Hydrogen generation device and manufacturing method thereof

Abstract

To provide a hydrogen generator capable of efficiently performing an operation of holding a CO reduction catalyst even when an outer diameter of a modification part is larger than an outer diameter of an evaporation part, according to the present disclosure.SOLUTION: A hydrogen generator according to the present disclosure is a hydrogen generator in which a CO reduction part is arranged between a portion whose evaporation part on a first partition wall is constituted, and whose evaporation and modification parts are arranged between a heating part partition wall and a first partition wall surrounding the heating part partition wall, and above a second partition wall surrounding the portion; and an outer diameter of a portion whose modification part on the first partition wall is constituted is larger than an outer diameter of the portion whose evaporation part on the first partition wall is constituted. A heat-transfer buffer cylinder is provided onto the first partition wall in such a manner that a space is interposed between the evaporation part and the CO reduction part, and an outer diameter of a portion where a constituent member of the CO reduction part of the heat-transfer buffer cylinder is arranged is made to be larger than the outer diameter of the portion whose modification part on the first partition wall is constituted.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present disclosure relates to a hydrogen generation device and a method for producing the same. [Background technology]

[0002] Patent Document 1 discloses a hydrogen generation device in which an evaporator section is configured on the upper side and a reformer section is configured on the lower side between a heating section partition and a first partition surrounding the outer periphery of the heating section partition, a CO reduction section is configured between the first partition and a second partition surrounding the outer periphery of the first partition, and the outer diameter of the part of the first partition where the reformer section is configured is larger than the outer diameter of the part of the first partition where the evaporator section is configured. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2018-118863 A Summary of the Invention [Problem to be solved by the invention]

[0004] The present disclosure provides a hydrogen generation device that can efficiently load a CO reduction catalyst and hold it in a predetermined position even if the outer diameter of the reforming section is larger than the outer diameter of the evaporation section. [Means for solving the problem]

[0005] In the hydrogen generation device of the present disclosure, an evaporator section and a reformer section are arranged between a cylindrical heating section partition wall having a central axis in the vertical direction and a cylindrical first partition wall having a central axis in the vertical direction and surrounding the outer periphery of the heating section partition wall, and a CO reduction section is arranged between a portion of the first partition wall where the evaporator section is configured and a cylindrical second partition wall having a central axis in the vertical direction and surrounding the outer periphery of the evaporator section.

[0006] Furthermore, a return flow path is formed between the portion of the first partition where the reforming section is configured and below a bottomed, cylindrical second partition having a vertical central axis, an upper end connected to the lower end on the second partition, and surrounding the outer periphery and bottom of the reforming section, and the outer diameter of the portion of the first partition where the reforming section is configured is larger than the outer diameter of the portion of the first partition where the evaporating section is configured.

[0007] The evaporator is configured to heat the raw material gas and water with heat transmitted through the heating section partition to evaporate the water, and the reformer is configured below the evaporator to generate a primary hydrogen-containing gas containing carbon monoxide through a reforming reaction from a mixed gas of the raw material gas and water vapor with heat transmitted through the heating section partition.

[0008] The CO reduction section is configured to generate a secondary hydrogen-containing gas by reducing the concentration of carbon monoxide contained in the primary hydrogen-containing gas flowing out from the reforming section through a shift reaction.

[0009] The return flow passage is a flow passage that redirects the flow of the primary hydrogen-containing gas that flows downward from the reforming section and guides it upward to the CO reduction section.

[0010] One feature of the hydrogen generation device according to the present disclosure is that a heat transfer buffer tube is provided between the portion of the first partition where the evaporator portion is configured and the CO reduction portion.

[0011] This heat transfer buffer tube is a member configured so that a space is formed between the evaporator section and the CO reduction section, has a central axis in the vertical direction, and has upper and lower ends bent inwardly and fixed to the outer peripheral surface of the portion of the first partition that forms the evaporator section.

[0012] The CO reduction section includes a CO reduction catalyst, a CO reduction section lower shelf plate, and a CO reduction section upper shelf plate. The CO reduction catalyst is a granular catalyst filled between the second partition and the heat transfer buffer tube. The CO reduction section lower shelf plate is a shelf plate arranged between the second partition and the heat transfer buffer tube so as to support the CO reduction catalyst from below, and the CO reduction section upper shelf plate is a shelf plate arranged between the second partition and the heat transfer buffer tube so as to cover the CO reduction catalyst from above.

[0013] The lower shelf plate of the CO reduction section and the upper shelf plate of the CO reduction section are doughnut-shaped and have ventilation holes smaller than the particle diameter of the CO reduction catalyst.

[0014] Another feature of the hydrogen generation device in the present disclosure is that the outer diameter of the portion of the heat transfer buffer tube where the CO reduction catalyst, the lower shelf plate of the CO reduction section, and the upper shelf plate of the CO reduction section are arranged is made larger than the outer diameter of the portion of the first partition where the reforming section is configured. Effect of the Invention

[0015] The hydrogen generation device of the present disclosure provides the following effects by providing a heat transfer buffer tube in the first partition so as to provide a space between the evaporation section and the CO reduction section, and by making the outer diameter of the portion of the heat transfer buffer tube where the components of the CO reduction section are arranged larger than the outer diameter of the portion of the first partition where the reforming section is arranged.

[0016] In other words, the hydrogen generation device can be manufactured to a state where the bottom of the second partition is not joined to the lower end of the top of the second partition, the CO reduction section upper shelf plate has been attached, but the CO reduction catalyst and the CO reduction section lower shelf plate have not been placed, and after filling the CO reduction catalyst with the hydrogen generation device in a state where it is inverted upside down (upside down) with respect to the direction of gravity when in use, the CO reduction catalyst can be held between the CO reduction section upper shelf plate and the CO reduction section lower shelf plate.

