layers for sequentially performing a plurality of gas phase catalytic reactions are arranged in separate layers and separated by upper and lower partition walls in a conventional cylindrical vessel, the above-described FIGS. As described above, from the characteristics of the CO removal catalyst and the CO conversion catalyst, it is essential that the diameter of the CO removal catalyst layer be smaller than the diameter of the CO conversion catalyst layer. In contrast, according to the present invention, as shown in FIGS. 5 to 8, the diameter of the CO removal catalyst layer 54 can be made the same as the diameter of the CO conversion catalyst layer 21, which corresponds to the characteristics of the CO removal catalyst. Thus, it can be elongated in the gas flow direction, and the heat insulating material can be thinned. As described above, the degree of freedom of the catalyst installation position is increased, and the gas flow can be configured three-dimensionally. Therefore, useless space is eliminated and the apparatus can be downsized.

  Here, instead of inclining the upper partition wall 55, the lower partition wall 51 may be inclined, and the upper partition wall 55 may be inclined and the lower partition wall 51 may be inclined. Also good. Of these, when the lower partition 51 is inclined instead of the upper partition 55 being inclined, the upper partition 55 is a donut-shaped partition, the lower partition 51 is a mortar-shaped partition, and the lower partition 51 is the outer periphery. It becomes the structure which has an inclination upward toward the direction. Further, when the upper partition wall 55 is inclined and the lower partition wall 51 is also inclined, the upper partition wall 55 has a reverse mortar shape, the lower partition wall 51 has a mortar shape, and the lower partition wall 51 faces downward toward the outer periphery. And the lower partition wall 51 is inclined upward toward the outer periphery. In the present invention, these are directions in which gas flows in at least one of the partition walls before and after partitioning the catalyst layer B so that the gas flows in a direction perpendicular to the axial direction of the cylindrical container and radially. This corresponds to a configuration with an inclination.

  In the operation of the present catalytic reactor, the reformed gas mixed with the CO removal air from the CO conversion catalyst layer 21 through the holes of the support plate 22 passes through the holes 28 of the partition wall (partition plate) 27 and the partition walls 27 and the lower part. It circulates through the gap 53 between the partition walls 51, is introduced into the gap between the second cylindrical body 2 and the cylindrical body 57 from the plurality of holes 52 of the lower partition wall 51, and passes through the communication holes of the cylindrical body 57 to remove the CO removal catalyst. Introduced into layer 54. The reformed gas flows radially in the direction of the cylindrical body 58 in the CO removal catalyst layer 54, but the upper partition wall 55 of the CO removal catalyst layer is inclined downward toward the cylindrical body 58. Is controlled.

  Here, as the CO conversion catalyst of the CO conversion catalyst layer 21, in addition to the granular CO conversion catalyst, a monolith type CO conversion catalyst is used, but a monolith type CO conversion catalyst (= honeycomb CO conversion catalyst) is preferably used. The monolith type CO shift catalyst is a catalyst in which a fixed catalyst bed is integrated, and is a catalyst in which a CO shift catalyst is supported on the inner surface of a ceramic or metal carrier having a large number of parallel through holes, that is, cells. When this catalytic reactor is used in, for example, a home cogeneration system (cogeneration system), it is necessary to start and stop frequently. Therefore, when a granular catalyst is used, there is a problem that the catalyst filled in the catalyst layer is crushed and pulverized due to repeated rise and fall of temperature and the catalytic activity is lowered. Thus, by using a monolithic CO conversion catalyst as the CO conversion catalyst, those problems in the case of using a granular CO conversion catalyst can be solved.

<3. A mode in which gas flow is made radial and the partition wall is inclined, and a cooling mechanism is further provided>
9-11 is a figure explaining the aspect which makes a gas distribution radial, makes a partition incline, and also provides a cooling mechanism. 9-11, the same code | symbol is used about the same member and site | part as FIGS. 1-2, FIGS. First, in the embodiment of FIG. 9, a cooling mechanism 59 is provided above the upper partition wall 55 of the CO removal catalyst layer 54. The cooling mechanism 59 is a pipe that is continuous with the water supply pipe 25 and is spirally disposed on the upper surface of the upper partition wall 55. In operation, the CO removal catalyst layer 54 is cooled through the wall surface of the upper partition wall 55 by circulating water through the pipe of the cooling mechanism 59. The water flows from the water supply pipe 25 as shown by an arrow a in FIG. 9 and circulates in the pipe of the cooling mechanism 59, then flows as shown by an arrow b to the water supply pipe 25 (returns), and continues to this. After passing through the cooling pipe 26, the raw material gas is mixed in the mixing unit 13. The cooling mechanism 59 can efficiently remove the heat of reaction in the CO removal catalyst layer 54. Further, when the lower partition 51 is inclined instead of the upper partition 55 being inclined, the cooling mechanism can be similarly arranged with respect to the lower partition 51. In this case, the same cooling effect as described above can be obtained.

