JP5065117B2 - Carbon monoxide removal device and hydrogen production device - Google Patents

Description

  The present invention relates to a carbon monoxide removal apparatus that removes carbon monoxide contained in a hydrogen-rich reformed gas produced from a raw material for hydrogen production such as kerosene, and a hydrogen production apparatus including the same.

  For example, Patent Document 1 discloses a hydrogen production apparatus that produces hydrogen for use in power generation by a fuel cell. In this apparatus, a raw material for hydrogen production such as methanol is reformed by a reforming catalyst layer to generate a hydrogen-rich reformed gas, and carbon monoxide (in the reformed gas that poisons the electrode catalyst of the fuel cell) In order to remove (CO), the reformed gas is passed through the CO shift catalyst layer to reduce CO by an aqueous shift reaction, and the reformed gas from the CO shift catalyst layer is passed through the CO selective oxidation catalyst layer by selective oxidation. CO is further reduced.

In this selective oxidation by the CO selective oxidation catalyst layer, an oxygen source for oxidizing CO is required, so that air is introduced into the oxidation removal section.
JP 200431280 A

  However, if the reformed gas and air are not sufficiently mixed, or if the gas temperature is not adjusted to a temperature range that maximizes the activation of the selective oxidation catalyst, the CO removal efficiency in the CO selective oxidation catalyst layer May decrease.

  The present invention has been made in view of the above circumstances, and a carbon monoxide removal apparatus capable of producing high-purity hydrogen from which carbon monoxide has been sufficiently removed, and a hydrogen production apparatus provided with the same. The purpose is to provide.

A carbon monoxide removal apparatus according to the present invention is a carbon monoxide removal apparatus that removes carbon monoxide contained in a hydrogen-rich reformed gas, and reduces carbon monoxide contained in the reformed gas by an aqueous shift reaction. A shift unit, a chamber for mixing the reformed gas and the oxygen-containing gas from the shift unit, a cooling unit for cooling the mixed gas from the chamber, and carbon monoxide in the mixed gas cooled by the cooling unit A selective oxidation portion that oxidizes, a first region having a substantially columnar shape, a second region that is located on the outer peripheral side of the first region and is an annular region coaxial with the first region, and an outer periphery of the second region A third region that is an annular region that is coaxial with the first region and a fourth region that is an annular region that is coaxial with the first region and is located on the outer peripheral side of the third region, , For introducing the reformed gas from the chamber and the shift unit into the chamber A central gas passage, a shift portion in the second region, a mixed gas passage and a selective oxidation portion through which the mixed gas from the chamber passes in the third region, and cooling in the fourth region. The annular mixed gas flow path in the third region is provided with an inlet for introducing the mixed gas from the chamber in a part of the circumferential direction, and the annular mixed gas channel in the third region The selective oxidation unit is provided with a lead-out port from which the selectively oxidized reformed gas is led out partially in the circumferential direction, and is guided to the introduction port in the circumferential positional relationship around the first region. The outlet is provided on the opposite side across the first region, and the shift unit includes a high temperature shift unit and a low temperature shift unit that performs an aqueous shift reaction at a lower temperature than the high temperature shift unit, and the high temperature shift unit The cooling unit is adjacent to the mixed gas flow path .

  In this carbon monoxide removal apparatus, it is possible to sufficiently mix the reformed gas and the oxygen-containing gas from the shift unit by providing a mixing chamber for mixing the reformed gas and the oxygen-containing gas from the shift unit. It has the characteristic of being. In addition, by providing a heat exchanger for the mixed gas and reforming water in the subsequent stage, the mixed gas is cooled and adjusted to a temperature suitable for selective oxidation in the selective oxidation unit, and heat is supplied to the reforming water. Thus, the modification efficiency can be improved. As described above, hydrogen can be efficiently produced in the reforming section, and selective oxidation in the selective oxidation section can be performed efficiently, so that high-purity hydrogen from which carbon monoxide has been sufficiently removed can be efficiently produced. Can be manufactured.

Further, by disposing the respective parts in a coaxial ring shape, it is possible to efficiently remove carbon monoxide with a compact configuration.