[0017] Therefore, even if the outer diameter of the reforming section is larger than the outer diameter of the evaporation section, the operation of filling the reforming catalyst and holding it in a designated position can be performed continuously and efficiently, along with the operation of filling the reforming catalyst and holding it in a designated position, thereby providing a hydrogen generation device that can reduce manufacturing costs.

[0018] In addition, the heat transfer buffer tube creates a space between the evaporation section and the CO reduction section, which prevents the CO reduction catalyst packed on the inner side from being locally cooled by heat exchange with the evaporation section (causing temperature unevenness in the CO reduction catalyst).This makes it easier to keep the entire CO reduction catalyst at a temperature suitable for the shift reaction, making it possible to reduce the carbon monoxide concentration in the secondary hydrogen-containing gas more than before and to reduce the amount of CO reduction catalyst packed in more than before. [Brief description of the drawings]

[0019] [Figure 1] Schematic diagram of a hydrogen generation device according to a first embodiment [Diagram 2] FIG. 1 is a schematic diagram showing three manufacturing steps related to catalyst loading in a hydrogen generation device according to a first embodiment. [Diagram 3] Schematic diagram of a hydrogen generating device according to another embodiment. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0020] (The knowledge and other information that formed the basis of this disclosure) At the time when the inventors arrived at the present disclosure, an evaporator section was configured on the upper side and a reformer section was configured on the lower side between the heating section partition wall and a first partition wall surrounding the outer periphery of the heating section partition wall, a CO reduction section was configured between the first partition wall and a second partition wall surrounding the outer periphery of the first partition wall, and the outer diameter of the part of the first partition wall where the reformer section was configured (the part surrounding the reforming catalyst) was There was technology for a hydrogen generation device with a multi-cylinder structure that was larger than the outer diameter of the part it was made of.

[0021] However, in conventional hydrogen generation devices, the reforming section is located below the evaporator section and the outer diameter of the reforming section is larger than that of the evaporator section. As a result, when loading the catalyst in the manufacturing process, the hydrogen generation device is turned upside down from the vertical direction when in use, loaded with the reforming catalyst, and the reforming catalyst is held in the designated position by sandwiching it between shelf boards from above and below, and then the device is turned from the upside-down state to the orientation when in use, loaded with the CO reduction catalyst, and the CO reduction catalyst is held in the designated position by sandwiching it between shelf boards from above and below.

[0022] This meant that there were many steps required for loading the reforming catalyst and CO reduction catalyst, which resulted in low efficiency.

[0023] Under these circumstances, the inventors came up with the idea that the catalyst loading process could be simplified if the hydrogen generation device was turned upside down from the vertical direction used during use and the loading operations of the reforming catalyst and CO reduction catalyst were carried out continuously.

[0024] However, to realize this idea, the inventors discovered a problem in that, when, after filling the CO reduction catalyst, a lower shelf plate that supports the CO reduction catalyst from below is introduced between the first and second partitions, the inner diameter of the lower shelf plate that supports the CO reduction catalyst is smaller than the outer diameter of the part of the first partition that constitutes the reforming section (the part that surrounds the reforming catalyst), and therefore the part of the first partition that constitutes the reforming section (the part that surrounds the reforming catalyst) gets in the way, making it impossible to introduce the lower shelf plate that supports the CO reduction catalyst to the position of the CO reduction catalyst.In order to solve this problem, the subject matter of the present disclosure has been formed.

[0025] Therefore, the present disclosure provides a water hydrogen generation device that provides a space between the evaporation section and the CO reduction section by providing a heat transfer buffer tube in the first partition and making the outer diameter of the portion of the heat transfer buffer tube where the components of the CO reduction section are arranged larger than the outer diameter of the portion of the first partition where the reforming section is arranged, thereby enabling the operation of filling the CO reduction catalyst and holding it in a predetermined position to be performed continuously and efficiently, along with the operation of filling the reforming catalyst and holding it in a predetermined position, thereby reducing manufacturing costs.

[0026] Hereinafter, the embodiments will be described in detail with reference to the drawings. However, more detailed description than necessary may be omitted. For example, detailed description of already well-known matters or duplicate description of substantially the same configuration may be omitted.

[0027] It should be noted that the accompanying drawings and the following description are provided to enable those skilled in the art to fully understand the present disclosure, and are not intended to limit the subject matter described in the claims.

[0028] (Embodiment 1) Hereinafter, the first embodiment will be described with reference to FIGS.

[0029] [1-1. Configuration] 1 and 2, the hydrogen generation apparatus 100 has a heating section 120, an evaporating section 121, a reforming section 122, a CO reduction section 123, a CO reduction section upper shelf plate 124, a CO reduction section lower shelf plate 125, a combustion tube 130, a heating section partition 131, a first partition 132, a second partition lower section 133, a second partition upper section 134, a heat transfer buffer tube 135, a combustion exhaust gas flow path 140, and a return flow path 141.

[0030] The heating unit 120 is disposed on the inner periphery side of a combustion tube 130 having a central axis in the vertical direction. The heating unit 120 includes a burner that burns combustible gas mixed with air and discharges combustion exhaust gas, a gas supply pipe that supplies the combustible gas to the burner, and a combustion air supply pipe that supplies combustion air to the burner. The burner of the heating unit 120 is configured to form a downward flame.

[0031] The combustible gas can be a raw material gas (city gas or LP gas), and when the hydrogen generation device 100 supplies a hydrogen-containing gas to the fuel cell as a fuel gas, the fuel gas (anode off-gas) discharged from the fuel cell without being used in the fuel cell can be used.

