JP2004262725A - Selective oxidation reactor - Google Patents

Abstract

A selective oxidation reactor is miniaturized and compactly housed in a narrow cylindrical space.
A selective oxidation reactor (6) is formed in a double cylindrical shape with a part cut off in a circumferential direction, and includes a plurality of reactor bodies (31, 32) partitioned by a partition plate (33). The vessel bodies 31, 32 are partitioned by upper and lower perforated plates 34, 35, 37, 38 through which a reformed gas mixed with oxidizing air can flow, and a chamber 36, in which a selective oxidation catalyst is loaded, is provided. In a chamber 47 formed above the chamber 36, a reformed gas introduction hole 49a into which the reformed gas from the chamber 36 flows is formed in the outer periphery, and oxidizing air 48 is supplied from the front end side. A gas that is introduced and mixes the reformed gas and the oxidizing air 48 so that the reformed gas mixed with the oxidizing air 48 can be supplied to the chamber 51 formed above the chamber 39 of the reactor main body 32. A mixing tube 49 is provided.
[Selection] Fig. 2

Description

[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a selective oxidation reaction device applied to a fuel reformer.
[0002]
[Prior art]
In general, a fuel cell combines hydrogen and oxygen, as opposed to the electrolysis of water, to extract electricity and heat generated at that time. The development of fuel cell cogeneration systems and fuel cell vehicles is being actively pursued.Hydrogen, the fuel for such fuel cells, is reformed from petroleum fuels such as naphtha and kerosene and city gas using a reformer. Manufactured.
[0003]
FIG. 10 shows an entire system of a stationary polymer electrolyte fuel cell (PEFC) as an example of equipment provided with a reformer, where 1 is a reformer and 2 is a reformer. A water evaporator for evaporating water by the heat of the exhaust gas discharged from the reformer 1 to generate water vapor; 3, a raw fuel vaporizer for vaporizing a raw fuel such as naphtha by the heat of the exhaust gas; A desulfurizer 5 for desulfurizing the raw material gas supplied to the reformer 1 lowers the temperature of the reformed gas reformed in the reformer 1 to a required temperature (about 200 to 250 ° C.) with cooling water,₂O to CO₂And H₂A low-temperature shift converter 6 converts the reformed gas passing through the low-temperature shift converter 5 with cooling water, and removes CO by an oxidation reaction represented by [Chemical Formula 1]. A humidifier for humidifying the reformed gas that has passed through the reactor 6; a solid polymer fuel cell 8 having a cathode 8a and an anode 8b; and 60, an outlet gas from the cathode 8a is guided and moisture is recovered from the outlet gas. This is a drain separator capable of exhausting residual gas.
[0004]
Embedded image
CO + 1 / 2O₂→ CO₂
[0005]
In the equipment shown in FIG. 10, water is converted into steam in a water evaporator 2 and raw fuel such as naphtha is vaporized in a raw fuel vaporizer 3 to form a raw material gas. The raw material gas desulfurized by the desulfurizer 4 is led to the reformer 1, and the reformed gas reformed by the reformer 1 is fed to the low-temperature shift converter 5 and the selective oxidation reactor 6. The air is guided to the anode 8b of the polymer electrolyte fuel cell 8 via the humidifier 7 and the air is guided to the cathode 8a of the polymer electrolyte fuel cell 8 via the humidifier 7 to generate power. Has become.
[0006]
Further, the anode off gas discharged from the anode 8b is reused as fuel gas in the reformer 1, while water discharged together with the outlet gas from the cathode 8a is separated from the outlet gas in the drain separator 60, The cooling water for the polymer electrolyte fuel cell 8, the selective oxidation reactor 6, and the low-temperature shift converter 5, and the water used as a part of the steam mixed with the raw material gas are used.
[0007]
Conventionally, the reformer 1 and the water evaporator 2, the raw fuel vaporizer 3, the desulfurizer 4, the low-temperature shift converter 5, and the selective oxidation reactor 6 as related devices are one unit as a fuel reformer. As such a fuel reforming device, for example, a burner combustion type device disclosed in the prior application 1 has been proposed.
[0008]
[Prior application 1]
Japanese Patent Application No. 2002-140149
[0009]
Thus, the fuel reforming apparatus of the prior application 1 is shown in FIG. 11 and FIG. 12, in which parts denoted by the same reference numerals as those shown in FIG. 10 represent the same parts. In the fuel reformer shown in FIGS. 11 and 12, the reformer 1 and its related devices (water evaporator 2, raw fuel vaporizer 3, desulfurizer 4, low-temperature shift converter 5, and selective oxidation reactor 6) The fuel reforming apparatus is configured by covering the unit consisting of a heat insulating container 9 having a heat insulating layer 9c formed between the inner cylinder 9a and the outer cylinder 9b.