  FIGS. 10-11 is a figure explaining the other aspect of a cooling mechanism. As shown in FIGS. 10 to 11, the cooling mechanism 60 is formed on the lower surface of the lower partition wall 51 of the CO removal catalyst layer 54. As shown in FIG. 11, the cooling mechanism 60 includes a lower surface of the lower partition wall 51 and a component member 61. FIG. 11A is a diagram showing a cross section of the lower partition wall 51 and the constituent member 61 in FIG. FIG. 11B is a plan view of the constituent member 61. As shown in FIG. 11, the component member 61 has a shape corresponding to the lower partition wall 51, and has a donut shape, that is, a disc shape having an annular space at the center thereof. The cooling mechanism 60 is configured with the upper surface of the component member 61 shown in FIG. 11B being in close contact with the lower surface of the lower partition wall 51. As shown in FIG. 11B, the component member 61 is provided with a groove 63 for circulating a cooling medium, and a hole 65 for circulating a gas (for example, a reformed gas mixed with CO removal air) is provided in the center thereof. It has been. Since the lower surface of the lower partition wall 51 is in close contact with the upper surface of the component member 61 in which the groove 63 is formed in this way, the groove 63 becomes a flow path for the cooling medium. When water is used as the cooling medium, the gap between the partition wall 51 and the member 61 is filled with water by surface tension. Therefore, the main flow path of water vapor or water as the cooling medium is the flow path along the groove 63. Become. In FIG. 11B, reference numeral 62 denotes a cooling medium introduction pipe to the flow path, and 64 denotes a cooling medium lead-out pipe from the flow path. FIG. 11A shows a case where the portion for forming the hole 65 is configured separately from the lower partition wall 51 and the component member 61. However, the lower partition wall 51 and the component member 61 are extended to the portion. A hole 65 may be provided in the extended portion.

  As a cooling medium, the water which flows through the cooling pipe 26 is used in the aspect of FIGS. In FIG. 10, the introduction and flow direction of water is schematically shown as an arrow c, which corresponds to c shown in FIGS. 11A and 11B, and is introduced into the cooling mechanism 60 from the introduction pipe 62. . The water that has contributed to the cooling of the CO removal catalyst layer 54 flows as shown by the arrow d in FIG. 10 and is mixed with the raw material gas in the mixing unit 13, which is shown in FIGS. 11 (a) and 11 (b). It is derived from the outlet pipe 64 and mixed with the raw material gas. 10 to 11, the cooling mechanism 60 is configured by disposing the constituent member 61 on the lower surface of the lower partition wall 51. However, the cooling mechanism 60 is configured by disposing the constituent member 61 on the upper surface of the lower partition wall 51. Also good. In this case, the component member 61 is positioned on the CO removal catalyst layer 54 side, and the surface of the component member 61 in which the groove 63 is formed is in contact with the upper surface of the lower partition wall 51. . Further, in the case where the lower partition wall 51 is inclined instead of the upper partition wall 55 being inclined, the cooling mechanism is configured in the same manner as described above for the corresponding upper partition wall having no inclination. Can do. In this case, the same cooling effect as described above can be obtained.