[0032] The combustion tube 130 is arranged coaxially with the heating section 120, and is a component that causes the combustion exhaust gas to flow vertically downward on the inner side of the combustion tube 130, and causes the combustion exhaust gas to flow vertically upward on the outer side of the combustion tube 130 (combustion exhaust gas flow path 140 formed between the combustion tube 130 and the heating section partition wall 131).

[0033] The lower end of the combustion tube 130 is located vertically lower than the lower end of the reforming section 122, and vertically higher than the bottom of a cylindrical heating section partition 131 that is arranged coaxially with the combustion tube 130 and surrounds the combustion tube 130.

[0034] The hydrogen generation apparatus 100 is configured such that the combustion exhaust gas generated by the combustion of the burner in the heating section 120 flows downward along the inner surface of the combustion tube 130, then turns back upward through the gap between the bottom of the heating section partition 131 and the lower end of the combustion tube 130, and exchanges heat with the reforming section 122 and then with the evaporating section 121 in the combustion exhaust gas flow path 140 formed between the combustion tube 130 and the heating section partition 131, and is discharged to the outside of the hydrogen generation apparatus 100 from a combustion exhaust gas outlet pipe provided at the upper part of the heating section partition 131.

[0035] The heating section partition 131 is a cylindrical metal component with a bottom, whose inner diameter is larger than the outer diameter of the combustion cylinder 130, and which is arranged so as to surround the outer peripheral surface of the combustion cylinder 130 and be coaxial with the combustion cylinder 130. The heating section partition 131 is a cylindrical metal component with a bottom that forms a combustion exhaust gas flow path 140 between the combustion cylinder 130 and the bottom of the combustion cylinder 130, and there is a gap between the bottom of the heating section partition 131 and the lower end of the combustion cylinder 130 through which the combustion exhaust gas flows.

[0036] The first partition wall 132 is a metal member whose inner diameter is larger than the outer diameter of the heating unit partition wall 131, and which is arranged so as to surround the outer circumferential surface of the heating unit partition wall 131 and be coaxial with the heating unit partition wall 131. A spirally bent rod material is arranged between the first partition wall 132 and the heating unit partition wall 131 to allow the raw material gas containing hydrocarbon and water to flow in a spiral shape, and a reforming catalyst 150 is filled below the spiral rod material for producing a primary hydrogen-containing gas (hydrogen-containing gas containing carbon monoxide) from a mixed gas of the raw material gas and water vapor through a reforming reaction.

[0037] The area between the first partition 132 and the heating section partition 131 where the spiral rod is arranged becomes the evaporation section 121 through which the raw material gas containing hydrocarbons and water pass while being heated by the heat transmitted from the heating section partition 131, and the area filled with the reforming catalyst 150 becomes the reforming section 122.

[0038] A supply pipe for supplying raw material gas and water to the evaporation section 121 is connected to a portion of the first partition 132 above where the spiral bar is disposed.

[0039] The first partition wall 132 is configured such that the diameter of the portion of the first partition wall 132 where the reforming section 122 is configured is larger than the diameter of the portion of the first partition wall where the evaporation section 121 is configured.

[0040] The second partition lower portion 133 is a cylindrical metal member with a bottom, the inner diameter of which is larger than the outer diameter of the portion of the first partition 132 where the reforming section 122 is configured, the second partition lower portion 133 is disposed so as to surround the outer circumferential surface of the portion of the first partition 132 where the reforming section 122 is configured and be coaxial with the first partition 132, and forms a return flow passage 141 between the portion of the first partition 132 where the reforming section 122 is configured, Between the bottom of the second partition lower portion 133 and the lower end of the first partition wall 132, there is a gap through which the primary hydrogen-containing gas flows.

[0041] The bottom of the second partition lower part 133 is larger than the bottom of the heating section partition wall 131, and is configured to be located lower than the bottom of the heating section partition wall 131. The diameter of the upper end part of the second partition lower part 133 is configured to be larger than the diameter of the part other than the upper end part of the second partition lower part 133 so that the upper end of the second partition lower part 133 can be joined to the lower end part of the second partition upper part 134.

[0042] The heat transfer buffer cylinder 135 is a cylindrical member whose upper and lower ends are bent inwardly and fixed to the outer circumferential surface of the portion of the first partition wall 132 where the evaporation section 121 is formed. The heat transfer buffer cylinder 135 is disposed so as to surround the outer circumferential surface of the portion of the first partition wall 132 where the evaporation section 121 is formed and to be coaxial with the first partition wall 132.

[0043] It is desirable to connect at least one of the upper and lower ends of the heat transfer buffer tube 135 to the first partition 132 as airtight as possible so that the amount of primary hydrogen-containing gas that flows out of the hydrogen generation apparatus 100 by passing between the heat transfer buffer tube 135 and the first partition 132 without passing through the CO reduction section 123 does not exceed the allowable amount.

[0044] The inner diameter of the heat transfer buffer cylinder 135 between the upper end and the lower end is larger than the outer diameter of the portion of the first partition wall 132 where the evaporator section 121 is configured, and a space is formed between the inner circumferential surface of the heat transfer buffer cylinder 135 and the inner circumferential surface of the portion of the first partition wall 132 where the evaporator section 121 is configured. In addition, the outer diameter of the portion of the heat transfer buffer cylinder 135 between the upper end and the lower end is larger than the outer diameter of the portion of the first partition wall 132 where the reformer section 122 is configured.

[0045] The heat transfer buffer tube 135 is a component for forming a space that prevents the components adjacent to the outer periphery of the heat transfer buffer tube 135 or the gas flowing along the outer periphery of the heat transfer buffer tube 135 from being locally cooled by heat exchange with the evaporation section 121.