In here, the inlet and outlet may be in the same side with respect to the first region, most of the mixed gas introduced into the selective oxidizing unit through the inlet is passed biased to a portion of the selective oxidation unit, moreover Although the shortest distance connecting the inlet and outlet may be derived without sufficient selective oxidation, the inlet and outlet are thus provided on the opposite side across the first region. Thus, carbon monoxide in the reformed gas can be sufficiently reduced because it can be passed through the selective oxidation portion without being biased to a specific portion and longer.

  A dispersion for dispersing the mixed gas introduced from the inlet in the circumferential direction may be provided in the annular mixed gas channel in the third region. In this way, the mixed gas can be dispersed in the circumferential direction and passed through the selective oxidation unit without being partially biased, so that carbon monoxide in the reformed gas can be sufficiently reduced.

  The selective oxidation unit and the mixed gas flow path may be characterized by being partitioned by an annular plate having a plurality of holes. In this way, the mixed gas can be further dispersed in the circumferential direction by restricting the flow rate of the mixed gas in the annular plate.

The oxygen containing gas may be introduced into the chamber through a central gas flow path. In this way, since the oxygen-containing gas is preheated via the shift unit, the reformed gas and the oxygen-containing gas can be easily mixed in the chamber.
The reforming water is caused to flow through the annular cooling section in the fourth region, and its inlet is provided in a part of the circumferential direction. In the cooling section, the reforming water is dispersed in the circumferential direction. A dispersion may be provided. In this way, since the reforming water can be dispersed in the circumferential direction and passed through the cooling unit without being partially biased, the temperature in the circumferential direction of the selective oxidation unit can be made uniform, and the reformed gas It becomes possible to sufficiently reduce carbon monoxide therein.

  A hydrogen production apparatus according to the present invention includes a reforming apparatus that reforms a raw material for hydrogen production to generate a hydrogen-rich reformed gas, and the above-described carbon monoxide removal apparatus. Since this hydrogen production apparatus includes the above-described carbon monoxide removal apparatus, it is possible to produce high-purity hydrogen from which carbon monoxide has been sufficiently removed from the raw material for hydrogen production.

  ADVANTAGE OF THE INVENTION According to this invention, the carbon monoxide removal apparatus which can manufacture the highly purified hydrogen from which carbon monoxide was fully removed, and a hydrogen production apparatus provided with the same can be provided.

  Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. In the description of the drawings, the same elements are denoted by the same reference numerals, and redundant description is omitted.

  FIG. 1 is a diagram showing an outline of a fuel cell system according to the present embodiment. In the fuel cell system 1, a hydrogen-rich reformed gas is generated from a raw material for hydrogen production in a hydrogen production apparatus 2, and electric power is generated by the fuel cell 3 using the reformed gas.

  As a raw material for producing hydrogen used in the fuel cell system 1, any substance that can obtain a reformed gas containing hydrogen by steam reforming can be used. For example, compounds having carbon and hydrogen in the molecule, such as hydrocarbons, alcohols, and ethers, can be used. Examples of raw materials that can be obtained inexpensively for industrial or consumer use include methanol, ethanol, dimethyl ether, methane, city gas, LPG (liquefied petroleum gas), and carbonized gasoline, naphtha, kerosene, light oil obtained from petroleum, etc. Mention may be made of hydrogen oil. Among these, liquid raw materials are preferable, and kerosene is particularly preferable because it is easily available and easy to handle.

  As shown in FIG. 1, the fuel cell system 1 includes a hydrogen production device (hereinafter referred to as “FPS”) 2 and a fuel cell 3. Examples of the fuel cell 3 include various types such as a solid polymer type (hereinafter referred to as “PEFC”), a phosphoric acid type, an alkali type, a molten carbonate type, and a solid oxide type. In particular, the description will be made on the premise of PEFC in which poisoning by carbon monoxide (CO) is a problem.

  The FPS 2 includes a reformer 21 and a carbon monoxide remover 22. The reformer 21 steam-reforms kerosene as a raw material for hydrogen production using the reforming water to generate a hydrogen-rich reformed gas. The carbon monoxide removing device 22 removes CO that becomes poisonous in the PEFC 3 from the reformed gas. The carbon monoxide removal apparatus 22 includes a shift unit 23, a chamber 24, and a selective oxidation unit 25.

