JP6197561B2 - Hydrogen generator - Google Patents

Description

  The present invention relates to a hydrogen generator that reacts a hydrocarbon gas with water vapor to generate a hydrogen-containing gas, and more particularly to a hydrogen generator that includes a hydrodesulfurizer.

In general, in a fuel cell power generation system, first, hydrogen, carbon dioxide, carbon monoxide, unreacted source gas, water vapor, and the like are generated by a steam reforming reaction using raw material gas (hydrocarbon gas) and steam as raw materials by a reforming unit. A reformed gas containing is generated. Next, carbon monoxide is removed by a carbon monoxide reduction unit such as a shift conversion unit or a selective oxidation unit to generate a hydrogen-containing gas, and electricity is generated in the fuel cell using the obtained hydrogen-containing gas. When the raw material gas is methane, the reforming reaction is typically expressed by the following equations (1) and (2).
CH ₄ + H ₂ O → CO + 3H ₂ (1)
CO + H ₂ O → CO ₂ + H ₂ (2)

  The water vapor necessary for the steam reforming reaction is obtained by evaporating water in an evaporation section provided upstream of the reforming section. As the heat required for evaporation, heat obtained by burning the anode off-gas discharged from the fuel cell in the combustion section or heat of the reformed gas is usually used.

  An organic sulfur compound is added as an odorant to a source gas such as city gas, LP gas, and natural gas. Since the reforming catalyst is poisoned by the sulfur compound and deteriorates its performance, a desulfurization step is provided as a pretreatment for passing the raw material gas through the reforming catalyst in order to remove the sulfur compound in the raw material gas to an allowable concentration or less. There is a need.

  There are a room temperature desulfurization method and a hydrodesulfurization method as desulfurization methods for removing sulfur compounds in the raw material gas. In the hydrodesulfurization method, hydrogen is mixed with a raw material gas to hydrogenate a sulfur compound, and then adsorbed and removed with an adsorbent. Since the adsorption capacity of the sulfur compound by the hydrodesulfurization method is larger than the adsorption capacity of the sulfur compound by the room temperature desulfurization method, the hydrodesulfurization method is advantageous in reducing the cost by long-term operation of the hydrogen generator.

  In a hydrodesulfurizer, a sulfur compound reacts with hydrogen by a hydrogenation catalyst and decomposes, and is adsorbed and removed by an adsorbent. CuZn-based, Ni-based, CoMo (cobalt / molybdenum) -based materials are used as hydrogenation catalysts, and ZnO (zinc oxide) -based materials and other metal oxides (for example, iron oxide and manganese oxide) are used as adsorbents. It is done. In order to cause an appropriate reaction in the catalyst, it is necessary to keep the catalyst at a high temperature of about 200 ° C. to 400 ° C., depending on the type of catalyst.

  In order to increase the efficiency of heat supply to the hydrodesulfurizer and to make the hydrodesulfurizer more compact, a hydrodesulfurizer installed concentrically around the reformer and around the transformer A hydrogen generation apparatus in which hydrodesulfurizers are installed concentrically has been proposed.

  In the hydrogen generator of Patent Document 1, a hydrodesulfurizer is installed so as to transfer heat with a shift converter or a CO remover. The hydrodesulfurization agent is composed of a hydrogenating agent and an adsorbent, or an agent having both hydrogenation and adsorption functions, and the agent having the adsorption function contains Cu. In the hydrogen generator of Patent Document 1, when all the hydrodesulfurization agents are installed around the transformer or the CO remover disposed on the outermost side of the fuel processor, the width of the fuel processor increases, and the installation is wide. It needs space.

  In the hydrogen generator of Patent Document 2, a hydrodesulfurizer is installed via a heat insulating material so as to transfer heat to the reformer. Further, it is installed so as to transfer heat to the reformer and to transfer heat to the CO purification unit (showing a transformer and a CO remover). Further, the preheating of the source gas is performed on the outer peripheral surface of the CO purification unit. In Patent Document 2, if a preheating pipe for raw material gas is installed in the CO purification section, the structure becomes complicated. In addition, when heat transfer to the hydrodesulfurizer is performed from the reformer via a heat insulating material, the temperature of the hydrodesulfurization agent is easily affected by load fluctuations of the fuel processing device, and the hydrodesulfurization agent is It becomes difficult to keep the temperature.

  In the hydrogen-containing gas generator of Patent Document 3, a hydrodesulfurizer is installed between the reformer and the transformer, and transfers heat with the reformer. Since the reformer has a high temperature, in Patent Document 3, it is difficult to obtain an appropriate temperature for the hydrodesulfurization agent. Therefore, there are difficulties such as limitations on the hydrodesulfurization agent used and difficulty in optimizing the amount of desulfurization agent used.