[0010]
In the case of the illustrated example, the inner cylinder 9a of the heat insulating container 9 itself is used as a part of the reformer 1, and the combustion gas injected from the combustor 10 is provided at a central portion inside the inner cylinder 9a. A flow path 12 for the combustion gas is formed between the furnace pipe 11 and the inner pipe 9a, and a reforming catalyst (not shown) is formed in the flow path 12 inside. A plurality of (six in the example of FIG. 11 and FIG. 12) reforming tubes 13 for flowing the raw material gas and reforming the raw material gas are arranged in parallel to constitute the reformer 1. . The reforming pipe 13 has a double pipe structure including an inner pipe 13a and an outer pipe 13b, and raises a raw material gas in a space formed between the inner pipe 13a and the outer pipe 13b to increase the After exchanging heat with the combustion gas, it is turned back at the upper end to lower the space in the inner tube 13a.
[0011]
The furnace tube 11 of the reformer 1 is connected to the upper end of a base inner tube 16 erected from the base plate 14, and has a short base outer tube 15 rising from the outer peripheral edge of the base plate 14. The lower end of the heat insulating container 9 is air-tightly connected to the upper end by fastening means such as bolts and nuts (not shown) so as to be detachable, and the base plate 14, the base inner cylinder 16, the base outer cylinder 15 are insulated from each other. In a cylindrical space 17 defined by the inner cylinder 9a of the container 9 and communicating with the combustion gas flow path 12, a water evaporator 2 and a raw fuel vaporizer 3 as related devices of the reformer 1 are provided. , A desulfurizer 4, a low-temperature shift converter 5, and a selective oxidation reactor 6 are provided.
[0012]
An air passage 18 for supplying air to the combustor 10 is formed inside the base inner cylinder 16, and an anode off-gas is supplied to the combustor 10 as a fuel gas at the axial center thereof. The anode off-gas supply pipe 19 is provided, and combustion fuel is supplied from the combustion fuel supply pipe 20 to the combustor 10 at the time of startup or steady combustion. Thus, the fuel for combustion is used as the fuel at the time of startup, and the anode off-gas and the fuel for combustion are mixed and used at the time of steady combustion.
[0013]
In the fuel reforming apparatus shown in FIGS. 11 and 12, the heat insulating layer 9c is constructed simply by covering the unit with the heat insulating container 9, so that the labor for constructing the heat insulating layer 9c is greatly reduced, and the reformer is further improved. At the time of maintenance such as replacement or inspection of the catalyst inside 1, it is only necessary to open the heat insulating container 9, and the operation can be performed quickly.
[0014]
Moreover, since the heat insulating container 9 in which the heat insulating layer 9c is formed between the inner cylinder 9a and the outer cylinder 9b is adopted as the container, the heat insulating performance becomes extremely high, the volume of the heat insulating layer 9c is reduced, and While it is possible to reduce the size, the amount of heat dissipated is suppressed, which also helps to improve the thermal efficiency. In addition, vacuum heat insulation is considered as one form of the high-performance heat insulation container.
[0015]
Further, since the inside of the inner cylinder 9a of the heat insulating container 9 is used as the flow path 12 of the combustion gas of the reformer 1, the structure of the entire apparatus becomes simple, leading to cost reduction. A furnace tube 11 through which the combustion gas injected from 10 flows, and a combustion gas flow path 12 formed between the furnace tube 11 and the inner cylinder 9 a of the heat insulating container 9, and a reforming catalyst is provided therein. And a plurality of reforming tubes 13 for circulating the raw material gas and reforming the raw material gas, so that the reforming tubes 13 are multiplexed and radiant heat transfer by high-temperature combustion in the combustor 10 is performed. Utilization makes it possible to shorten the overall length of the reformer 1, and accordingly, related equipment such as a water evaporator 2, a raw fuel vaporizer 3, a desulfurizer 4, a low-temperature shift converter 5, and a selective oxidation reactor 6. Can be arranged below the reformer 1, and the height of the fuel reformer can be reduced. Kill.
[0016]
During a normal operation, the raw material gas generated from the raw fuel is supplied to the reformer 1, and the combustion gas obtained by burning the anode off gas as the fuel gas is supplied to the reformer 1, the water evaporator 2, and the raw fuel. Heat exchange with the raw material gas is performed in the vaporizer 3, and the temperature is reduced to about 200 ° C. and the temperature of the reaction in the low-temperature shift converter 5 and the selective oxidation reactor 6 is increased. Even if bare reactors such as the low-temperature shift converter 5 and the selective oxidation reactor 6 are disposed in the space 17, there is no possibility that unnecessary heat exchange will occur.
[0017]
Thus, the size of the apparatus can be reduced and the thermal efficiency can be improved. Further, the labor for installing the heat insulating layer 9c can be greatly reduced, and the maintenance can be easily performed.
[0018]
[Problems to be solved by the invention]
As described above, the burner combustion type fuel reformer shown in FIGS. 11 and 12 has various excellent advantages. On the other hand, in the selective oxidation reactor 6 described above, CO having a concentration of several thousand ppm must be selectively reduced to several ppm or less from various components in the introduced reformed gas by an oxidation reaction. Therefore, in order to reduce this concentration, it is necessary to keep the reaction temperature constant. Therefore, in many cases, a multi-stage reactor having two to three stages is used as the selective oxidation reactor 6. The reformed gas introduced into the selective oxidation reactor 6 is H₂About 59%, CO about 0.5%, CO₂About 19%, H₂O is about 21.5%.