[0046] The second partition 134 is a metal component whose inner diameter is larger than the outer diameter of the heat transfer buffer tube 135, and which is arranged so as to surround the portion of the first partition 132 where the evaporation section 121 is formed and the outer peripheral surface of the heat transfer buffer tube 135 and is coaxial with the first partition 132 (heat transfer buffer tube 135), and which constitutes the CO reduction section 123 between itself and the heat transfer buffer tube 135.

[0047] The CO reduction section 123 is configured to generate a secondary hydrogen-containing gas by reducing the concentration of carbon monoxide contained in the primary hydrogen-containing gas flowing out from the reforming section 122 through a shift reaction, and is equipped with a CO reduction catalyst 151, a CO reduction section lower shelf plate 125, and a CO reduction section upper shelf plate 124.

[0048] The CO reduction catalyst 151 is a granular Cu-Zn-based catalyst having a diameter of 2 to 3 mm, which is filled between the second partition top 134 and the heat transfer buffer cylinder 135 .

[0049] The CO reduction section lower shelf 125 is a shelf arranged between the second partition top 134 and the heat transfer buffer tube 135 so as to support the CO reduction catalyst 151 from below, and the CO reduction section upper shelf 124 is a shelf arranged between the second partition top 134 and the heat transfer buffer tube 135 so as to cover the CO reduction catalyst 151 from above.

[0050] The CO reduction section lower shelf plate 125 and the CO reduction section upper shelf plate 124 are doughnut-shaped and have vent holes with a diameter of 1 mm, which is smaller than the particle diameter of the CO reduction catalyst 151 .

[0051] The heat transfer buffer tube 135 forms a space that prevents the CO reduction catalyst 151 filled between the outer peripheral surface of the heat transfer buffer tube 135 and the inner peripheral surface of the second partition wall 134 from being locally cooled by heat exchange with the evaporation section 121 (occurrence of temperature unevenness in the CO reduction catalyst 151).

[0052] The heat transfer buffer tube 135 forms a space between the inner circumferential surface of the heat transfer buffer tube 135 and the inner circumferential surface of the portion of the first partition 132 where the evaporation section 121 is configured, and this space suppresses heat transfer (heat exchange) between the evaporation section 121 and the CO reduction section 123.

[0053] The second partition upper portion 134 is provided with an outlet pipe for discharging (supplying) the secondary hydrogen-containing gas to the outside of the hydrogen generation apparatus 100, above the portion of the second partition upper portion 134 where the CO reduction portion 123 is configured.

[0054] Between the second partition 134 and the heat transfer buffer tube 135 or between it and the first partition 132 whose outer peripheral surface is not covered by the heat transfer buffer tube 135, there is also formed a flow path that guides the primary hydrogen-containing gas that has passed through the return flow path 141 to the CO reduction section lower shelf plate 125 (CO reduction section 123), and a flow path that guides the secondary hydrogen-containing gas that has flowed out from the CO reduction section upper shelf plate 124 (CO reduction section 123) to the outlet pipe.

[0055] The reforming section 122 includes a reforming catalyst 150 filled between the first partition wall 132 and the heating section partition wall 131, a reforming section lower shelf plate 127, and a reforming section upper shelf plate 126.

[0056] The reforming section lower shelf plate 127 is a shelf plate arranged between the first partition wall 132 and the heating section partition wall 131 so as to support the reforming catalyst 150 from below, and the reforming section upper shelf plate 126 is a shelf plate arranged between the first partition wall 132 and the heating section partition wall 131 so as to cover the reforming catalyst 150 from above. The reforming section lower shelf plate 127 and the reforming section upper shelf plate 126 are doughnut-shaped and have vent holes smaller than the particle diameter of the reforming catalyst 150 formed therein.

[0057] (Hydrogen production equipment manufacturing process) In FIG. 2, the method for producing a hydrogen generator 100 includes a catalyst loading preparation step 101, a catalyst loading step 102, and a catalyst sealing step 103.

[0058] The catalyst filling preparation process 101 is a process of manufacturing a hydrogen generation apparatus and then inverting the top and bottom of the hydrogen generation apparatus with respect to the direction of gravity when it is used (turning it upside down) until the following state is reached: the second lower partition 133 has not yet been joined to the lower end of the second upper partition 134 that has already been attached to the first partition 132; the reforming section upper shelf plate 126 has been attached between the heating section partition 131 and the first partition 132, but the reforming section lower shelf plate 127 has not yet been positioned between the heating section partition 131 and the first partition 132; and the CO reduction section upper shelf plate 124 has been attached between the second upper partition 134 and the heat transfer buffer tube 135, but the CO reduction section lower shelf plate 125 has not yet been positioned between the second upper partition 134 and the heat transfer buffer tube 135, so that the reforming catalyst 150 and the CO reduction catalyst 151 can be filled in a later process.

[0059] The catalyst filling process 102 is a process in which, after the catalyst filling preparation process 101 is completed, the space surrounded by the heating section partition 131, the first partition 132, and the reforming section upper shelf plate 126 is filled with the reforming catalyst 150, and the space surrounded by the second partition top 134, the heat transfer buffer tube 135, and the CO reduction section upper shelf plate 124 is filled with the CO reduction catalyst 151.

[0060] The catalyst sealing step 103 includes, after the catalyst filling step 102 is completed, an operation of introducing the reforming section lower shelf 127 from above in the vertical direction toward the portion filled with the reforming catalyst 150 and placing it in a position where it abuts against the upper end of the portion filled with the reforming catalyst 150, and an operation of introducing the CO reduction section lower shelf 125 from above in the vertical direction toward the portion filled with the CO reduction catalyst 151 and placing the CO reduction section lower shelf 125 in a position where it abuts against the upper end of the portion filled with the CO reduction catalyst 151. and installing the catalyst 151 at a position where it abuts against the upper end of the portion filled with the catalyst 151.