  The shift unit 23 removes CO in the reformed gas by an aqueous shift reaction using a shift catalyst. The selective oxidation unit 25 removes CO in the reformed gas by selective oxidation using a selective oxidation catalyst. The chamber 24 mixes air (oxygen-containing gas) as an oxygen supply source for selective oxidation and the reformed gas. A mixed gas flow path 26 through which the mixed gas mixed in the chamber 24 flows is provided between the chamber 24 and the selective oxidation unit 25, and this is used for reforming as a cooling unit through which the reforming water flows. The mixed gas is cooled by heat exchange in contact with the water flow path 27.

  The fuel cell 3 generates power through an electrochemical reaction with oxygen using the hydrogen-rich reformed gas thus produced with the FPS 2.

  FIG. 2 is a longitudinal sectional view showing a specific configuration of the FPS 2 provided in the fuel cell system 1 of FIG. As shown in FIG. 2, the reformer 21 of the FPS 2 is disposed so as to surround the combustion cylinder 31 having a burner as a heat source and the combustion cylinder 31, and steam reforming the raw material for hydrogen production to improve the hydrogen rich reform. A reforming unit 32 for generating a quality gas, an exhaust gas channel 33 provided between the reforming unit 32 and the combustion cylinder 31, and an upper water channel 34 through which reforming water introduced into the reforming unit 32 passes. Have.

  As shown in FIGS. 2 and 3, the reforming section 32 includes a cylindrical inner body 35 disposed coaxially with the combustion cylinder 31 on the outer side of the combustion cylinder 31, and an inner side of the inner cylinder 35. And an outer body portion 36 disposed coaxially with the body portion 35. An exhaust gas flow path 33 through which exhaust gas from the combustion cylinder 31 passes is formed between the combustion cylinder 31 and the inner body portion 35.

  As shown in FIG. 2, a reduced diameter portion 36 a having a diameter smaller than that of the upper portion is formed at the lower portion of the outer body portion 36. A reforming catalyst that generates a reformed gas by promoting a steam reforming reaction between the raw material gas and the steam is accommodated between the inner barrel portion 35 and the outer barrel portion 36, and the lower end of the reduced diameter portion 36a. Is provided with an annular perforated plate 32a for supporting the reforming catalyst. Thereby, the reformed gas flows out through the porous plate 32a. A reformed gas outflow portion is formed by the reduced diameter portion 36a, the perforated plate 32a, and the lower portion of the inner cylinder portion 35 facing the reduced diameter portion 36a.

  As shown in FIGS. 2 and 4, an annular partition wall 37 is disposed outside the reduced diameter portion 36 a. The partition wall 37 is fixed to a circular guide plate 38 disposed below the outflow portion, and the guide plate 38 is fixed to the lower end of the inner body portion 35. The partition wall 37 has a heat insulating structure. For example, it may be formed thicker than other cylinders, and a known heat insulating material such as WDS (trade name: manufactured by Wacker Chemie GmbH, Germany) or glass wool may be used. Alternatively, a double wall structure in which a gas such as air is sealed inside or the inside is evacuated may be used. A cylindrical outer wall portion 39 having the same diameter as the upper portion of the outer body portion 36 is disposed outside the partition wall 37, and the outer wall portion 39 is fixed to the upper lower end of the outer body portion 36. A reformed gas passage 42 through which the reformed gas flows is formed by the guide plate 38 and the partition wall 37. That is, the reformed gas flowing out from the outflow portion collides with the guide plate 38 and changes its flow direction, rises along the outer peripheral surface of the reduced diameter portion 36 a while being guided by the partition wall 37, and then the upper end of the partition wall 37. It returns through the inner wall of the outer wall 39 and descends. As described above, the reformed gas flowing through the reformed gas channel 42 has a temperature higher than that of the reforming catalyst in the vicinity of the upper portion of the reduced diameter portion 36a. , Preventing the temperature reduction of the reforming catalyst.