  In the fuel reformer of Patent Document 4, a hydrodesulfurizer is installed so as to transfer heat to the transformer. Also, unvaporized reforming water and raw materials are introduced from the top. In Patent Document 4, when all the hydrodesulfurization agents are installed around the transformer disposed on the outermost side of the fuel reformer, the width of the fuel reformer becomes large and a large installation space is required.

  In the hydrodesulfurizer-integrated cylindrical steam reformer of Patent Documents 5 and 6, the hydrodesulfurizer is installed via a heat insulating material so as to transfer heat to the reformer. Further, the hydrodesulfurization agent is composed of three types of hydrogenation catalyst layer, first adsorbent layer, and second adsorbent layer. In Patent Documents 5 and 6, when heat transfer from the catalyst layer surface of the fuel processor is performed via a heat insulating material, it is difficult to keep the temperature of the hydrodesulfurization agent constant. When the temperature of the main body changes, it becomes difficult to keep the hydrodesulfurizing agent at an appropriate temperature.

JP 2012-240893 A JP 2013-23421 A JP 2003-160306 A JP 2007-15911 A JP 2012-176897 A JP 2010-58995 A

  When a hydrodesulfurizer is installed around the reformer, the hydrodesulfurizer is easily exposed to high temperatures. For example, since the reformer is usually used in a temperature range of 400 ° C. to 700 ° C., the hydrodesulfurizer becomes hot, and the hydrodesulfurization catalyst is thermally deteriorated so that the performance of the hydrogenation reaction and the adsorption reaction is improved. descend.

  In addition, when a hydrodesulfurizer is installed around the transformer, the hydrodesulfurizer temperature is lower than when installed around the reformer, but depending on the type of adsorbent, the adsorption capacity of hydrogen sulfide. Is small.

  The present invention has been made in view of such circumstances, and provides a hydrogen generator that can be reduced in size by improving the adsorption capacity of hydrogen sulfide by a hydrodesulfurizer compared to a conventional hydrogen generator. The purpose is to do.

  In the hydrogen generator of the present invention, a burner is installed in a cylindrical combustion chamber whose vertical direction is the cylinder axis direction, and a reforming catalyst packed bed and a shift catalyst packing are formed on the outer periphery of the combustion chamber from the lower stage side. A hydrogenation catalyst packed bed, a first adsorbent packed bed, and a second adsorbent packed bed are provided around the outer periphery, and a hydrogen absorbing catalyst packed bed is provided. The additive raw material gas is supplied to the hydrogenation catalyst packed bed, and sequentially, the first adsorbent packed bed, the second adsorbent packed bed, the reforming catalyst packed bed, the shift catalyst packed bed, and the selective oxidation catalyst In the hydrogen generator that passes through the packed bed, at least a part of the first adsorbent packed bed is disposed adjacent to the gas flow path (17a) leading from the reformed catalyst packed bed to the shift catalyst bed, A second adsorbent packed bed is disposed on the outer periphery of the shift catalyst packed bed. It is intended.

  It is preferable that preheating means for preheating the hydrogenated raw material gas by heat transfer from the first adsorbent packed layer or the raw material gas exiting the first adsorbent packed layer is provided.

  The reforming catalyst packed bed and the shift catalyst packed bed are separated from each other in the vertical direction, and the hydrogenation catalyst layer is disposed adjacent to the gas flow path (17a) leading from the reformed catalyst packed bed to the shift catalyst packed bed. It is preferable that

  In the present invention, it is preferable that the hydrogenation catalyst packed bed is provided on the outer periphery of the packed bed of the first adsorbent.

  In one aspect of the present invention, a packed bed of the first adsorbent is provided in the lower part of the hydrogen generator, and metal cylinders are installed in a concentric five-fold manner in the lower part of the apparatus. The second cylinder is the combustion chamber, and the passage between the first and second cylinders is an upward flow path for the combustion gas from the combustion chamber, and the second and third cylinders Between the reforming catalyst packed bed and the mixed gas flow path of the raw material gas and water vapor, the third and fourth cylinders serve as the rising flow path of the gas passing through the reforming catalyst packed bed. In addition, a hydrogenation catalyst packed bed is provided on the upper side between the fourth and fifth cylinders, and a first adsorbent packed bed is provided on the lower side.