[0061] [1-2. Operation] The operation and function of the hydrogen generation device 100 configured as above will be described below.

[0062] (Operation of hydrogen generator) In the hydrogen generation apparatus 100, in order to obtain the required amount of hydrogen, raw material gas and water are supplied in an appropriate ratio from a supply pipe to the evaporation section 121. The supplied water flows along the spiral flow path of the evaporation section 121 and becomes water vapor due to the heat (including the heat of the combustion exhaust gas) of the heating section 120 transmitted through the heating section partition wall 131, and is mixed with the raw material gas.

[0063] The mixed gas of the raw material gas and steam is supplied to the reforming section 122, and a steam reforming reaction is carried out by the reforming catalyst 150, which is heated to a temperature suitable for the reforming reaction by the heat of the heating section 120 (including the heat of the combustion exhaust gas) transmitted through the heating section partition 131, to produce a primary hydrogen-containing gas.

[0064] The primary hydrogen-containing gas discharged from the reforming section 122 flows through the return flow path 141 and is supplied to the CO reduction catalyst 151 from below, and the CO concentration in the primary hydrogen-containing gas is reduced to approximately 0.1 to 0.2% by a transformation reaction in the CO reduction catalyst 151, thereby producing a secondary hydrogen-containing gas.

[0065] At this time, the CO reduction catalyst 151 is heated to a temperature suitable for the shift reaction by the heat of the primary hydrogen-containing gas discharged from the reforming section 122 (reforming catalyst 150) and flowing into the CO reduction catalyst 151, and by the cold heat transferred from the evaporating section 121 to the CO reduction catalyst 151 through the space formed by the first partition 132 and the heat transfer buffer tube 135, and through the heat transfer buffer tube 135.

[0066] The secondary hydrogen-containing gas discharged from the CO reduction catalyst 151 exits the hydrogen generation device 100 through an outlet pipe, and is supplied to a hydrogen-utilizing device such as a fuel cell.

[0067] The combustion exhaust gas generated by the combustion of the burner of the heating section 120 flows downward along the inner surface of the combustion tube 130, then turns back upward through the gap between the bottom of the heating section partition 131 and the lower end of the combustion tube 130, and exchanges heat with the reforming section 122 through the combustion exhaust gas flow path 140 formed between the combustion tube 130 and the heating section partition 131.Then, it exchanges heat with the evaporating section 121 and is discharged to the outside of the hydrogen generation apparatus 100 from a combustion exhaust gas outlet pipe provided at the upper part of the heating section partition 131.

[0068] (Manufacturing process related to catalyst loading for hydrogen generation equipment) The catalyst filling preparation process 101 is a process of manufacturing a hydrogen generation apparatus and then inverting the top and bottom of the hydrogen generation apparatus with respect to the direction of gravity when it is used (turning it upside down) until the following state is reached: the second lower partition 133 has not yet been joined to the lower end of the second upper partition 134 that has already been attached to the first partition 132; the reforming section upper shelf plate 126 has been attached between the heating section partition 131 and the first partition 132, but the reforming section lower shelf plate 127 has not yet been positioned between the heating section partition 131 and the first partition 132; and the CO reduction section upper shelf plate 124 has been attached between the second upper partition 134 and the heat transfer buffer tube 135, but the CO reduction section lower shelf plate 125 has not yet been positioned between the second upper partition 134 and the heat transfer buffer tube 135, so that the reforming catalyst 150 and the CO reduction catalyst 151 can be filled in a later process.

[0069] As a result, in the hydrogen generation apparatus in a state where the catalyst filling preparation step 101 is completed, the catalyst can be introduced from above into the space surrounded by the heating section partition 131, the first partition 132, and the reforming section upper shelf plate 126, and into the space surrounded by the second partition top 134, the heat transfer buffer tube 135, and the CO reduction section upper shelf plate 124. Therefore, the catalyst filling of the reforming catalyst 150 and the CO reduction catalyst 151 can be performed in the catalyst filling step. This can be continued at step 102.

[0070] In the catalyst sealing step 103, in order to seal (hold in place) the catalyst filled in the catalyst sealing step 103, when the catalyst filling step 102 is completed, the reforming section lower shelf 127 is introduced from above in the vertical direction towards the section filled with the reforming catalyst 150 and installed in a position where it abuts against the upper end of the section filled with the reforming catalyst 150, and the CO reduction section lower shelf 125 is introduced from above in the vertical direction towards the section filled with the CO reduction catalyst 151 and installed in a position where it abuts against the upper end of the section filled with the CO reduction catalyst 151.

[0071] Since the outer diameter of the heat transfer buffer tube 135 is larger than the outer diameter of the portion of the first partition 132 where the reforming section 122 is configured, the inner diameter of the CO reduction section lower shelf plate 125 installed on the outer periphery of the heat transfer buffer tube 135 can be larger than the outer diameter of the portion of the first partition 132 where the reforming section 122 is configured.

[0072] Therefore, when the CO reduction section lower shelf 125 is passed through the portion of the first partition 132 in which the reforming section 122 is configured and installed in a predetermined position, the CO reduction section lower shelf 125 can be introduced to a position where it abuts the portion filled with the CO reduction catalyst 151 without being obstructed by the portion of the first partition 132 in which the reforming section 122 is configured.

[0073] Therefore, in the catalyst sealing step 103, the work of sealing (holding in place) the reforming catalyst 150 and the CO reduction catalyst 151 by the reforming section lower shelf plate 127 and the CO reduction section lower shelf plate 125 can be performed continuously.