<4. A mode in which gas flow is made radial and the partition wall is inclined, a cooling mechanism is provided, and a cooling fin is provided in the CO removal catalyst layer>
FIG. 12 is a diagram for explaining a mode in which cooling fins are provided on the CO removal catalyst layer 54. Here, the other structure is the same as that of FIGS. 12A is a cross-sectional view, FIG. 12B is a side view of the cooling fin, and FIG. 12C is a cross-sectional view of the cooling fin. Although the example of a dimension of the fin is shown in Drawing 12 (b)-(c), this is a thing as an example. As shown in FIG. 12, the CO removal catalyst layer 54 is disposed in a space in which the gas flow is made radial and the upper partition wall is inclined, and a plurality of cooling fins 66 are provided in the CO removal catalyst layer 54. The cooling fins 66 are arranged radially from the center toward the outer periphery, and the cooling fins 66 are arranged at equal intervals. Each cooling fin 66 may be fixed to the lower partition wall 51 (see FIGS. 5 to 11), may be fixed to the upper partition wall 55 (see FIGS. 5 to 11), or may be fixed to both of them. , Preferably fixed to both. Fixing can be performed, for example, by welding or a metal brazing material. Thus, by providing the fin for cooling in the CO removal catalyst layer, the CO removal catalyst can be cooled uniformly, and the CO removal reaction can be performed uniformly. The embodiment in which the cooling fin is provided in the CO removal catalyst layer can be applied to the embodiments shown in FIGS. 3 to 4 described above, and in this case, the same cooling effect as described above can be obtained.

This catalytic reaction apparatus can be used as an apparatus for performing various catalytic reactions. In particular, in a hydrogen production apparatus that produces hydrogen by reforming a hydrocarbon-based fuel by a steam reforming reaction, a CO conversion catalyst is used as the catalyst of the catalyst layer A, and a CO removal catalyst is used as the catalyst of the catalyst layer B. In an exhaust gas treatment apparatus for removing unburned components such as NOx (= nitrogen oxides such as NO) and CH ₄ in combustion exhaust gas, a denitration catalyst is used as a catalyst for catalyst layer A, and combustion is performed as a catalyst for catalyst layer B It is suitably applied when using a catalyst. Among these, a hydrogen production apparatus using a steam reforming reaction is useful as a hydrogen production apparatus that supplies hydrogen to a fuel cell.

  When this catalytic reaction apparatus is configured as a hydrogen production apparatus from a hydrocarbon-based fuel, the following (1) to (8) can be employed. (1) A first cylindrical body, a second cylindrical body, and a third cylindrical body, which are arranged concentrically and spaced apart from each other in order, and a fourth cylinder whose diameter is larger than that of the third cylindrical body at the top of the third cylindrical body. A cylindrical body is provided. (2) A radiation cylinder is provided in the first cylindrical body with the central axis being coaxial. (3) A reforming catalyst layer that is provided with a burner in the axial direction in the radiation cylinder and is filled with the reforming catalyst is disposed in a gap defined by the first cylinder and the second cylinder. (4) A CO shift catalyst layer and a CO removal catalyst layer are sequentially arranged between the second cylinder and the fourth cylinder with an interval in the axial direction through a partition wall. (5) The flow of the reformed gas in the CO removal catalyst layer is configured to flow radially from the central axis side toward the outer periphery.

  Here, with regard to the configuration of (5) above, in addition to making the flow of the reformed gas in the CO removal catalyst layer circulate radially from the central axis side toward the outer periphery, (6) CO removal One or both of the upper partition wall and the upper partition wall that partition the catalyst layer may be inclined from the central axis side toward the outer periphery. This slope is a slope that descends from the central axis side toward the outer periphery in the upper partition wall, and a slope that rises from the central axis side toward the outer periphery in the lower partition wall. (7) In addition to the configurations of (1) to (5) or (1) to (6), the above-described cooling mechanism may be provided for the CO removal catalyst layer. You may provide the fin for cooling.

As described above, in the present catalytic reactor, a heat-resistant alloy, preferably stainless steel, is used as a constituent member excluding the catalyst. Moreover, as a catalyst of each catalyst layer in this catalyst reaction apparatus, it is used according to the kind of catalytic reaction. For example, the reforming catalyst is appropriately selected from metal catalysts such as Ni and Ru, and other reforming catalysts, and the CO conversion catalyst is a Cu / Zn-based catalyst, Fe / Cr-based catalyst, white metal catalyst, or the like. , A catalyst that contains platinum as a main component and a metal oxide such as CeO ₂ as an accessory component, a base metal catalyst such as Al, Cu, Fe, Cr, and Mo, and other CO conversion catalysts, and is used as appropriate. Are appropriately selected from Ru-based metal catalysts and other CO removal catalysts. The combustion catalyst is appropriately selected from white metal catalysts such as Pd and Pt, and other combustion catalysts, and the denitration catalyst is a noble metal catalyst such as Pt, Rh, and Pd, TiO ₂ , Cr ₂ O _3. , Fe ₂ O ₃ and other oxide catalysts, and other denitration catalysts are appropriately selected and used. These catalysts are configured to be supported on an alumina or other support.