[0019]
FIG. 13 shows an outline of an apparatus flow when a general selective oxidation reactor applied to a fuel reformer has two sets of reactor bodies. In the figure, reference numeral 21 denotes an upstream reactor body into which a reformed gas 22a fed from the low-temperature shift converter 5 (see FIGS. 10 and 11) and mixed with oxidizing air 23 is introduced, and 24 is a reactor body A gas mixer for mixing the oxidizing air 25 with the reformed gas 22a from 21; a downstream side 26 where the oxidizing air 25 is mixed and the reformed gas 22b sent from the gas mixer 24 is introduced; The reactor bodies 21 and 26 are provided with coolers 21a and 26a, and are loaded with a selective oxidation catalyst containing Ru or the like as an active component.
[0020]
In the selective oxidation reactor shown in the apparatus flow of FIG. 13, oxidizing air 23 is added to and mixed with the reformed gas containing several thousand ppm of CO from the low-temperature shift converter 5, and the oxidizing air 23 is mixed. The raw gas 22a is introduced into the reactor main body 21, the oxidation reaction represented by [Chemical Formula 1] is performed by the action of the catalyst to reduce CO, and is sent from the reactor main body 21 to the gas mixer 24 to oxidize air. Mixed with 25. The reformed gas 22b mixed with the oxidizing air 25 generated by the gas mixer 24 is introduced into the reactor main body 26, and an oxidation reaction is performed in the same manner as in the reactor main body 21, and CO is reduced to several ppm. The fuel is reduced and introduced from the humidifier 7 to the anode 8b of the polymer electrolyte fuel cell 8 (see FIG. 10).
[0021]
In the reactor bodies 21 and 26, a cooling medium such as cooling water is supplied to the coolers 21a and 26a to perform cooling, and the temperature of the reformed gases 22a and 22b is preferably 120 ° C to 200 ° C, at which the oxidation reaction is easily performed. Is controlled at 150 ° C. Also, at the inlet side of the reactor body 21, the reforming gas 22a and the oxidizing air 23 can be easily mixed without providing a gas mixer because the flow rate of the oxidizing air 23 is large. On the inlet side, since the flow rate of the oxidizing air 25 is small, it is difficult to mix the reformed gas 22a and the oxidizing air 25. Therefore, the gas mixing is performed so that the reformed gas 22a and the oxidizing air 25 can be sufficiently mixed. Vessel 24 is required.
[0022]
In the selective oxidation reactor shown in FIG. 13, when a plurality of reactor bodies 21 and 26 are provided, a connecting pipe is usually required to connect the reactor bodies 21 and 26. When the reactor bodies 21 and 26 have a general cylindrical shape, a gap is formed between the reactor bodies 21 and 26 when a plurality of reactor bodies 21 and 26 are arranged side by side. It cannot be used effectively for arranging equipment, and the air gap becomes a dead space. Further, the gas mixer 24 must be provided between the reactor bodies 21 and 26 as described above. Therefore, the size of the selective oxidation reactor cannot be reduced as a whole.
[0023]
Further, when the selective oxidation reactor shown in FIG. 13 is applied to the fuel reformer shown in FIG. 11, the selective oxidation reactor is composed of a cylindrical base inner cylinder 16 and an outer Must be housed in a space 17 formed by the inner cylinder 9 a of the heat insulating container 9 and the base outer cylinder 15 which are arranged concentrically.
[0024]
However, the selective oxidation reactor cannot be housed in the space 17 unless it is miniaturized, so that the structure of the selective oxidation reactor needs to be devised.
[0025]
In view of the above-described circumstances, the present invention can reduce the size of a selective oxidation reaction device as a related device of a reformer and store it compactly in a narrow cylindrical space of a fuel reformer to save the space of the device. It was done for the purpose of doing so.
[0026]
[Means for Solving the Problems]
The invention according to claim 1 is a selective oxidation reaction device disposed as a related device of a reformer in a cylindrical space of a fuel reformer,
The selective oxidation reaction device is formed in a double cylindrical shape with a part cut off in the circumferential direction, and includes a plurality of rows of reactor bodies partitioned in the circumferential direction,
Each reactor body is partitioned by a perforated plate through which a reformed gas mixed with an oxidizing gas can flow, and is provided with three chambers, and a central oxidation chamber is loaded with a selective oxidation catalyst,
The reformed gas is configured to be fed upward or downward through the chamber of each reactor body in which the selective oxidation catalyst is loaded, and to react with the oxidizing gas by the action of the selective oxidation catalyst to remove CO. ,
When the reformed gas is sent from the reactor body of a given row to the reactor body of the next row, the reformed gas flows upward from the chamber of the reactor body of the row in which the selective oxidation catalyst is loaded. Alternatively, it is configured to flow through the lower perforated plate and to be introduced from a reformed gas introduction hole provided on the outer periphery into a gas mixing tube arranged in a chamber of the reactor body in the row where the selective oxidation catalyst is not loaded, in a gas mixing tube. ,
In the gas mixing pipe, the reformed gas is mixed with an oxidizing gas introduced from a portion different from the reformed gas inlet, and the reformed gas mixed with the oxidizing gas flows from the gas mixing pipe to the next row of reaction. It is configured so that it can be fed to a chamber connected to a chamber in which the gas mixing tube is arranged, wherein the selective oxidation catalyst of the vessel body is not loaded,
The reformed gas that has passed through the chamber loaded with the selective oxidation catalyst is taken out from the reactor body in the last row.