  In another aspect of the present invention, a packed bed of the first adsorbent is provided in the lower part of the hydrogen generator, and six metal cylinders are installed concentrically in the lower part of the apparatus. The first cylinder from the combustion chamber is the combustion chamber, and between the first and second cylinders is a combustion gas rising passage from the combustion chamber. The second and third cylinders The reforming catalyst packed bed and the mixed gas flow path of the raw material gas and water vapor are provided between the bodies, and the gas rising path passing through the reforming catalyst packed bed is provided between the third and fourth cylinders. The first adsorbent packed bed is provided between the fourth and fifth cylinders, and the hydrogenation catalyst packed bed is provided between the fifth and sixth cylinders.

  In the present invention, a packed bed of the second adsorbent is provided in the middle part of the hydrogen generating apparatus in the vertical direction, and a metal cylinder is installed in a six-fold concentric manner in the middle part of the apparatus. The first cylinder from the combustion chamber is the combustion chamber, and between the first and second cylinders is a combustion gas rising passage from the combustion chamber. The second and third cylinders Between the bodies is an evaporation section, and between the third and fourth cylinders is a mixing chamber of water vapor and source gas and a source gas flow path, between the fourth and fifth cylinders It is preferable that a packed bed of the shift catalyst is provided, and a second adsorbent packed bed is provided between the fifth and sixth cylinders.

  In the present invention, the preheating means is provided so as to heat the hydrogenated raw material gas by heat transfer from the first adsorbent packed bed or the raw material gas exiting the first adsorbent packed bed. It is preferable.

  It is preferable that the hydrogenation catalyst has an optimum temperature of 250 to 400 ° C, the first adsorbent has an optimum temperature of 350 to 400 ° C, and the second adsorbent has an optimum temperature of 200 to 300 ° C.

  In the hydrogen generator of the present invention, a sulfur compound in a sulfur compound-containing raw material gas is reacted with hydrogen to decompose the sulfur compound, and the raw material gas containing the decomposition product is used as the first adsorbent and the second adsorbent. The decomposition product is adsorbed and removed sequentially, and then this raw material gas is subjected to a reforming reaction. According to the hydrogen generator of the present invention, the first adsorbent and the second adsorbent can be maintained at appropriate temperatures, respectively, and the adsorption capacity of hydrogen sulfide and the like by the hydrodesulfurizer is improved.

  The hydrogen generator of the present invention has the following advantages over those of Patent Documents 1-6.

  In Patent Documents 1 and 4, since all hydrodesulfurization agents are installed around the transformer and the CO remover, the outer diameter of the fuel processing device becomes large, and a large installation space is required when installing the fuel processing device in the fuel cell. Need. In the present invention, the hydrogen generating device and the first adsorbent are installed from the upstream portion of the reformer having a small outer diameter in front of the transformer, thereby reducing the outer diameter of the hydrogen generator and making it compact. It is possible.

  In Patent Document 2, the source gas is preheated on the outer periphery of the CO purifier. However, when a hydrodesulfurizing agent is installed on the outer periphery of the CO purifier, the structure becomes complicated. In addition, when heat transfer to the hydrodesulfurizer is performed from the reformer via a heat insulating material, the temperature of the hydrodesulfurization agent is easily affected by load fluctuations of the fuel processing device, and the hydrodesulfurization agent is It becomes difficult to keep the temperature. In the present invention, the structure can be simplified by performing preheating by heat transfer from the outer periphery of the first adsorbent.

  In Patent Document 3, the raw material gas is preheated on the outer periphery of the reformer. However, since the reformer is at a high temperature, the type of hydrodesulfurization agent and the place where it can be installed may be limited. In the present invention, by arranging the hydrogenation catalyst, the first adsorbent, and the second adsorbent separately, the appropriate temperature range of the hydrogenation catalyst and each adsorbent can be widened. In addition, in the case of a fuel processor specification (high S / C specification) in which the ratio of the amount of water vapor to the amount of raw material gas is high, the reaction is promoted by increasing the amount of water vapor and the temperature of the reformer can be lowered. Therefore, the appropriate temperature range of the hydrogenation catalyst and each adsorbent can be widened. These features make it possible to optimize the temperature of the hydrogenation catalyst and each adsorbent, reducing the amount of hydrodesulfurization catalyst mounted, making the hydrodesulfurizer compact, and thus reducing the cost of the hydrogen generator. It becomes.

  In Patent Document 5, since the heat is transferred from the reformer via the heat insulating material, it is difficult to keep the temperature of the hydrogenation catalyst and the adsorbent constant, especially when the flow rate changes due to load fluctuations. It becomes difficult to keep the adsorbent at an appropriate temperature. In the present invention, since heat is transferred to the hydrogenation catalyst and the adsorbent without using a heat insulating material, the temperatures of the hydrogenation catalyst and the adsorbent can be maintained appropriately.