  EXAMPLES Hereinafter, although this invention is demonstrated in more detail based on an Example, of course, this invention is not limited to these Examples. An experimental example is described in Example 1, and Examples 2 to 5 are various configuration examples of the present invention.

<Example 1>
The catalytic reaction apparatus shown in FIGS. 5 to 7 was tested as a hydrogen production apparatus. This hydrogen production apparatus is an apparatus capable of producing 1 Nm ³ of hydrogen per hour. This was connected to a PEFC with an output of 1 kW. Power can be generated for 1kW with hydrogen 0.75 nm ³ of hydrogen 1 nm ^3. Each catalyst was filled in each of the reforming catalyst layer 16, the CO shift catalyst layer 21, and the CO removal catalyst layer 54. As the reforming catalyst, a ruthenium-based catalyst [a catalyst having Ru supported on alumina, granular, average particle diameter (diameter) ≈3 mm] was used. As the CO conversion catalyst, a Cu / Zn-based catalyst [a catalyst obtained by extruding Cu and Zn on alumina, a cylindrical shape, 3 mm (diameter) × 3 mm (length)] was used. As the CO removal catalyst, a ruthenium / platinum-based catalyst (a catalyst in which Ru is supported on granular alumina, granular, average particle diameter (diameter) ≈3 mm) was used.

  Desulfurized city gas (13A) was used as the raw material gas, supplied at a flow rate of 4.1 NL / min, and water (pure water) was supplied at a flow rate of 10.0 g / min. Steam ratio (S / C ratio) = 2.5. Further, CO removal air was supplied at a flow rate of 1.5 NL / min. City gas was used as the fuel for the burner. Thus, the reformed gas was obtained at a flow rate (dry base): 23.1 NL / min. Table 1 shows the space velocity and linear velocity of the gas in the reforming catalyst layer, the CO shift catalyst layer, and the CO removal catalyst layer measured during steady operation. As shown in Table 1, the linear velocity LV particularly in the CO removal catalyst layer could be made substantially equal at the inlet and the outlet of the CO removal catalyst layer.

<Example 2>
FIG. 13 shows the second embodiment. This catalytic reaction apparatus is cylindrical, and is shown as a longitudinal sectional view in FIG. In FIG. 13, reference numeral 77 denotes a CO shift catalyst layer, and reference numeral 82 denotes a CO removal catalyst layer. Reference numeral 72 denotes a bottom plate of the cylindrical body 71, and 73 denotes a reformed gas introduction pipe provided on the bottom plate 72. 74 is an upper cover of the cylindrical body 71, and 75 is a reformed gas outlet pipe provided on the upper cover 74. The CO shift catalyst layer 77 is filled between the perforated plate 76 and the upper perforated plate 78 spaced from the bottom plate 72. The CO removal catalyst layer 82 is filled between the upper perforated plate 78, the plate body 80 disposed at a distance from the upper porous plate 78, and the inverted mortar-shaped partition wall 83. The plate body 80 has a disk shape and includes a reformed gas introduction pipe 81 at the center thereof. Reference numeral 79 denotes a CO removal air introduction pipe. Reference numeral 84 denotes a bottom portion of the inverted mortar-shaped partition wall 83 (because the partition wall 83 has an inverted mortar shape), and 85 is a cylindrical body having a number of holes. The entire reactor thus configured is insulated with a heat insulating material 86.