[0027]
The invention according to claim 2 is a selective oxidation reaction device disposed as a related device of a reformer in a cylindrical space of a fuel reformer,
The selective oxidation reaction device is formed in a double cylindrical shape with a part cut off in the circumferential direction, and includes a plurality of rows of reactor bodies partitioned in the circumferential direction,
Each reactor body is provided with a chamber partitioned by upper and lower perforated plates through which a reformed gas mixed with an oxidizing gas can flow and loaded with a selective oxidation catalyst between the upper and lower perforated plates,
In the reactor body of the odd-numbered rows in the reformed gas flow direction of the reactor body,
A reformed gas mixed with an oxidizing gas is supplied from a chamber between the lower perforated plate and the bottom plate to a chamber loaded with the selective oxidation catalyst, and
The chamber between the upper perforated plate and the ceiling plate is provided with an oxidizing gas supplied from one end side and a plurality of reforming gases supplied from the chamber loaded with the selective oxidation catalyst and provided on the outer periphery. The reformed gas introduced from the introduction hole is mixed, and the reformed gas mixed with the oxidizing gas is supplied to the chamber between the upper perforated plate and the ceiling plate in the reactor body of the next even-numbered row. A gas mixing tube adapted to obtain
In the reactor body of the even-numbered rows of the reformed gas flow direction in the reactor body,
A reformed gas mixed with an oxidizing gas is supplied from a chamber between the upper perforated plate and the ceiling plate to a chamber loaded with the selective oxidation catalyst, and
An oxidizing gas supplied from one end side and a plurality of reformed gas supplied from a chamber loaded with the selective oxidation catalyst and provided on the outer periphery are provided in a chamber between the lower perforated plate and the bottom plate. The reformed gas introduced from the holes is mixed, and the reformed gas mixed with the oxidizing gas can be supplied to the chamber between the lower perforated plate and the bottom plate in the next odd-numbered reactor body. A gas mixing tube is provided,
From the reactor body in the last row, the reformed gas that has passed through the chamber loaded with the selective oxidation catalyst can be taken out.
[0028]
The invention according to claim 3 is a selective oxidation reaction device disposed as a related device of a reformer in a cylindrical space of a fuel reformer,
The selective oxidation reaction device is formed in a double cylindrical shape with a part cut off in the circumferential direction, and includes a plurality of rows of reactor bodies partitioned in the circumferential direction,
Each reactor body is provided with a chamber partitioned by upper and lower perforated plates through which a reformed gas mixed with an oxidizing gas can flow and loaded with a selective oxidation catalyst between the upper and lower perforated plates,
In the reactor body of the odd-numbered rows in the reformed gas flow direction of the reactor body,
A reformed gas mixed with an oxidizing gas is supplied from a chamber between the upper perforated plate and the ceiling plate to a chamber loaded with the selective oxidation catalyst, and
An oxidizing gas supplied from one end side and a plurality of reformed gas supplied from a chamber loaded with the selective oxidation catalyst and provided on the outer periphery are provided in a chamber between the lower perforated plate and the bottom plate. The reformed gas introduced from the holes is mixed, and the reformed gas mixed with the oxidizing gas can be supplied to the chamber between the lower perforated plate and the bottom plate in the reactor body of the next even-numbered row. A gas mixing tube is provided,
In the reactor body of the even-numbered rows of the reformed gas flow direction in the reactor body,
A reformed gas mixed with an oxidizing gas is supplied from a chamber between the lower perforated plate and the bottom plate to a chamber loaded with the selective oxidation catalyst, and
The chamber between the upper perforated plate and the ceiling plate is provided with an oxidizing gas supplied from one end side and a plurality of reforming gases supplied from the chamber loaded with the selective oxidation catalyst and provided on the outer periphery. The reformed gas introduced from the introduction hole is mixed, and the reformed gas mixed with the oxidizing gas is supplied to the chamber between the upper perforated plate and the ceiling plate in the next odd-numbered reactor body. A gas mixing tube adapted to obtain
From the reactor body in the last row, the reformed gas that has passed through the chamber loaded with the selective oxidation catalyst can be taken out.
[0029]
The invention according to claim 4 is provided with a means for cooling the reformed gas mixed with the oxidizing gas in the reactor body.
[0030]
According to the above invention, a separate gas mixer is not required for mixing the reforming gas and the oxidizing gas for reacting in the downstream reactor body, so that the apparatus can be downsized and narrow. As a result of being compactly stored in a cylindrical room, the space of the device can be saved.
[0031]
Also, since the reactor body has a structure in which a part of the double cylinder is cut, the center and the cut part of the double cylinder are assembled with other components of the fuel reformer. The space can be passed through, so that the space can be effectively used and no dead space occurs.
[0032]
Further, the oxidizing gas mixed with the reformed gas from which CO has been removed in the upstream reactor body is sufficiently efficiently mixed in the gas mixing pipe, so that the CO can be favorably reduced in the downstream reactor body. Can be removed.
[0033]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, embodiments of the present invention will be described with reference to the accompanying drawings.