It is a longitudinal cross-sectional view of the hydrogen generator which concerns on embodiment. It is a longitudinal cross-sectional view of the hydrogen generator which concerns on another embodiment.

  Hereinafter, embodiments will be described with reference to the drawings. FIG. 1 is a longitudinal sectional view of a hydrogen generator 1 according to the first embodiment.

  In this hydrogen generator 1, a reforming catalyst 4, a shift catalyst 5, a selective oxidation catalyst 6, an evaporator 8 and a desulfurizer 9 are arranged around the outer periphery of a combustion chamber 3 equipped with a burner 2. After the raw material gas is desulfurized by the desulfurizer 9, the steam from the evaporation section 8 is added and mixed, reformed by the reforming catalyst 4, passed through the shift catalyst 5 and the selective oxidation catalyst 6, and hydrogen is supplied from the hydrogen-containing gas outlet 14 b. The contained gas is taken out.

  The combustion chamber 3 is surrounded by a cylindrical first cylinder 11, and a burner 2 is inserted into the axial center portion from above. Combustion gas flows out from the gap between the first cylinder 11 and the bottom surface of the combustion chamber, and the flow path 11a between the first cylinder 11 and the second cylinder 12 surrounding the first cylinder 11 rises. And flows out from the gas discharge port 11b.

  A spiral rod 12 a is disposed between the second cylinder 12 and the third cylinder 13 surrounding the second cylinder 12, and an evaporation section 8 formed of a spiral passage is formed between the cylinders 12 and 13. Has been. Water is introduced into the evaporation section 8 from the water supply port 8a and is heated and evaporated while flowing through the spiral evaporation section 8 to become water vapor.

  The first cylinder 11 and the second cylinder 12 extend in the vertical direction over almost the entire height of the hydrogen generator 1, but the third cylinder 13 extends from the upper part of the second cylinder 12 to the second cylinder. 12 extends slightly below the middle in the vertical direction.

  A fourth cylinder 14 is provided so as to surround the upper part of the third cylinder 13, and a hydrogen-containing gas flow path 14 a is formed between the cylinders 13 and 14. The upper end of the flow path 14a communicates with the hydrogen-containing gas outlet 14b.

  A fifth cylinder 15 surrounding the second cylinder 12 is provided below the third cylinder 13. A sixth cylinder 16 is provided so as to surround the lower part of the third cylinder 13, the fifth cylinder 15, and the lower part of the second cylinder 12, and the lower part of the third cylinder 13 and the fifth A space between the cylinder 15 and the upper portion of the sixth cylinder 16 is a first mixing chamber 16a. A spiral rod 16b is installed between the fifth cylinder 15 and the sixth cylinder 16, and the lower part of the first mixing chamber 16a is formed in a spiral shape.

  A gap is formed between the lower end of the third cylinder 13 and the upper end of the fifth cylinder 15, and water vapor from the evaporator 8 flows into the first mixing chamber 16 a through this gap.

  A space between the second cylinder 12 and the fifth cylinder 15 is a second mixing chamber 15a. A spiral rod 15b is installed in the second mixing chamber 15a, and the second mixing chamber 15a is formed in a spiral shape.

  The second mixing chamber 15a communicates with the lower portion of the first mixing chamber 16a (below the spiral rod 16b) through an opening 15c provided in the fifth cylinder 15. A space between the lower end of the fifth cylinder 15 and the sixth cylinder 16 is closed by a partition wall 15d.

  The reforming catalyst 4 is filled between the lower part of the sixth cylinder 16 and the lower part of the second cylinder 12.

  A seventh cylinder 17 surrounds the lower part of the sixth cylinder 16, and a gas rising channel 17 a is formed between the cylinders 16 and 17. A spiral rod (not shown) may be installed on the upper part of the ascending channel 17a, and the channel 17a may be spiral. In addition, it is not necessary to install about the spiral bar of the upper part of the ascending flow path 17a.

  An eighth cylinder 18 surrounds the upper part of the seventh cylinder 17, and a space between the cylinders 17 and 18 is a catalyst and adsorbent filling chamber. The upper portion of the filling chamber is filled with a hydrogenation catalyst 24, and the lower portion is filled with a high temperature type first adsorbent 25. As this 1st adsorption agent, what has the adsorption | suction characteristic best in 350-400 degreeC is preferable. As such a first adsorbent, for example, a ZnO-based material and other metal oxides (for example, iron oxide and manganese oxide) can be used.