  In the operation of the catalytic reaction apparatus configured as described above, the reformed gas introduced from the introduction pipe 73 passes from the gap between the bottom plate 72 and the porous plate 76 to the CO conversion catalyst layer 77 through the holes of the porous plate 76. When introduced, the shift reaction converts CO in the reformed gas into carbon dioxide, and hydrogen is also generated. The reformed gas after the CO transformation is mixed with the air for removing CO from the conduit 79, passes through the introduction pipe 81 from the gap between the upper porous plate 78 and the plate body 80, and the flow of the inverted mortar-shaped partition wall 83. By striking the bottom or upper partition 84, the reformed gas and the CO removal air are sufficiently mixed. Thereafter, the gas is introduced into the CO removal catalyst layer 82 through the hole of the cylindrical body 85. By the CO removal reaction here, CO in the reformed gas is changed to carbon dioxide. The reformed gas after CO removal is led out from the outlet pipe 75 and taken out. In FIG. 13, the flow of the reformed gas is indicated by a dotted line. In this way, the CO concentration in the reformed gas having a CO concentration of 10 vol% or more can be reduced to 10 ppm or less. In addition, between the upper porous plate 78 and the plate body 80, as shown in FIGS. 1-2 and FIGS. 5-6, the structure which has arrange | positioned the partition (partition plate) 27 which has one communicating hole 28 at intervals. It may be. The one communication hole 28 has a function of mixing the reformed gas and the CO removing air, and the introduction pipe 81 has a structure having the same function.

<Example 3>
The third embodiment is a desulfurization in which a hydrocarbon-based raw material gas (fuel) serving as a raw material for the reforming reaction flows in the axial direction of the central portion of the cylindrical vessel to remove the sulfur content in the hydrocarbon-based fuel. A hydrocarbon-based fuel in which a CO conversion catalyst is disposed as the catalyst of the catalyst layer A, a CO removal catalyst is disposed as the catalyst of the catalyst layer B, and a sulfur content is removed by the desulfurization agent This is an example of a catalytic reaction device configured to sequentially flow the reformed gas subjected to steam reforming to the catalyst layer A and the catalyst layer B. FIG. 14 is a diagram showing the third embodiment. In the catalytic reaction apparatus of FIG. 13 showing the second embodiment, a desulfurizing agent is arranged in the axial direction of the central portion, and a hydrocarbon-based fuel reforming apparatus is separately provided. This corresponds to the example of the arrangement.

  In FIG. 14, the upper part is a reactor in which a desulfurizing agent is arranged in the axial direction of the central part of the cylindrical container of the catalytic reactor as shown in FIG. In FIG. 14, parts that are the same as those in FIGS. 5 and 13 are given the same reference numerals. As shown in FIG. 14, a cylindrical body 88 filled with a desulfurizing agent is disposed in the axial direction of the central portion of the catalytic reaction apparatus as shown in FIG. 13, that is, in the central portion and in the axial direction. The upper cover 89 is provided with a raw material gas introduction pipe 90 which is a hydrocarbon-based fuel, and the lower cover 91 is provided with a desulfurized raw material gas outlet pipe 92. The cylindrical body 88 is filled with a desulfurizing agent between the upper and lower perforated plates 93 and 94. In FIG. 14, the lower half is a reformer, and its configuration basically corresponds to the lower half of the catalytic reaction apparatus shown in FIG.

  During the operation of the catalytic reactor configured as described above, the raw material gas introduced from the introduction pipe 90 is desulfurized while flowing through the desulfurizing agent layer. The desulfurized source gas is led out from the lead-out pipe 92, mixed with water (steam) on the way, and introduced into the reforming catalyst layer of the reformer. Since the reforming catalyst layer is heated by the combustion gas generated in the burner 6, the reforming reaction proceeds, the reforming gas is introduced into the CO shift catalyst layer 77 through the introduction pipe 73, and reformed by the shift reaction. CO in the quality gas is converted to carbon dioxide, and hydrogen is generated. The reformed gas after CO conversion is introduced into the CO removal catalyst layer 82, and CO in the reformed gas is changed to carbon dioxide by the CO removal reaction. The reformed gas after CO removal is led out from the outlet pipe 75 and taken out. In this way, the CO concentration in the reformed gas having a CO concentration of 10 vol% or more can be reduced to 10 ppm or less. In this example, since the raw material gas desulfurization agent is arranged and integrated in the catalyst reaction apparatus, the entire system can be reduced in size as compared with the case where the desulfurization apparatus is provided separately.