1 to 9 show an example of an embodiment of the present invention, in which parts denoted by the same reference numerals as those in FIG. 11 represent the same parts.
[0034]
Thus, in the illustrated example, the planar shape of the selective oxidation reactor 6 applied to the fuel reformer is one in the circumferential direction as shown in FIG. A cylindrical space defined by a base plate 14, a base inner cylinder 16, a base outer cylinder 15, and an inner cylinder 9 a of a heat insulating container 9 and having a cut-away portion and communicating with the combustion gas flow path 12. 17.
[0035]
As shown in detail in FIGS. 2 to 9, the selective oxidation reactor 6 includes a double-cylindrical first-row reactor body 31 and a partition plate 33 on a circumferential side surface of the reactor body 31. And a second column of reactor bodies 32 of a double cylindrical shape connected via a via hole, and are formed in a plurality of rows that are partitioned in the circumferential direction. It has a bent shape. Thus, the inner diameter D1 of the reactor bodies 31, 32 is slightly larger than the outer diameter of the base inner cylinder 16, and when the reactor bodies 31, 32 are stored in the space 17, the reactor bodies 31, 32 are formed. Is adapted to exactly match the outer circumference of the base inner cylinder 16.
[0036]
The reactor body 31 includes a large-diameter arc-shaped outer peripheral plate 31a and a small-diameter arc-shaped inner peripheral plate 31b, a ceiling plate 31c arranged to connect the upper ends of the outer peripheral plate 31a and the inner peripheral plate 31b, and an outer peripheral plate 31a. And a bottom plate 31d arranged to connect the lower end of the inner peripheral plate 31b, a side plate 31e covering a side part separated from the reactor main body 32, and the partition plate 33 to form a sealed double arc container. Have been.
[0037]
The inside of the reactor main body 31 is partitioned by upper and lower two-stage perforated plates 34 and 35 formed of punching metal or the like provided with a large number of holes, and formed between the perforated plates 34 and 35 in the reactor main body 31. The chamber 36 is loaded with a selective oxidation catalyst containing Ru or the like as an active component.
[0038]
The reactor main body 32 includes a large-diameter arc-shaped outer peripheral plate 32a, a small-diameter arc-shaped inner peripheral plate 32b, a ceiling plate 32c arranged to connect the upper ends of the outer peripheral plate 32a and the inner peripheral plate 32b, and an outer peripheral plate 32a. And a bottom plate 32d arranged to connect the lower end of the inner peripheral plate 32b, a side plate 32e covering a side part separated from the reactor main body 31, and the partition plate 33 to form a sealed double arc container shape. Have been.
[0039]
Therefore, the reactor main bodies 31 and 32 are joined to each other with the partition plates 33 forming a part of each of the reactor main bodies 31 and 32 in a substantially double cylindrical container shape partially cut off in the circumferential direction. The connecting pipe for connecting the reactor bodies 31 and 32 is not required.
[0040]
The inside of the reactor main body 32 is partitioned by upper and lower two-stage perforated plates 37 and 38 formed of punching metal or the like provided with a large number of holes, and formed between the perforated plates 37 and 38 in the reactor main body 31. The chamber 39 is loaded with a selective oxidation catalyst containing Ru or the like as an active component.
[0041]
A reformed gas supply pipe 42 is connected to the side plate 31e so that the reformed gas 41a can be supplied to the chamber 40 between the perforated plate 35 and the bottom plate 31d in the reactor main body 31. That is, the reformed gas supply pipe 42 is connected to the lower end of the side plate 31e and extends to near the upper end of the reactor body 31 connected to the horizontal part 42a so as to communicate with the chamber 40. A vertical portion 42b and a horizontal portion 42c connected near the upper end of the vertical portion 42b are provided, and an orifice 43 is provided in the vertical portion 42b. Thus, the reformed gas 41 a can be supplied to the reformed gas supply pipe 42 from the lower end of the vertical pipe connected to the horizontal portion of the reformed gas supply pipe 42.
[0042]
At a position above the orifice 43 on the upstream side in the vertical portion 42b of the reformed gas supply pipe 42, the oxidizing air 44 used for the oxidation reaction in the first-stage reactor body 31 is placed on the upper side in the vertical portion 42b. An oxidizing air supply pipe 45 is inserted so as to be able to be introduced upstream of the orifice 43. The oxidizing air supply pipe 45 is bent horizontally outside the vertical portion 42b of the reformed gas supply pipe 42, and can supply the oxidizing air 44 to the horizontal end from below.
[0043]
In a chamber 47 between the perforated plate 34 and the ceiling plate 31c in the reactor main body 31, a gas having an arc shape in plan view and capable of supplying oxidizing air 48 to be used for an oxidation reaction in the reactor main body 32. The mixing tube 49 is inserted. The gas mixing tube 49 extends from the reactor main body 31 to the outside, and an oxidizing air 48 can be introduced into the outer end from below.
[0044]
The distal end of the gas mixing pipe 49 is connected to the partition plate 33 so that the outer periphery is completely sealed by welding or the like, and opens to the chamber 51 side of the reactor main body 32 between the porous plate 37 and the ceiling plate 32c. At the same time, a large number of reformed gas introduction holes 49a are formed in the outer peripheral portion, and the reformed gas introduced into the chamber 47 through the perforated plate 34 after ascending in the chamber 36 in the reactor body 31 is The gas is introduced into the gas mixing pipe 49 from the reformed gas introduction hole 49a.