  A ninth cylinder 19 is installed so as to surround the outer periphery of the upper part of the sixth cylinder 16 and the lower part of the third cylinder 13. A space between the cylinders 16 and 13 and the cylinder 19 is a catalyst filling chamber. This catalyst filling chamber is divided into two upper and lower chambers by a horizontal partition plate 19a, the lower chamber is filled with the shift catalyst 5, and the upper chamber is filled with the selective oxidation catalyst 6.

  The lower part of the lower chamber filled with the shift catalyst 5 communicates with the ascending flow path 17a. An air supply port 19b is provided so as to blow air into the upper space of this chamber (the space between the shift catalyst 5 and the partition plate 19a).

  The upper catalyst filling chamber containing the selective oxidation catalyst 6 communicates with the flow path 14 a between the cylinders 13 and 14. The upper chamber containing the selective oxidation catalyst 6 and the lower chamber containing the shift catalyst 5 are communicated with each other through an opening 19c provided in the partition plate 19a.

  In FIG. 1, the eighth cylinder 18 and the ninth cylinder 19 have the same diameter, but may be different.

  A tenth cylindrical body 20 is provided in the ninth cylindrical body 19 so as to surround the outer periphery of the charging portion of the shift catalyst 5, and a low temperature type chamber is provided in the chamber between the ninth cylindrical body 19 and the tenth cylindrical body 20. The second adsorbent 27 is filled. As the second adsorbent, those having the best adsorption characteristics at 200 to 300 ° C. are preferable. As such a second adsorbent, for example, a CuZn-based one can be used.

  A source gas heating tube (pipe) 22 is spirally wound so as to surround the outer periphery of the lower portion of the first adsorbent 25 in the eighth cylindrical body 18. The tube 22 cools the raw material gas exiting the first adsorbent 25 by heat transfer, and heats the raw material gas entering the hydrogenation catalyst 24. The end of the tube 22 communicates with the upper part of the filling portion of the hydrogenation catalyst 24. The lower end of the filling portion of the first adsorbent 25 is connected to the lower end of the filling portion of the second adsorbent 27 in the tenth cylindrical body 20 via the pipe 26. The upper end of the filling portion of the second adsorbent 27 communicates with the first mixing chamber 16a via a pipe 28. The desulfurizer 9 includes the tube 22, a hydrogenation catalyst 24, adsorbents 25 and 27, pipes 26 and 28, and the like. As the hydrogenation catalyst 24, CuZn-based, Ni-based, CoMo-based, or the like is used.

  The cylinders 11 to 20 and the cylinder 21 described later are all made of metal such as stainless steel.

  In this embodiment, a packed bed of the first adsorbent 25 is provided in the lower part of the hydrogen generator 1, and the metal cylinders 11, 12, 16, 17, 18 is installed, the inside of the first cylinder 11 from the inside is the combustion chamber 3, and the rising flow path of the combustion gas from the combustion chamber 3 is between the first and second cylinders 11, 12. 11a, a packed bed of the reforming catalyst 4 and a mixed gas flow path of source gas and water vapor are provided between the second and third cylinders 12 and 16, and the third and fourth cylinders A gas flow path 17a that passes through the reforming catalyst packed bed is formed between 16 and 17, and a packed bed of the hydrogenation catalyst 24 is disposed on the upper side between the fourth and fifth cylindrical bodies 17 and 18. And a packed layer of the first adsorbent 25 is provided on the lower side.

  Further, in this embodiment, a packed bed of the second adsorbent 27 is provided in the middle part of the hydrogen generator 1 in the vertical direction, and the metal cylinder is concentrically arranged in the middle part of the apparatus. 11, 12, 13, 16, 19, and 20 are installed, the inside of the first cylinder 11 from the inside is the combustion chamber 3, and the combustion is between the first and second cylinders 11 and 12. Combustion gas ascending flow path 11a from the chamber 3 is formed between the second and third cylinders 12 and 13, and an evaporation section 8 is formed. The third and fourth cylinders 13 and 16 A first mixing chamber 16a for mixing the water vapor and the raw material gas is provided between them, a packed bed of the shift catalyst 5 is provided between the fourth and fifth cylinders 16 and 19, and the fifth And the sixth cylinders 19 and 20 are provided with a packed bed of the second adsorbent 27.

  Examples of the raw material gas processed by the hydrogen generator 1 include city gas, LP gas, and natural gas. Examples of the sulfur compound added as an odorant include mercaptans.