<Example 4>
The fourth embodiment is an example in which the present invention is applied to purification of combustion exhaust gas (combustion exhaust gas). FIG. 15 shows the fourth embodiment. This catalytic reaction apparatus is cylindrical and is shown as a longitudinal sectional view. In FIG. 15, 96 is a NOx treatment catalyst layer, and 99 is a combustion catalyst layer (combustion treatment catalyst layer) of unburned components such as CO and methane. Both layers are sequentially arranged in the flow direction of the combustion exhaust gas in the cylindrical body 95. The NOx treatment catalyst layer 96 is disposed between the lower porous plate 97 and the upper porous plate 98. The combustion treatment catalyst layer 99 is disposed in a space formed between the lower partition wall 100, the upper partition wall 101, the small-diameter porous cylinder body 102, and the large-diameter porous cylinder body 103, and the cylindrical body 95 and the large-diameter porous body. The air gap 104 forms a flow path for the treated gas. The NOx treatment catalyst and the combustion catalyst may be granular or may be a honeycomb type catalyst, but a honeycomb type catalyst is preferred.

  During the operation of the catalyst reaction apparatus configured as described above, the combustion exhaust gas introduced from the lower part of the apparatus passes through the NOx treatment catalyst layer 96, and after NOx is treated and removed, it passes through the upper perforated plate 98. Then, it flows in from the lower part of the small-diameter porous cylinder 102 and flows into and through the combustion catalyst layer 99 through the holes of the cylinder 102. Here, the unburned components are burned and removed, and are discharged through the gap 104 between the cylindrical body 95 and the large-diameter porous cylindrical body 103. In FIG. 15, the flow of the combustion exhaust gas is indicated by a dotted line. Combustion with a combustion catalyst generally has a high reaction rate, and therefore the amount of catalyst may be small. Further, in the combustion catalyst layer, it is necessary to shorten the contact time between the catalyst and the gas to be treated and to reduce the linear velocity LV, so that the catalyst arrangement having the shape as in this embodiment is optimal.

<Example 5>
The fifth embodiment is an example applied to the purification of combustion exhaust gas as in the fourth embodiment. However, the flow direction of the gas to be treated in the combustion catalyst layer is different from that in the fourth embodiment. FIG. 16 is a diagram illustrating the fifth embodiment. This catalytic reaction apparatus is cylindrical and is shown as a longitudinal sectional view. In FIG. 16, the same members as those shown in FIG. As shown in FIG. 16, the combustion exhaust gas introduced from the lower part of the apparatus passes through the NOx treatment catalyst layer 96, and after NOx is treated and removed, the gap between the cylindrical body 95 and the large-diameter porous cylindrical body 103. From 104 through the hole of the large-diameter porous cylinder 103, the combustion catalyst layer 99 flows in the direction of the small-diameter porous cylinder 102. Here, the unburned components are burned and removed, and discharged through the holes of the small-diameter porous cylindrical body 102 upward. The other points are the same as in the fourth embodiment.

The figure which shows an example of an integrated fuel processor as a longitudinal section The figure which expanded and showed centering on the part of the CO removal catalyst layer 34 in FIG. The figure explaining the aspect which makes gas distribution radial The figure explaining the aspect which makes gas distribution radial and makes a partition incline The figure explaining the aspect which makes gas distribution radial and makes a partition incline The figure explaining the aspect which makes gas distribution radial and makes a partition incline The figure explaining the aspect which makes gas distribution radial and makes a partition incline The figure explaining the aspect which makes gas distribution radial and makes a partition incline The figure explaining the aspect which makes a gas distribution radial, gives an inclination to a partition, and also provides a cooling mechanism The figure explaining the aspect which makes a gas distribution radial, gives an inclination to a partition, and also provides a cooling mechanism The figure explaining the aspect which makes a gas distribution radial, gives an inclination to a partition, and also provides a cooling mechanism The figure explaining the aspect which makes a gas distribution radial and makes a partition incline, provides a cooling mechanism, and also provides a fin for cooling in a CO removal catalyst layer The figure which shows Example 2. The figure which shows Example 3. The figure which shows Example 4. The figure which shows Example 5.