[0045]
Thus, the reformed gas and the oxidizing air 48 are mixed well in the gas mixing pipe 49 and introduced into the chamber 51 of the reactor main body 32.
[0046]
A reformed gas outlet pipe 53 is connected to the side plate 32e of the reactor main body 32 so as to communicate with a chamber 52 between the perforated plate 38 and the bottom plate 32d. The reformed gas 41b can be sent downward.
[0047]
From the lower surface of the bottom plate 32d of the reactor main body 32 near the partition plate 33, a cooling fluid supply pipe 55 for supplying a cooling fluid 54 is laid in the chamber 39 through the chamber 52, and the inside of the chamber 39 is zigzag. It is laid on the upper part. In the upper part of the chamber 39, the cooling fluid supply pipe 55 extends through the partition plate 33 into the chamber 36 of the reactor main body 31, and is laid downward in a zigzag manner in the chamber 36. Through to the outside. In addition, the penetration part of the partition plate 33 of the cooling fluid supply pipe 55 is held densely.
[0048]
Since the reactor bodies 31 and 32 have a substantially double cylindrical shape and are partially cut off at both ends in the circumferential direction, the side plates 31e and 32e are viewed in plan as shown in FIGS. And have a close shape.
[0049]
Next, the operation of the above embodiment will be described.
The reformed gas 41a sent from the low-temperature shift converter 5 in FIG. 10 is introduced from a horizontal portion 42c of the reformed gas supply pipe 42 to a vertical portion 42b. The oxidizing air 44 is introduced from the oxidizing air supply pipe 45 to the vertical portion 42b of the reformed gas supply pipe 42. Thus, the reformed gas 41a and the oxidizing air 44 are mixed when passing through the orifice 43 in the vertical portion 42b, and are introduced from the chamber 40 through the perforated plate 35 into the chamber 36.
[0050]
Since a selective oxidation catalyst containing Ru or the like as an active component is stored in the chamber 36, several thousand ppm of CO contained in the reformed gas 41a is oxidized in the chamber 36 by the action of the selective oxidation catalyst. Reaction with oxygen in the air 44 as shown in [Chemical Formula 1]₂Therefore, CO in the reformed gas 41a is removed.
[0051]
The reformed gas 41a from which CO has been removed to some extent is sent from the chamber 36 to the chamber 47 through the perforated plate 34, and is introduced from the chamber 47 into the gas mixing pipe 49 through the reformed gas introduction hole 49a.
[0052]
The oxidizing air 48 is supplied from the outer end of the gas mixing pipe 49 into the gas mixing pipe 49, mixed with the reformed gas introduced from the reformed gas introduction hole 49a, and mixed with the oxidizing air 48. The reformed gas is supplied to the chamber 51 of the reactor main body 32. The flow rate of the oxidizing air 48 in the gas mixing pipe 49 is smaller than that of the reformed gas 41a, and the reformed gas 41a is introduced into the gas mixing pipe 49 from the reformed gas introduction hole 49a at a high flow rate. In order to change the flow direction, the oxidizing air 48 is satisfactorily stirred and mixed with the reformed gas 41 a in the gas mixing pipe 49, and is supplied to the chamber 51 of the reactor main body 32.
[0053]
The reformed gas mixed with the oxidizing air 48 sent to the chamber 51 passes through the perforated plate 37 and flows down into the chamber 39. Since the selective oxidation catalyst containing Ru or the like as an active component is stored in the chamber 39, the CO contained in the reformed gas is supplied to the chamber 39 by the action of the selective oxidation catalyst. And the reaction as shown in₂Therefore, CO in the reformed gas is removed up to about several ppm.
[0054]
Thus, the reformed gas 41b from which CO has been removed to a desired state is sent from the chamber 39 to the reformed gas outlet pipe 53 through the chamber 52, and is led out of the reformed gas outlet pipe 53 to be humidified. The fuel is supplied from the container 7 to the anode 8 b of the polymer electrolyte fuel cell 8.
[0055]
The cooling fluid 54 passes through the cooling fluid supply pipe 55 and cools the gas in the chamber 39 and the reformed gas in the chamber 36 to a predetermined temperature. As in the case shown in FIG. 13, the temperature of the reformed gas is controlled at 120 ° C. to 200 ° C., in which the oxidation reaction is easily performed, preferably 150 ° C.
[0056]
According to the illustrated example, a connecting pipe is not required for the reactor bodies 31 and 32 of the selective oxidation reactor 6, and the reformed gas to be reacted in the second-stage reactor body 32 and the oxidizing air are mixed. Therefore, a separate gas mixer is not required, so that the size of the apparatus can be reduced, and the reactor main bodies 31, 32 can be compactly stored in the narrow cylindrical space 17, resulting in space saving of the apparatus. Becomes possible.
[0057]
Further, since the double cylinder has a structure in which a part of the double cylinder is cut away, the center part and the cut part of the double cylinder are not used for other components of the fuel reformer, for example, the combustor 10 shown in FIG. The space for passing the cylindrical base inner cylinder 16, the anode off-gas supply pipe 19, the fuel supply pipe 20 for combustion, and the like for supplying combustion air to the unit can be effectively used. No dead space occurs.