  A cylindrical upper channel wall 40 disposed coaxially with the outer trunk portion 36 and the outer wall portion 39 is provided outside the outer trunk portion 36 and the outer wall portion 39. An upper water channel 34 through which reforming water for steam reforming flows is formed between the outer body 36 and the outer wall 39 and the upper water channel wall 40. The reforming water is heated by exchanging heat with the reformed gas passing through the reformed gas channel 42 via the outer wall portion 39, and then rises in the upper water channel 34 as water vapor and is supplied to the introduction portion of the reforming portion 32. Is done. The reformed gas that flows out from the outflow part of the reforming part 32 and flows through the reformed gas channel 42 is cooled by heat exchange with the reforming water via the outer wall part 39.

  The carbon monoxide (CO) removing device 22 removes carbon monoxide in the reformed gas generated by the reforming device 21. The CO removing device 22 is disposed adjacent to the lower side of the reforming device 21 and constitutes a vertical FPS 2. As described above, the reformer 21 that requires heat supply is disposed at the top, while the CO remover 22 that requires cooling is disposed at the bottom, so that the CO remover surrounds the reformer 21 coaxially. As compared with the case, the thermal efficiency can be increased and a slim configuration can be achieved.

  The CO removing device 22 has a substantially cylindrical first region S1, a second region S2 that is an annular region coaxial with the first region S1, and an outer periphery of the second region S2. A third region S3 that is an annular region that is coaxial with the first region S1 and a fourth region S4 that is an annular region that is coaxial with the first region S1 and located on the outer peripheral side of the third region S3. ing.

  The second region S2 is provided with a shift unit 23 that reduces carbon monoxide by an aqueous shift reaction that converts carbon monoxide in the reformed gas into water and carbon dioxide. The shift unit 23 includes a high temperature shift unit 23a and a low temperature shift unit 23b, and shift catalysts that are activated in different temperature ranges are provided. The reformed gas from the reformer 21 has a very high temperature of about 700 ° C., and the high temperature shift unit 23a contains a shift catalyst that is advantageous for promoting the aqueous shift reaction at high temperatures. An example of the shift catalyst is a mixed oxide of Fe—Cr. The low temperature shift unit 23b accommodates a shift catalyst that is advantageous for promoting the aqueous shift reaction at a lower temperature than the shift catalyst of the high temperature shift unit 23a. An example of the shift catalyst is a mixed oxide of Zn—Cu. By the aqueous shift reaction by the shift unit 23, the CO concentration contained in the reformed gas is reduced to about 1%. A dispersion plate 49 is provided at the entrance of the shift unit 23 to disperse the reformed gas from the reformer 21 over the entire entrance. The dispersion plate 49 is, for example, a punching metal having a plurality of holes, and disperses the reformed gas in the circumferential direction by limiting the gas flow rate.

  The first region S1 is provided with a central gas passage 51 through which the reformed gas from the shift section 23 flows, and a chamber 52 for mixing the reformed gas from the central gas passage 51 and air as an oxygen-containing gas. It has been. The central gas flow path 51 is provided with a small-diameter air introduction pipe 53 so that air is introduced into the chamber 52 from the outside of the FPS 2 through the air introduction pipe 53.

  The third region S3 is provided with a mixed gas flow path 26 through which the mixed gas from the chamber 52 flows, and a selective oxidation unit 25 that selectively oxidizes carbon monoxide in the mixed gas cooled by the mixed gas flow path 26. ing. The chamber 52 and the mixed gas flow path 26 are connected to each other by a communication flow path 54 that penetrates the high temperature shift portion 23a, as shown in FIGS. In this way, the mixed gas inlet 55 to the mixed gas flow path 26 is concentrated and concentrated in a part of the circumferential direction. As shown in FIG. 6, the mixed gas channel 26 is provided with a dispersion 56 on the outer surface of the inner peripheral wall that defines the mixed gas channel 26. The dispersion 56 disperses the mixed gas introduced into the mixed gas flow path 26 from the introduction port 55 in the circumferential direction, and covers an angular range of about 270 degrees with the angular position directly below the introduction port 55 as the center. It is arranged so as to block about half of the channel width.