Explanation of symbols

1 to 4 1st cylinder to 4th cylinder 5 Radiation tube 6 Burner 7 Upper lid / burner mounting base 8 Bottom plate 9 Exhaust passage for combustion exhaust gas 10 Partition 21 CO shift catalyst layer 35, 54 CO removal catalyst layer 47 Upper partition 47 ' Upper partition wall 51 configured in a reverse mortar shape 51 Lower partition wall having a plurality of holes 52 53 A gap formed between the partition plate 27 and the lower partition wall 51 55 A reverse mortar-shaped upper partition wall having a plurality of holes 56 at the bottom. 2 Cylindrical body having a plurality of communication holes spaced from the cylindrical body 2 58 Cylinder bodies having a plurality of communication holes spaced from the cylindrical body 24 59, 60 Cooling mechanism 61 Constituent member of cooling mechanism 62 Cooling medium introduction pipe 63 Groove 64 Cooling medium outlet pipe a to d Water flow direction as cooling medium 93, 94 Upper and lower perforated plates 95 Cylindrical body 96 NOx treatment catalyst Layer 97 Lower porous plate 98 Upper porous plate 99 Combustion catalyst layer 100 Lower partition wall 101 Upper partition wall 102 Small-diameter porous cylinder 103 Large-diameter porous cylinder 104 Void

Claims (10)

(A) In a catalytic reaction apparatus in which a plurality of types of catalyst layers for sequentially performing a plurality of gas phase catalytic reactions are divided into separate layers and arranged integrally in a cylindrical container, the cylindrical container In a space partitioned by a catalyst layer A through which gas flows in the axial direction and partition walls before and after the axial direction of the cylindrical container so that gas flows in a direction perpendicular to the axial direction of the cylindrical container and radially. A catalyst reaction apparatus in which a catalyst layer B is disposed and a reaction gas having passed through the catalyst layer A is introduced into the catalyst layer B,
For (ii) the cylindrical container, of the cylindrical container, a portion was placed the catalyst layer B, as well as partition so that the gas flows into and radially perpendicular to the axial direction of its,
(C) A catalytic reaction apparatus having an inverted mortar-shaped upper partition so that the inlet linear velocity and the outlet linear velocity of the catalyst layer B are substantially equal.
2. The catalytic reaction apparatus according to claim 1 , wherein the cooling medium flows in at least one of the partition walls before and after partitioning so that the gas flows in a direction perpendicular to the axial direction of the cylindrical container and radially. A catalytic reaction apparatus, wherein a cooling mechanism is provided, and the heat of reaction of the catalyst layer B is removed by the cooling mechanism. 3. The catalytic reaction apparatus according to claim 2 , wherein the cooling mechanism is configured by arranging a cooling pipe in which a cooling medium flows spirally on a surface of a partition wall inclined with respect to a direction in which the gas flows. A catalytic reactor characterized by comprising: The catalytic reactor according to claim 2 , wherein the cooling mechanism has a shape corresponding to the partition partitioning the catalyst layer B, and a structural member having a groove through which a cooling medium flows on one surface thereof, the partition partitioning the catalyst layer B. A catalytic reaction device comprising a surface having the groove in contact with any one of the two surfaces. In the catalytic reactor according to any one of claims 1 to 4, between the front and rear of the partition wall partitioning the catalyst layer B, a plurality of cooling fins for removing the reaction heat of the catalyst layer B Is fixed to at least one of the front and rear partition walls. The catalytic reaction apparatus according to any one of claims 1 to 5 , wherein the catalyst of the catalyst layer A is a CO shift catalyst, and the catalyst of the catalyst layer B is a CO removal catalyst. apparatus. 7. The catalytic reaction apparatus according to claim 6 , wherein a burner is disposed in the axial direction of the central portion of the cylindrical container, and a reforming catalyst layer is disposed on the outer periphery thereof. 7. The catalyst reaction apparatus according to claim 6 , wherein a desulfurization agent is disposed in the axial direction of the central portion of the cylindrical container, a CO shift catalyst is disposed as a catalyst of the catalyst layer A on the outer periphery thereof, and the catalyst of the catalyst layer B A reformed gas obtained by arranging a CO removal catalyst and steam-reforming hydrocarbon-based fuel from which sulfur has been removed with the desulfurizing agent is circulated sequentially through the catalyst layer A and the catalyst layer B. A catalytic reactor characterized by the above. The catalyst reactor according to any one of claims 1 to 8 , which is a catalyst reactor for producing hydrogen from a hydrocarbon-based fuel for supplying hydrogen to a fuel cell. Reactor. The catalyst reaction apparatus according to any one of claims 1 to 5 , wherein the catalyst reaction apparatus for exhaust gas treatment removes NOx and unburned components such as CH _{4 in} combustion exhaust gas, and the catalyst of the catalyst layer A Is a denitration catalyst, and the catalyst of the catalyst layer B is a combustion catalyst.

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