  As the reforming catalyst 4, Ru-based, Pt-based or the like is used. As the shift catalyst 5, a transition metal type such as Cu—Zn type or a noble metal type such as Pt, Ru type is used. As the CO selective oxidation catalyst 6, for example, a granular alumina carrier such as Pt or Ru is used. Those carrying a noble metal are used. As the fuel for the burner 2 that supplies reaction heat necessary for the steam reforming reaction, anode off-gas discharged from the fuel cell is used.

  In the hydrogen generator 1 configured as described above, a gas obtained by adding hydrogen to the raw material gas is supplied to the tube 22, and is preferably heated to 250 to 400 ° C. by heat transmitted through the cylinder 18, and then hydrogenated. In contact with the catalyst 24, the sulfur compound reacts with hydrogen and decomposes into hydrogen sulfide and the like. The hydrocarbon gas containing hydrogen sulfide or the like preferably passes through the packed bed of the first adsorbent 25 maintained at 350 to 400 ° C., and after most of the hydrogen sulfide is adsorbed and removed, from the pipe 26, Preferably, it is guided to the packed bed of the second adsorbent 27 maintained at 200 to 300 ° C., and the remaining hydrogen sulfide is adsorbed and removed.

  The hydrocarbon gas from which the sulfur compound has been removed is introduced from the pipe 28 into the first mixing chamber 16a.

  The water supplied from the water supply port 8a is heated to flow into the water vapor while flowing down the evaporating section 8 composed of a spiral space (flow path) partitioned by the spiral rod 12a. This water vapor flows into the first mixing chamber 16a and is added to and mixed with the hydrocarbon gas from the pipe 28.

  The water vapor and the hydrocarbon gas are mixed while flowing spirally along the spiral rod 16b in the first mixing chamber 16a, and then flow into the second mixing chamber 15a from the opening 15c and spiral along the spiral rod 15b. Flow and mix thoroughly. This mixed gas of hydrocarbon gas and water vapor passes through the packed bed of the reforming catalyst 4, and by the action of the reforming catalyst 4, the hydrocarbon and water vapor react to produce hydrogen, carbon dioxide, carbon monoxide, A reformed gas containing methane, water vapor and the like is generated.

  The reformed gas goes around the lower end of the cylindrical body 16, rises in the ascending flow path 17 a, passes through the packed bed of the shift catalyst 4, and carbon monoxide contained in the reformed gas is reformed by the shift catalyst 5. It reacts with water vapor in the gas and is reduced to a concentration of about 1% or less.

  The reformed gas that has passed through the packed bed of the shift catalyst 4 is mixed with the air supplied from the air supply port 19b, and the carbon monoxide is selectively oxidized by the selective oxidation catalyst 6 to a CO concentration of about 10 ppm or less. A reduced hydrogen-containing gas is produced. The generated hydrogen-containing gas is taken out from the hydrogen-containing gas outlet 14b through the flow path 14a and supplied to the fuel cell. A part of this hydrogen-containing gas is added to the raw material gas (hydrocarbon gas) facing the tube 22.

  In this embodiment, the hydrogenation catalyst 24 is disposed between the packed bed of the reforming catalyst 4 and the packed bed of the shift catalyst 5, and is maintained at a temperature of 250 to 400 ° C. The reaction proceeds efficiently.

  In addition, the first adsorbent 25 is disposed at the outer peripheral position of the reforming catalyst 4, and the tube 22 is disposed at the outer periphery thereof, and the first adsorbent 25 maintained at a temperature of 350 to 400 ° C. In particular, the raw material gas is preheated by heat transfer from the raw material gas exiting the first adsorbent 25. Further, the second adsorbent 27 is disposed on the outer periphery of the shift catalyst 5, and the raw material gas exiting the first adsorbent 25 is cooled by the pipe 26 and maintained at a temperature of 200 to 300 ° C. Hydrogen sulfide is often adsorbed.

  In this embodiment, the heat transfer area of the evaporator 8 is preferably increased. Thereby, the water evaporation capability is improved, and the fuel processor specification (high S / C specification) in which the ratio of the water vapor amount to the raw material gas amount is high can be achieved. By increasing the amount of water vapor, the reforming reaction is promoted, the temperature of the reforming catalyst can be lowered, the temperature of the hydrogenation catalyst 24 is 250-400 ° C., and the temperature of the first adsorbent 25 is 350- It becomes easy to maintain at 400 ° C.

  In this embodiment, the packed bed of the first adsorbent 25 is provided below the packed bed of the hydrogenation catalyst 24, the temperature of the hydrogenated catalyst 24 can be easily controlled, and the structure is simplified. I can do it.