  As shown in FIGS. 2 and 7, the mixed gas channel 26 and the selective oxidation unit 25 are partitioned by an annular plate 57 having a plurality of holes. In the selective oxidation unit 25, the CO concentration is reduced to 10 ppm or less. As shown in FIG. 2, a reformed gas outflow portion 58 through which a reformed gas containing high-purity hydrogen gas flows out is provided below the selective oxidation unit 25. The reformed gas is led out from the outlet 59 to the reformed gas outlet 58. In this manner, the reformed gas outlet 59 to the reformed gas outlet 58 is concentrated in a part of the circumferential direction. Here, as shown in FIGS. 2 and 8, the inlet 55 to the mixed gas passage 26 and the outlet to the reformed gas outlet 58 in the circumferential positional relationship with the first region S1 as the center. 59 is provided on the opposite side across the first region S1. The opposite side means at least the other 180-degree angle area different from the 180-degree angle area advanced 90 degrees to the left and right around the angle position where the introduction port 55 is provided. In particular, in the present embodiment, the outlet port 59 is provided at the opposite angular position advanced 180 degrees left and right around the angular position where the inlet port 55 is provided.

In the fourth region S4, a cooling unit for cooling the mixed gas from the chamber 52 is provided. The cooling section is configured as a reforming water flow path 27 between an inner cylinder 60 that divides the third region and the fourth region and an outer cylinder 61 that surrounds the inner cylinder 60. When the reforming water flows through the reforming water flow path 27 as the cooling unit, the reforming water and the mixed gas exchange heat at a portion of the mixed gas flow path 26, and the mixed gas is cooled. The reforming water channel 27 extends to the lower part of the selective oxidation unit 25 provided below the mixed gas channel 26 and also cools the selective oxidation unit 25.
Here, as shown in FIG. 2 and FIG. 9, the reforming water inlet is provided at a partial angular position in the circumferential direction, but directly above the portion where the inlet is provided. The dispersion 63 is arranged on the outer peripheral surface of the inner cylindrical body 60 so as to block about half of the flow path width over an angle range of about 120 degrees centered on the angle position of the introduction port.

  Here, a connecting portion between the reforming device 21 and the CO removing device 22 will be described. The lower end of the reformer 21 is closed by a circular inner corrugated plate 21a having a small-diameter hole in the center and an outer corrugated plate 21b having a large-diameter hole in the center. On the other hand, the upper end of the CO removing device 22 is closed by a circular inner corrugated plate 22a having a small-diameter hole in the center and an outer corrugated plate 22b having a large-diameter hole in the center. Then, the annular communication channel 41 is inserted through the holes of the outer corrugated plates 21b and 22b. The inner corrugated plate 21 a on the reforming device 21 side is sealed with the inner peripheral portion connected to the annular communication channel 41 and the outer peripheral portion connected to the outer wall portion 39. Further, the outer corrugated plate 21 b on the reforming device 21 side is sealed by connecting the inner peripheral portion with the annular communication channel 41 and connecting the outer peripheral portion with the upper water channel wall 40. On the other hand, the inner corrugated plate 22a on the CO removing device 22 side is sealed with the inner peripheral portion connected to the annular communication channel 41, and the outer peripheral portion defining the third region S3 and the fourth region S4. It is connected to the cylindrical body 60 and sealed. The outer corrugated plate 22b on the CO removing device 22 side is sealed by connecting the outer peripheral portion with the outer cylindrical body 61 with the inner peripheral portion being separated from the annular communication channel 22b.

  Next, the operation of the FPS 2 described above will be described.

  First, the reforming water cools the selective oxidation unit 25 through the reforming water flow path 27 of the CO removing device 22 and further rises while cooling the mixed gas with the mixed gas flow path 26. The reforming water inlet is provided at a part in the circumferential direction, and the angular position of the inlet is centered on the outer peripheral surface of the inner cylindrical body 60 immediately above the portion where the inlet is provided. The dispersion 63 is disposed so as to block about half of the flow path width over an angle range of about 120 degrees. Accordingly, the reforming water can be dispersed in the circumferential direction and passed through the reforming water flow path 27 without being partially biased, so that the temperature in the circumferential direction of the selective oxidation unit 25 can be made uniform. It becomes possible to sufficiently reduce carbon monoxide in the gas. The reforming water that has reached the top of the CO removing device 22 passes between the inner corrugated plate 22a and the outer corrugated plate 22b on the CO removing device 22 side, travels along the side surface of the annular communication channel 41, and is reformed. It passes between the inner corrugated plate 21 a and the outer corrugated plate 21 b and is introduced into the reforming section 32 through the upper water channel 34. Further, kerosene as a raw material for hydrogen production is introduced into the reforming unit 32.