[0074] [1-3. Effects] As described above, in the hydrogen generation apparatus 100 of this embodiment, the evaporation section 121 and the reforming section 122 are arranged between the cylindrical heating section partition wall 131 having a central axis in the vertical direction and the cylindrical first partition wall 132 having a central axis in the vertical direction and surrounding the outer periphery of the heating section partition wall 131, and the CO reduction section 123 is arranged between the part of the first partition wall 132 where the evaporation section 121 is configured and the cylindrical second partition wall 134 having a central axis in the vertical direction and surrounding the outer periphery of the evaporation section 121.

[0075] Furthermore, a return flow path 141 is formed between the portion of the first partition 132 where the reforming section 122 is configured and a bottomed, cylindrical second lower partition 133 having a vertical central axis, an upper end connected to the lower end of the second upper partition 134, and surrounding the outer periphery and bottom of the reforming section 122, and the outer diameter of the portion of the first partition 132 where the reforming section 122 is configured is larger than the outer diameter of the portion of the first partition 132 where the evaporation section 121 is configured.

[0076] The evaporator section 121 is configured to heat the raw material gas and water with heat transmitted through the heating section partition 131 to evaporate the water, and the reformer section 122 is configured below the evaporator section 121 to generate a primary hydrogen-containing gas containing carbon monoxide through a reforming reaction from a mixed gas of the raw material gas and water vapor with heat transmitted through the heating section partition 131.

[0077] The CO reduction section 123 is configured to reduce the concentration of carbon monoxide contained in the primary hydrogen-containing gas flowing out from the reforming section 122 through a shift reaction, thereby generating a secondary hydrogen-containing gas.

[0078] The return flow passage 141 is a flow passage that redirects the flow of the primary hydrogen-containing gas flowing downward from the reforming section 122 to the upward direction and guides it to the CO reducing section 123 .

[0079] One feature of the hydrogen generation device 100 in the present disclosure is that a heat transfer buffer tube 135 is provided between the portion of the first partition wall 132 in which the evaporation section 121 is configured and the CO reduction section 123. That is the thing.

[0080] The heat transfer buffer tube 135 is a member configured to form a space between the evaporator section 121 and the CO reduction section 123, has a central axis in the vertical direction, and has upper and lower ends bent inwardly and fixed to the outer peripheral surface of the portion of the first partition 132 where the evaporator section 121 is configured.

[0081] The CO reduction section 123 includes a CO reduction catalyst 151, a CO reduction section lower shelf plate 125, and a CO reduction section upper shelf plate 124. The CO reduction catalyst 151 is a granular catalyst filled between the second partition top 134 and the heat transfer buffer cylinder 135. The CO reduction section lower shelf plate 125 is a shelf plate arranged between the second partition top 134 and the heat transfer buffer cylinder 135 so as to support the CO reduction catalyst 151 from below, and the CO reduction section upper shelf plate 124 is a shelf plate arranged between the second partition top 134 and the heat transfer buffer cylinder 135 so as to cover the CO reduction catalyst 151 from above.

[0082] The CO reduction section lower shelf plate 125 and the CO reduction section upper shelf plate 124 are doughnut-shaped, and have vent holes smaller than the particle diameter of the CO reduction catalyst 151 formed therein.

[0083] Another feature of the hydrogen generation apparatus 100 in the present disclosure is that the outer diameter of the portion of the heat transfer buffer tube 135 in which the CO reduction catalyst 151, the CO reduction section lower shelf plate 125, and the CO reduction section upper shelf plate 124 are arranged is made larger than the outer diameter of the portion of the first partition 132 in which the reforming section 122 is configured.

[0084] In the hydrogen generation apparatus 100 of this embodiment, when the reforming section 122 has a structure in which the reforming catalyst 150 is held between the reforming section lower shelf plate 127 and the reforming section upper shelf plate 126, a manufacturing method thereof includes a catalyst filling preparation step 101, a catalyst filling step 102, and a catalyst sealing step 103.

[0085] The catalyst filling preparation process 101 is a process of manufacturing a hydrogen generation apparatus and then inverting the top and bottom of the hydrogen generation apparatus with respect to the direction of gravity when it is used (turning it upside down) until the following state is reached: the second lower partition 133 has not yet been joined to the lower end of the second upper partition 134 that has already been attached to the first partition 132; the reforming section upper shelf plate 126 has been attached between the heating section partition 131 and the first partition 132, but the reforming section lower shelf plate 127 has not yet been positioned between the heating section partition 131 and the first partition 132; and the CO reduction section upper shelf plate 124 has been attached between the second upper partition 134 and the heat transfer buffer tube 135, but the CO reduction section lower shelf plate 125 has not yet been positioned between the second upper partition 134 and the heat transfer buffer tube 135, so that the reforming catalyst 150 and the CO reduction catalyst 151 can be filled in a later process.

[0086] The catalyst filling process 102 is a process in which, after the catalyst filling preparation process 101 is completed, the space surrounded by the heating section partition 131, the first partition 132, and the reforming section upper shelf plate 126 is filled with the reforming catalyst 150, and the space surrounded by the second partition top 134, the heat transfer buffer tube 135, and the CO reduction section upper shelf plate 124 is filled with the CO reduction catalyst 151.

[0087] In the hydrogen generation apparatus after completion of the catalyst filling preparation step 101, catalyst can be introduced from above into the space surrounded by the heating section partition 131, the first partition 132, and the reforming section upper shelf plate 126, and into the space surrounded by the second partition top 134, the heat transfer buffer tube 135, and the CO reduction section upper shelf plate 124. Therefore, catalyst filling of the reforming catalyst 150 and the CO reduction catalyst 151 can be continuously performed in the catalyst filling step 102.