  In the embodiment of FIG. 1, the filling chamber between the cylinders 17 and 18 is filled with the hydrogenation catalyst and the adsorbent 25. However, in the present invention, the hydrogen generation according to the second embodiment shown in FIG. As in the apparatus 1 ′, an eleventh cylinder 21 may be provided on the outer periphery of the cylinder 18, and the filling chamber between the cylinders 18 and 21 may be filled with the hydrogenation catalyst 24. The filling chamber between the cylinders 17 and 18 is filled only with the adsorbent 25.

  The vertical length of the cylinder 21 is shorter than that of the cylinder 18. The upper end of the cylinder 21 is the same as the upper end of the cylinder 18, but may be slightly lower. The lower end of the cylinder 21 is higher than the lower end of the cylinder 18. The lower part of the cylinder 18 is not surrounded by the cylinder 21, and a tube 22 is wound around the lower part of the cylinder 18.

  The end of the tube 22 is connected to the lower end of the cylindrical body 21 and communicates with the filling chamber of the hydrogenation catalyst 24. The filling chamber between the cylinders 17 and 18 and the filling chamber between the cylinders 18 and 21 are communicated with each other through an opening 18 b provided in the upper part of the cylinder 18. The hydrogenated source gas heated through the tube 22 comes into contact with the hydrogenation catalyst 24 between the cylinders 18 and 21, and then passes through the opening 18b to fill the adsorbent 25 between the cylinders 17 and 18. be introduced.

  In this hydrogen generator 1 ′, metal cylinders 11, 12, 16, 17, 18, and 21 are installed in a concentric manner in the lower part of the apparatus 1 ′, and the inside of the first cylinder 11 from the inside is formed. Combustion chamber 3, and between the first and second cylinders 11, 12 is a combustion gas rising passage 11 a from the combustion chamber 3, and the second and third cylinders 12. , 16 is provided with a packed bed of the reforming catalyst 4, and the third and fourth cylinders 16, 17 constitute a gas ascending flow path 17a passing through the reforming catalyst packed bed. A packed bed of the first adsorbent 25 is provided between the fifth and fifth cylinders 17, 18, and a packed bed of the hydrogenation catalyst 24 is provided between the fifth and sixth cylinders 18, 21. ing.

  Other configurations of the embodiment of FIG. 2 are the same as those of FIG. 1, and the same reference numerals denote the same parts.

  In this embodiment, the hydrogenation catalyst 24 is maintained at 250 to 400 ° C. by the heat transferred from the first adsorbent 25. The first adsorbent 25 is maintained at 350 to 400 ° C., and the low temperature adsorbent 27 is maintained at 200 to 300 ° C.

  In this embodiment, the height of the packed bed of the hydrogenation catalyst 24 and the first adsorbent 25 can be made longer than that in the embodiment of FIG. 1, and the L of the hydrogenation catalyst 24 and the first adsorbent 25 can be increased. / D (catalyst layer length / catalyst layer cross-sectional area ratio) can be increased, gas blow-off can be prevented, and sulfur compound hydrogenation and adsorption reactions can be performed more efficiently.

  In the embodiment shown in FIGS. 1 and 2, the tube 22 is wound around the outer periphery of the cylindrical body 18, but the tube 22 may be disposed in the packed bed of the first adsorbent 25. Although the tube 22 is used in the above embodiment, a jacket surrounding the outer periphery of the cylinder 18 may be provided, and the hydrogenated source gas may be passed through the jacket.

  Each of the above embodiments is an example of the present invention, and the present invention may be configured other than illustrated.

DESCRIPTION OF SYMBOLS 1,1 'Hydrogen generator 2 Burner 3 Combustion chamber 4 Reforming catalyst 5 Shifting catalyst 6 Selective oxidation catalyst 8 Evaporating part 11-21 Cylindrical body 15a 2nd mixing chamber 16a 1st mixing chamber 19b Air supply port 24 Hydrogenation catalyst 25 High temperature type first adsorbent 27 Low temperature type second adsorbent

Claims (9)