  In the reforming unit 32, kerosene is steam reformed while receiving heat from the combustion cylinder 31 to generate hydrogen-rich reformed gas. The reformed gas is sent out to the reformed gas channel 42 through the perforated plate 32a at the outflow portion. The reformed gas that has flowed out of the outflow portion collides with the guide plate 38, changes its flow direction, rises along the outer peripheral surface of the reduced diameter portion 36a while being guided by the partition wall 37, and then passes through the upper end of the partition wall 37. And then descends along the inner peripheral surface of the outer wall 39. As a result, the reformed gas flowing through the inner reformed gas flow path 42 has a temperature higher than that of the reforming catalyst in the vicinity of the upper portion of the reduced diameter portion 36a, so heat exchange with the reforming catalyst is performed via the reduced diameter portion 36a. Thus, the temperature reduction of the reforming catalyst is prevented. On the other hand, the reformed gas passing through the outer reformed gas passage 42 is cooled by heat exchange with the reforming water and the outer wall portion 39.

  The reformed gas generated by the reformer 21 is introduced into the CO removing device 22 through the annular communication channel 41. The introduced reformed gas is dispersed in the circumferential direction by restricting the flow rate by the dispersion plate 49. And it introduce | transduces sequentially to the high temperature shift part 23a and the low temperature shift part 23b, and CO is removed by aqueous | water-based shift reaction. Next, the reformed gas that has reached the lower end of the shift unit 23 passes through the disk-like space at the lower end and ascends in the inner central gas flow path 51. A chamber 52 is provided in the upper part of the central gas flow path 51, where the air introduced from the air introduction pipe 53 and the reformed gas are mixed. The mixed gas mixed in the chamber 52 is introduced into the mixed gas channel 26 from the introduction port 55 through the communication channel 54. Here, the mixed gas is cooled by heat exchange with the reforming water. Further, the mixed gas introduced from the inlet 55 into the mixed gas flow path 26 is dispersed in the circumferential direction by the dispersion 56. Furthermore, the flow rate is limited by the annular plate 57 that partitions the mixed gas flow path 26 and the selective oxidation unit 25, so that the mixed gas is further dispersed in the circumferential direction. Thus, the mixed gas dispersed in the circumferential direction is introduced into the selective oxidation unit 25 through the hole of the annular plate 57. In the selective oxidation unit 25, CO in the reformed gas is sufficiently removed by selective oxidation, and then is led out from the outlet 59 to the reformed gas outflow unit 58. In this way, the reformed gas led out to the reformed gas outflow portion 58 is sent to the fuel cell to generate power.

  As described above in detail, according to the carbon monoxide removal apparatus 22 according to the present embodiment, the reformed gas and air from the shift unit 23 can be sufficiently mixed in the chamber 52 before cooling, Thereafter, the mixed gas can be cooled and adjusted to a temperature suitable for selective oxidation in the selective oxidation unit 25 in the cooling unit where the reforming water flow channel 27 and the mixed gas flow channel 26 are in contact with each other. Thus, selective oxidation can be performed efficiently. This makes it possible to produce high-purity hydrogen from which carbon monoxide has been sufficiently removed.

  In addition, by disposing each part of the carbon monoxide removing device 22 coaxially, it is possible to efficiently remove carbon monoxide with a compact configuration.

  In addition, since the mixed gas introduction port 55 to the mixed gas flow path 26 is concentrated in a part in the circumferential direction, the residence time is increased to promote the mixing of the reformed gas and air in the chamber 52. Can do. In addition, since the reformed gas outlet 59 from the selective oxidation unit 25 is concentrated in a part in the circumferential direction, the selective oxidation in the selective oxidation unit 25 can be promoted by increasing the residence time. Further, when the mixed gas introduction port 55 to the mixed gas passage 26 and the selectively oxidized reformed gas outlet 59 are on the same side with respect to the first region S1, the mixed gas passage 26 extends from the introduction port 55. Most of the mixed gas introduced into the gas flows through a portion of the selective oxidation unit 25 and may be derived without sufficient selective oxidation at the shortest distance connecting the introduction port 55 and the discharge port 59. However, as shown in FIGS. 5 and 8, by providing the inlet 55 and the outlet 59 on opposite sides of the first region S1 as in the present embodiment, the mixed gas is selectively oxidized 25. Therefore, carbon monoxide in the reformed gas can be sufficiently reduced because the catalyst can be passed through the catalyst in the selective oxidation unit 25 for a long time.