[0058]
Further, the reformed gas from which CO has been removed in the reactor main body 31 and the oxidizing air 48 are sufficiently efficiently mixed in the gas mixing pipe 49, so that the CO in the second-stage reactor main body 32 is also good. Can be removed.
[0059]
The selective oxidation reaction device of the fuel reformer of the present invention can be modified in various ways without departing from the gist of the present invention. For example, in the illustrated example of the present invention, a case where two sets of the reactor main bodies are provided in the circumferential direction has been described, but any number of sets of the plurality of sets may be implemented.
[0060]
When three or more reaction vessel bodies are provided, the mixing pipe for mixing the reformed gas and the oxidizing air needs to be arranged as described below. That is, in the odd-numbered reactor main body from the upstream side to the downstream side in the gas flow direction, when the gas mixing pipe is arranged in the chamber between the upper perforated plate and the ceiling plate, the even-numbered stage reaction vessel main body is When it is necessary to arrange a gas mixing tube in a chamber between the lower perforated plate and the bottom plate, and in a case where a gas mixing tube is arranged in a chamber between the lower perforated plate and the bottom plate in the odd-numbered reactor main body, Therefore, in the reaction vessel body of the even-numbered stage, it is necessary to arrange a gas mixing pipe in a chamber between the upper perforated plate and the ceiling plate.
[0061]
Further, the gas for oxidizing CO is not limited to air, and any gas containing oxygen can be used.
[0062]
【The invention's effect】
As described above, according to the selective oxidation reactor according to claims 1 to 4 of the present invention,
I) Since a gas mixer for mixing the reforming gas and the oxidizing gas to be reacted in the reactor body on the downstream side becomes unnecessary, the apparatus can be downsized and can be housed compactly in a narrow cylindrical chamber. As a result, space saving of the device becomes possible.
II) The reactor body has a structure in which a part of a double cylinder is cut off, so that the center and the cut part of the double cylinder are assembled with other components of the fuel reformer. It can be used as a space to pass through, so that space can be used effectively and dead space does not occur,
III) The reformed gas and the oxidizing gas from which CO has been removed in the reactor body are sufficiently efficiently mixed in the gas mixing pipe, so that CO can be satisfactorily removed.
And various other excellent effects.
[Brief description of the drawings]
FIG. 1 is a plan view of an example of an embodiment of a selective oxidation reaction device of a fuel reformer of the present invention, and is a view as seen in a direction of an arrow II in FIG.
FIG. 2 is an exploded front view of the selective oxidation reaction apparatus shown in FIG. 1, and is a view taken in the direction of arrows II-II in FIG.
FIG. 3 is a view in the direction of arrows III-III in FIG. 2;
FIG. 4 is a view in the direction of arrows IV-IV in FIG. 2;
FIG. 5 is a view as viewed in the direction of the arrow V in FIG. 2;
6 is a view in the direction of arrows VI in FIG. 2;
FIG. 7 is a view taken in the direction of the arrow VII in FIG. 2;
8 is a schematic perspective view of the selective oxidation reaction device shown in FIG.
9 is a perspective view showing a gas mixing tube housed in a chamber above a reactor main body in a first row in the selective oxidation reaction apparatus shown in FIG.
FIG. 10 is an overall system diagram showing an example of equipment provided with a reformer.
FIG. 11 is a longitudinal sectional front view showing an example of a fuel reforming apparatus.
FIG. 12 is a view taken in the direction of arrows XII-XII in FIG. 11;
FIG. 13 is a schematic diagram of a general selective oxidation reactor applied to a fuel reformer, in which there are two sets of reactor bodies.