[0088] The catalyst sealing step 103 includes, after the catalyst filling step 102 is completed, an operation of introducing the reforming section lower shelf 127 from above in the vertical direction toward the portion filled with the reforming catalyst 150 and placing it in a position where it abuts against the upper end of the portion filled with the reforming catalyst 150, and an operation of introducing the CO reduction section lower shelf 125 from above in the vertical direction toward the portion filled with the CO reduction catalyst 151 and placing the CO reduction section lower shelf 125 in a position where it abuts against the upper end of the portion filled with the CO reduction catalyst 151. and installing the catalyst 151 at a position where it abuts against the upper end of the portion filled with the catalyst 151.

[0089] Since the outer diameter of the heat transfer buffer tube 135 is larger than the outer diameter of the portion of the first partition 132 where the reforming section 122 is configured, the inner diameter of the CO reduction section lower shelf plate 125 installed on the outer periphery of the heat transfer buffer tube 135 can be made larger than the outer diameter of the portion of the first partition 132 where the reforming section 122 is configured.

[0090] Therefore, when the CO reduction section lower shelf 125 is passed through the portion of the first partition 132 in which the reforming section 122 is configured and installed in a predetermined position, the CO reduction section lower shelf 125 can be introduced to a position where it abuts the portion filled with the CO reduction catalyst 151 without being obstructed by the portion of the first partition 132 in which the reforming section 122 is configured.

[0091] Therefore, in the catalyst sealing step 103, the work of sealing (holding in place) the reforming catalyst 150 and the CO reduction catalyst 151 by the reforming section lower shelf plate 127 and the CO reduction section lower shelf plate 125 can be performed continuously.

[0092] The hydrogen generation apparatus 100 in this embodiment is provided with a heat transfer buffer tube 135 in the first partition 132 so that a space is provided between the evaporation section 121 and the CO reduction section 123, and the outer diameter of the portion of the heat transfer buffer tube 135 where the components of the CO reduction section 123 are arranged is made larger than the outer diameter of the portion of the first partition 132 where the reforming section 122 is arranged, thereby obtaining the following effects.

[0093] In other words, the hydrogen generation apparatus 100 is manufactured to a state in which the second lower partition 133 is not joined to the lower end of the second upper partition 134, the CO reduction section upper shelf plate 124 has been attached, but the CO reduction catalyst 151 and the CO reduction section lower shelf plate 125 have not been arranged.The hydrogen generation apparatus 100 is then inverted (upside down) in the direction of gravity when in use, and the CO reduction catalyst 151 is then filled in.The CO reduction section lower shelf plate 125 can then be attached to a predetermined position without being hindered by the size of the outer diameter of the reforming section 122, and the CO reduction catalyst 151 can be held between the CO reduction section upper shelf plate 124 and the CO reduction section lower shelf plate 125.

[0094] Therefore, if the reforming section 122 is structured to hold the reforming catalyst 150 between the reforming section lower shelf 127 and the reforming section upper shelf 126, even if the outer diameter of the reforming section 122 is larger than the outer diameter of the evaporation section 121, the work of filling with the CO reduction catalyst 151 and holding it in a predetermined position can be performed continuously and efficiently along with the work of filling with the reforming catalyst 150 and holding it in a predetermined position, thereby providing a hydrogen generation device 100 that can reduce manufacturing costs.

[0095] In addition, since the heat transfer buffer tube 135 forms a space between the evaporation section 121 and the CO reduction section 123, it is possible to prevent the CO reduction catalyst 151 filled on the inner side from being locally cooled by heat exchange with the evaporation section 121 (occurrence of temperature unevenness in the CO reduction catalyst 151).

[0096] This makes it easier to heat the entire CO reduction catalyst 151 to a temperature suitable for the shift reaction, making it possible to reduce the carbon monoxide concentration in the secondary hydrogen-containing gas more than before and to reduce the amount of CO reduction catalyst 151 filled more than before.

[0097] (Other embodiments) As described above, the first embodiment has been described as an example of the technology disclosed in the present application. However, the technology in the present disclosure is not limited to this, and can be applied to embodiments in which modifications, substitutions, additions, omissions, etc. are made. In addition, each component described in the first embodiment It is also possible to combine these to form new embodiments.

[0098] Therefore, another embodiment will be illustrated below with reference to FIG.

[0099] In the first embodiment, a configuration in which the reforming catalyst 150 and the CO reduction catalyst 151 are provided as catalysts has been described.

[0100] As shown in FIG. 3, the hydrogen generation device 200 may be provided with a CO removal section 142 filled with a CO removal catalyst downstream (upper) of the CO reduction catalyst 151, which generates a tertiary hydrogen-containing gas by further reducing the concentration of carbon monoxide contained in the secondary hydrogen-containing gas flowing out from the CO reduction section 123 through a selective oxidation reaction.

[0101] The CO removal catalyst is a granular Ru-based catalyst with a diameter of 2 to 3 mm. The CO removal catalyst is supported from below by the CO removal section lower shelf plate 144 (its downward movement is restricted) and covered from above by the CO removal section upper shelf plate 143 (its upward movement is restricted), and is held between the CO removal section lower shelf plate 144 and the CO removal section upper shelf plate 143.

[0102] The CO removal section lower shelf plate 144 and the CO removal section upper shelf plate 143 are both doughnut-shaped plates in which air holes with a diameter of 1 mm, which is smaller than the particle diameter of the CO removal catalyst, are formed.

[0103] This allows the CO removal catalyst to further reduce the concentration of carbon monoxide contained in the hydrogen-containing gas discharged (supplied) from the hydrogen generation device 200, as compared with the hydrogen generation device 100 of embodiment 1. Therefore, a highly reliable hydrogen generation device 200 can be provided.