  Further, since the dispersion 56 for dispersing the mixed gas introduced from the introduction port 55 in the circumferential direction is provided in the mixed gas flow path 26, the mixed gas is dispersed in the circumferential direction and partially formed. It can be passed through the selective oxidation unit 25 without being biased, and carbon monoxide in the reformed gas can be sufficiently reduced.

  Further, since the selective oxidation unit 25 and the mixed gas flow path 26 are partitioned by the annular plate 57 having a plurality of holes, the flow rate of the mixed gas is limited in the annular plate 57, so that the mixed gas is moved in the circumferential direction. Can be further dispersed.

In addition, since air is preheated through the shift unit 23 by introducing air into the chamber 52 through the central gas flow path 51 through the air introduction pipe 53, the reformed gas and air are mixed in the chamber 52. It becomes easy.
Further, a cooling unit that also serves as the reforming water flow path 27 is provided on the outer periphery of the selective oxidation unit 25, and the reforming water inlet is provided in a part of the circumferential direction. A dispersion 63 is arranged immediately above the portion where the port is provided so as to block about half of the channel width over an angle range of about 120 degrees centered on the angle position of the inlet port. Accordingly, the reforming water can be dispersed in the circumferential direction and passed through the reforming water flow path 27 without being partially biased, so that the temperature in the circumferential direction of the selective oxidation unit 25 can be made uniform. It becomes possible to sufficiently reduce carbon monoxide in the gas.

  Moreover, since FPS2 which concerns on this embodiment can remove CO in the reformed gas produced | generated with the reformer 21 with the carbon monoxide removal apparatus 22 mentioned above, carbon monoxide is fully removed from the raw material for hydrogen production. It is possible to produce highly pure hydrogen.

  Further, the reforming apparatus 21 according to the present embodiment includes a partition wall 37 provided between the reforming unit 32 and the upper water channel 34, so that the reformed gas derived from the reforming unit 32 is reduced in diameter. By guiding along the outer peripheral surface of the reforming section 32 in the section 36a, the heat of the reformed gas can be recovered by heat exchange with the reforming section 32 where the endothermic reaction is performed, and the upper water channel 34 is used. By guiding along the inner peripheral surface, the heat of the reformed gas can be recovered by heat exchange with the reforming water flowing in the upper water channel 34, and the thermal efficiency can be increased. In addition, the combustion cylinder 31, the exhaust gas flow path 33, the reforming part 32, and the upper water channel 34 are sequentially surrounded from the outside, and a partition wall 37 is provided between the reforming part 32 and the upper water channel 34. Therefore, a compact configuration can be achieved.

  In addition, since the partition wall 37 has a heat insulating structure, heat recovery can proceed in a well-balanced manner on both the reforming portion 32 side and the upper water channel 34 side of the reformed gas channel 42, and the upper water channel 34 having a lower temperature. It is possible to prevent more heat from being recovered on the side.

  In addition, the FPS 2 according to the present embodiment can disperse the reformed gas over the entire inlet of the shift unit 23 by the dispersion plate 49, thereby preventing the reformed gas from being biased to a part of the shift unit 23, It is possible to remove carbon monoxide in the reformed gas by efficiently performing a shift reaction using the whole.

  In addition, this invention is not limited to the said embodiment, A various deformation | transformation is possible. For example, in the above-described embodiment, only one communication channel 54 between the chamber 52 and the mixed gas channel 26 is provided, but a plurality of communication channels 54 may be provided. However, in this case, it is preferable to dispose the introduction port 55 in a part of the circumferential direction. The outlet 59 to the reformed gas outlet 58 is the same.

  Further, in the above-described embodiment, the reforming portion 32 is reduced in diameter at the lower portion, and the partition wall 37 is provided only in the height range of the reduced diameter portion. The length of the reformed gas flow path 42 may be increased by extending the partition wall 37 to the upper end of the reforming section 32.