[Explanation of symbols]
1 Reformer
6. Selective oxidation reactor (selective oxidation reactor)
17 Space
31 Reactor body
31c ceiling board
31d bottom plate
32 reactor body
32c ceiling board
32d bottom plate
34 perforated plate
35 perforated plate
36 rooms
37 perforated plate
38 perforated plate
39 rooms
40 rooms
41a Reformed gas
41b Reformed gas
44 Oxidizing air (oxidizing gas)
47 rooms
48 Oxidizing air (oxidizing gas)
49 gas mixing tube
49a Reformed gas inlet
51 rooms
52 rooms
54 Cooling fluid (cooling means)
55 Cooling fluid supply pipe (cooling means)

Claims (4)

A selective oxidation reaction device disposed as a related device of a reformer in a cylindrical space of a fuel reformer,
The selective oxidation reaction device is formed in a double cylindrical shape with a part cut off in the circumferential direction, and includes a plurality of rows of reactor bodies partitioned in the circumferential direction,
Each reactor body is partitioned by upper and lower perforated plates through which a reformed gas mixed with an oxidizing gas can flow, and each has three chambers, and a central chamber is loaded with a selective oxidation catalyst,
The reformed gas is configured to be fed upward or downward through the chamber of each reactor body in which the selective oxidation catalyst is loaded, and to react with the oxidizing gas by the action of the selective oxidation catalyst to remove CO. ,
When the reformed gas is sent from the reactor body of a given row to the reactor body of the next row, the reformed gas flows upward from the chamber of the reactor body of the row in which the selective oxidation catalyst is loaded. Alternatively, it is configured to flow through the lower perforated plate and to be introduced from a reformed gas introduction hole provided on the outer periphery into a gas mixing tube arranged in a chamber of the reactor body in the row where the selective oxidation catalyst is not loaded, in a gas mixing tube. ,
In the gas mixing pipe, the reformed gas is mixed with an oxidizing gas introduced from a portion different from the reformed gas inlet, and the reformed gas mixed with the oxidizing gas flows from the gas mixing pipe to the next row of reaction. It is configured so that it can be fed to a chamber connected to a chamber in which the gas mixing tube is arranged, wherein the selective oxidation catalyst of the vessel body is not loaded,
A selective oxidation reaction apparatus characterized in that a reformed gas that has passed through a chamber loaded with a selective oxidation catalyst is taken out of a reactor body in the last row. A selective oxidation reaction device disposed as a related device of a reformer in a cylindrical space of a fuel reformer,
The selective oxidation reaction device is formed in a double cylindrical shape with a part cut off in the circumferential direction, and includes a plurality of rows of reactor bodies partitioned in the circumferential direction,
Each reactor body is provided with a chamber partitioned by upper and lower perforated plates through which a reformed gas mixed with an oxidizing gas can flow and loaded with a selective oxidation catalyst between the upper and lower perforated plates,
In the reactor body of the odd-numbered rows in the reformed gas flow direction of the reactor body,
A reformed gas mixed with an oxidizing gas is supplied from a chamber between the lower perforated plate and the bottom plate to a chamber loaded with the selective oxidation catalyst, and
The chamber between the upper perforated plate and the ceiling plate is provided with an oxidizing gas supplied from one end side and a plurality of reforming gases supplied from the chamber loaded with the selective oxidation catalyst and provided on the outer periphery. The reformed gas introduced from the introduction hole is mixed, and the reformed gas mixed with the oxidizing gas is supplied to the chamber between the upper perforated plate and the ceiling plate in the reactor body of the next even-numbered row. A gas mixing tube adapted to obtain
In the reactor body of the even-numbered rows of the reformed gas flow direction in the reactor body,
A reformed gas mixed with an oxidizing gas is supplied from a chamber between the upper perforated plate and the ceiling plate to a chamber loaded with the selective oxidation catalyst, and
An oxidizing gas supplied from one end side and a plurality of reformed gas supplied from a chamber loaded with the selective oxidation catalyst and provided on the outer periphery are provided in a chamber between the lower perforated plate and the bottom plate. The reformed gas introduced from the holes is mixed, and the reformed gas mixed with the oxidizing gas can be supplied to the chamber between the lower perforated plate and the bottom plate in the next odd-numbered reactor body. A gas mixing tube is provided,
A selective oxidation reaction apparatus characterized in that a reformed gas that has passed through a chamber loaded with a selective oxidation catalyst can be taken out of a reactor body in the last row. A selective oxidation reaction device disposed as a related device of a reformer in a cylindrical space of a fuel reformer,
The selective oxidation reaction device is formed in a double cylindrical shape with a part cut off in the circumferential direction, and includes a plurality of rows of reactor bodies partitioned in the circumferential direction,
Each reactor body is provided with a chamber partitioned by upper and lower perforated plates through which a reformed gas mixed with an oxidizing gas can flow and loaded with a selective oxidation catalyst between the upper and lower perforated plates,
In the reactor body of the odd-numbered rows in the reformed gas flow direction of the reactor body,
A reformed gas mixed with an oxidizing gas is supplied from a chamber between the upper perforated plate and the ceiling plate to a chamber loaded with the selective oxidation catalyst, and
An oxidizing gas supplied from one end side and a plurality of reformed gas supplied from a chamber loaded with the selective oxidation catalyst and provided on the outer periphery are provided in a chamber between the lower perforated plate and the bottom plate. The reformed gas introduced from the holes is mixed, and the reformed gas mixed with the oxidizing gas can be supplied to the chamber between the lower perforated plate and the bottom plate in the reactor body of the next even-numbered row. A gas mixing tube is provided,
In the reactor body of the even-numbered rows of the reformed gas flow direction in the reactor body,
A reformed gas mixed with an oxidizing gas is supplied from a chamber between the lower perforated plate and the bottom plate to a chamber loaded with the selective oxidation catalyst, and
The chamber between the upper perforated plate and the ceiling plate is provided with an oxidizing gas supplied from one end side and a plurality of reforming gases supplied from the chamber loaded with the selective oxidation catalyst and provided on the outer periphery. The reformed gas introduced from the introduction hole is mixed, and the reformed gas mixed with the oxidizing gas is supplied to the chamber between the upper perforated plate and the ceiling plate in the next odd-numbered reactor body. A gas mixing tube adapted to obtain
A selective oxidation reaction apparatus characterized in that a reformed gas that has passed through a chamber loaded with a selective oxidation catalyst can be taken out of a reactor body in the last row. 4. The selective oxidation reaction apparatus according to claim 1, further comprising means for cooling the reformed gas mixed with the oxidizing gas in the reactor body.

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