A burner is installed in a cylindrical combustion chamber whose vertical direction is the cylinder axis direction, and a reforming catalyst packed bed, a shift catalyst packed bed, and a selective oxidation catalyst packed bed are formed around the outer periphery of the combustion chamber from the lower stage side. Is installed, and further, a hydrogenation catalyst packed bed, a first adsorbent packed bed, and a second adsorbent packed bed are provided on the outer periphery,
A hydrogenation source gas is supplied to the hydrogenation catalyst packed bed, and in turn, a first adsorbent packed bed, a second adsorbent packed bed, a reforming catalyst packed bed, a shift catalyst packed bed, and a selective oxidation catalyst In the hydrogen generator that passes through the packed bed of
At least a portion of the first adsorbent packed bed is disposed adjacent to a gas flow path leading from the reforming catalyst packed bed to the shift catalyst bed;
The second adsorbent packed bed is disposed on the outer periphery of the shift catalyst packed bed ;
A hydrogen generating apparatus , comprising preheating means for preheating the hydrogenated raw material gas by heat transfer from the first adsorbent packed bed . 2. The hydrogenation catalyst filling according to claim 1 , wherein the reforming catalyst filling layer and the shift catalyst filling layer are separated from each other in the vertical direction, and adjacent to the gas flow path leading from the reforming catalyst filling layer to the shift catalyst layer. A hydrogen generator characterized in that a layer is arranged. 2. The hydrogen generation apparatus according to claim 1 , wherein the hydrogenation catalyst packed bed is provided on an outer periphery of the packed bed of the first adsorbent. 3. In Claim 2 , a packed bed of the first adsorbent is provided in the lower part of the hydrogen generator, and metal cylinders are installed in five layers concentrically in the lower part of the apparatus.
The first cylinder from the inside is the combustion chamber,
Between the first and second cylinders is an upward flow path for the combustion gas from the combustion chamber,
Between the second and third cylinders, the reforming catalyst packed bed and a mixed gas flow path of the raw material gas and water vapor are provided,
Between the third and fourth cylinders is an upward flow path for the gas that has passed through the reforming catalyst packed bed,
A hydrogen generating apparatus, wherein a hydrogenation catalyst packed bed is provided on the upper side between the fourth and fifth cylinders, and a first adsorbent packed bed is provided on the lower side. In Claim 3 , the packed bed of the 1st adsorbent is provided in the lower part of the hydrogen generating device, and metal cylinders are installed in six layers concentrically in the lower part of the device.
The first cylinder from the inside is the combustion chamber,
Between the first and second cylinders is an upward flow path for the combustion gas from the combustion chamber,
Between the second and third cylinders, the reforming catalyst packed bed and a mixed gas flow path of the raw material gas and water vapor are provided,
Between the third and fourth cylinders is an upward flow path for the gas that has passed through the reforming catalyst packed bed,
A first adsorbent packed bed is provided between the fourth and fifth cylinders;
A hydrogen generating apparatus, wherein a hydrogenation catalyst packed bed is provided between the fifth and sixth cylinders. Installation according to claim 4 or 5, the filling layer of the second adsorbent in the middle portion in the vertical direction is provided in the hydrogen generating apparatus, a metallic cylindrical body to sextuple concentrically in said apparatus middle portion And
The first cylinder from the inside is the combustion chamber,
Between the first and second cylinders is an upward flow path for the combustion gas from the combustion chamber,
The evaporation part is between the second and third cylinders,
Between the third and fourth cylinders is a mixing chamber of water vapor and source gas and a source gas flow path,
A packed bed of the shift catalyst is provided between the fourth and fifth cylinders;
A hydrogen generating apparatus, wherein a second adsorbent packed bed is provided between the fifth and sixth cylinders. In claims 4 to any one of 6, the preheating means, it is provided to heat the hydrogenation feed gas by heat transfer from the first gas exiting the packed bed of adsorbent A hydrogen generator characterized by this. In any one of claims 1 to 7, wherein the hydrogenation catalyst is a temperature optimum 250 to 400 ° C., the first adsorbent is optimal temperature is 350 to 400 ° C., the second adsorbent Is a hydrogen generator characterized in that the optimum temperature is 200 to 300 ° C.   A burner is installed in a cylindrical combustion chamber whose vertical direction is the cylinder axis direction, and a reforming catalyst packed bed, a shift catalyst packed bed, and a selective oxidation catalyst packed bed are formed around the outer periphery of the combustion chamber from the lower stage side. Is installed, and further, a hydrogenation catalyst packed bed, a first adsorbent packed bed, and a second adsorbent packed bed are provided on the outer periphery,
  A hydrogenation source gas is supplied to the hydrogenation catalyst packed bed, and in turn, a first adsorbent packed bed, a second adsorbent packed bed, a reforming catalyst packed bed, a shift catalyst packed bed, and a selective oxidation catalyst In the hydrogen generator that passes through the packed bed of
  At least a portion of the first adsorbent packed bed is disposed adjacent to a gas flow path leading from the reforming catalyst packed bed to the shift catalyst bed;
  The second adsorbent packed bed is disposed on the outer periphery of the shift catalyst packed bed;
  The hydrogen generating apparatus, wherein the hydrogenation catalyst packed bed is provided on the outer periphery of the packed bed of the first adsorbent.

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