It is a figure showing the outline of the fuel cell system concerning this embodiment. It is a longitudinal cross-sectional view which shows the specific structure of the hydrogen production apparatus with which the fuel cell system of FIG. 1 is provided. It is the III-III sectional view taken on the line of FIG. It is the IV-IV sectional view taken on the line of FIG. It is the VV sectional view taken on the line of FIG. It is the VI-VI sectional view taken on the line of FIG. It is the VII-VII sectional view taken on the line of FIG. It is the VIII-VIII sectional view taken on the line of FIG. It is the IV-IV sectional view taken on the line of FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Fuel cell system, 2 ... Hydrogen production apparatus (FPS), 3 ... Fuel cell, 21 ... Reformer, 22 ... Carbon monoxide removal apparatus, 23 ... Shift part, 25 ... Selective oxidation part, 26 ... Mixed gas flow , 27 ... reforming water flow path (cooling section), 31 ... combustion cylinder, 32 ... reforming section, 33 ... exhaust gas flow path, 34 ... upper water path, 37 ... partition wall, 42 ... reformed gas flow path, 49 ... Dispersion plate, 51 ... Central gas flow path, 52 ... Chamber, 53 ... Air introduction pipe, 55 ... Inlet, 56 ... Dispersion, 57 ... Ring plate, 59 ... Outlet, 63 ... Dispersion, S1 ... First Region S2, second region, S3, third region, S4, fourth region.

Claims (6)

A carbon monoxide removal apparatus for removing carbon monoxide contained in a hydrogen-rich reformed gas,
A shift unit for reducing carbon monoxide contained in the reformed gas by an aqueous shift reaction;
A chamber for mixing the reformed gas and the oxygen-containing gas from the shift unit;
A cooling unit for cooling the mixed gas from the chamber;
A selective oxidation unit that selectively oxidizes carbon monoxide in the mixed gas cooled in the cooling unit;
Equipped with a,
Furthermore, a substantially columnar first region, a second region located on the outer peripheral side of the first region and an annular region coaxial with the first region, and the first region located on the outer peripheral side of the second region A third region that is an annular region that is coaxial with the fourth region, and a fourth region that is located on the outer peripheral side of the third region and is coaxial with the first region,
In the first region, the chamber and a central gas flow path for introducing the reformed gas from the shift unit into the chamber,
In the second region, the shift portion is provided,
In the third region, the mixed gas flow path through which the mixed gas from the chamber passes and the selective oxidation unit,
Having the cooling section in the fourth region;
In the annular mixed gas flow path in the third region, an introduction port into which the mixed gas from the chamber is introduced is provided so as to be biased toward a part in the circumferential direction,
The annular selective oxidation portion in the third region is provided with a discharge port through which the selectively oxidized reformed gas is led out partially in the circumferential direction,
In the circumferential positional relationship around the first region, the inlet and the outlet are provided on opposite sides of the first region,
The shift unit includes a high temperature shift unit and a low temperature shift unit that performs an aqueous shift reaction at a lower temperature than the high temperature shift unit,
The high temperature shift part and the cooling part are adjacent to each other with the mixed gas flow path interposed therebetween,
The carbon monoxide removal apparatus characterized by the above-mentioned. Wherein the third annular of the mixed gas passage in the region, claim, characterized in that the dispersion for dispersing the mixed gas introduced from the inlet port in a circumferential direction are provided 1 An apparatus for removing carbon monoxide according to 1. The carbon monoxide removal apparatus according to claim 1 or 2 , wherein the selective oxidation unit and the mixed gas flow path are partitioned by an annular plate having a plurality of holes. The carbon monoxide removing apparatus according to any one of claims 1 to 3 , wherein the oxygen-containing gas is introduced into the chamber through the central gas flow path. Water for reforming is caused to flow in the annular cooling section in the fourth region, and the inlet is provided in a part of the circumferential direction,
Wherein the cooling portion is carbon monoxide oxidizer according to any one of claims 1 to 4, characterized in that dispersions for dispersing the reforming water to the circumferential direction is provided. A reformer that reforms a raw material for hydrogen production to produce the hydrogen-rich reformed gas;
A carbon monoxide removal apparatus according to any one of claims 1 to 5 ;
A hydrogen production apparatus comprising:

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