[0104] The CO removal catalyst is filled by installing the CO removal section lower shelf plate 144 before filling, and the hydrogen generation apparatus is placed in the orientation for use (normal upside down). After filling the CO removal catalyst, the CO removal section upper shelf plate 143 is installed, so that the CO removal catalyst can be held between the CO removal section lower shelf plate 144 and the CO removal section upper shelf plate 143.

[0105] When the top and bottom are in the normal state and the CO removal section upper shelf plate 143 is to be installed after the CO removal catalyst is loaded, it is necessary to configure the second partition upper plate 134 etc. so that there are no obstacles above the CO removal section upper shelf plate 143 installed between the second partition upper plate 134 and the heat transfer buffer cylinder 135 that would prevent the CO removal catalyst from being loaded from above and the CO removal section upper shelf plate 143 from being installed.

[0106] It should be noted that the above-described embodiments are intended to illustrate the technology of the present disclosure, and various modifications, substitutions, additions, omissions, and the like can be made within the scope of the claims or their equivalents. [Industrial Applicability]

[0107] The present disclosure is applicable to a hydrogen generation device in which an evaporator section and a reformer section are arranged between a heating section partition and a first partition surrounding the heating section partition, a CO reduction section is arranged between a portion of the first partition where the evaporator section is configured and a second partition surrounding that portion, and the outer diameter of the portion of the first partition where the reformer section is configured is larger than the outer diameter of the portion of the first partition where the evaporator section is configured. [Explanation of symbols]

[0108] 100 Hydrogen generator 101 Catalyst filling preparation process 102 Catalyst filling process 103 Catalyst sealing process 120 Heating section 121 Evaporation section 122 Reforming section 123 CO reduction section 124 CO reduction section upper shelf 125 CO reduction section lower shelf 126 Modification section upper shelf 127 Modification section lower shelf 130 Combustion tube 131 Heating section bulkhead 132 1st bulkhead 133 Under the second bulkhead 134 On the second bulkhead 135 Heat transfer buffer tube 140 Combustion exhaust gas flow path 141 Return flow path 142 CO removal section 143 CO removal section upper shelf 144 CO removal section lower shelf 150 Reforming catalyst 151 CO reduction catalyst 200 Hydrogen generator

Claims

1. an evaporation section configured to heat a raw material gas and water by heat transmitted through the heating section partition wall and evaporate the water between a cylindrical heating section partition wall having a central axis in a vertical direction and a cylindrical first partition wall having a central axis in a vertical direction and surrounding an outer periphery of the heating section partition wall; and a reforming section configured below the evaporation section to generate a primary hydrogen-containing gas containing carbon monoxide by a reforming reaction from a mixed gas of the raw material gas and water vapor by heat transmitted through the heating section partition wall, a CO reduction unit configured to generate a secondary hydrogen-containing gas by reducing a concentration of carbon monoxide contained in the primary hydrogen-containing gas flowing out from the reforming unit by a shift reaction is disposed between a portion of the first partition wall where the evaporation unit is configured and a cylindrical second partition wall having a central axis in a vertical direction and surrounding an outer periphery of the evaporation unit, a return flow passage is formed between a portion of the first partition wall where the reforming section is configured and a bottom of a cylindrical second partition wall having a central axis in a vertical direction, an upper end of which is connected to a lower end of the second partition wall and which surrounds an outer periphery and a bottom of the reforming section, the return flow passage redirects a flow of the primary hydrogen-containing gas flowing downward from the reforming section and guides the flow upward to the CO reduction section, a portion of the first partition wall where the reforming section is configured has an outer diameter larger than an outer diameter of a portion of the first partition wall where the evaporating section is configured, a heat transfer buffer cylinder having a vertical center axis and upper and lower ends bent inwardly and fixed to an outer circumferential surface of a portion of the first partition wall where the evaporator portion is configured, so that a space is formed between the portion of the first partition wall where the evaporator portion is configured and the CO reduction portion; the CO reduction section includes: a granular CO reduction catalyst filled between the second partition and the heat transfer buffer cylinder; a CO reduction section lower shelf plate having a doughnut disk shape and having air holes smaller than a particle diameter of the CO reduction catalyst, the shelf plate being arranged between the second partition and the heat transfer buffer cylinder so as to support the CO reduction catalyst from below; and a CO reduction section upper shelf plate having a doughnut disk shape and having air holes smaller than a particle diameter of the CO reduction catalyst, the shelf plate being arranged between the second partition and the heat transfer buffer cylinder so as to cover the CO reduction catalyst from above. A hydrogen generation device characterized in that the outer diameter of the portion of the heat transfer buffer tube in which the CO reduction catalyst, the CO reduction section lower shelf plate, and the CO reduction section upper shelf plate are arranged is larger than the outer diameter of the portion of the first partition in which the reforming section is configured.

2. the reforming section includes: a granular reforming catalyst filled between the first partition wall and the heating section partition wall; a donut-shaped reforming section lower shelf plate disposed between the first partition wall and the heating section partition wall so as to support the reforming catalyst from below, the donut-shaped reforming section upper shelf plate being disposed between the first partition wall and the heating section partition wall so as to cover the reforming catalyst from above, the donut-shaped reforming section upper shelf plate being disposed between the first partition wall and the heating section partition wall so as to cover the reforming catalyst from above, the donut-shaped reforming section upper shelf plate being formed with air holes smaller than the particle diameter of the reforming catalyst; The method for producing a hydrogen generation apparatus according to claim 1, comprising: a catalyst loading preparation process in which a hydrogen generation apparatus is manufactured to a state in which the second partition bottom has not yet been joined to the lower end of the upper second partition that has been attached at a predetermined position, the reforming section upper shelf plate has been attached between the first partition and the heating section partition, but the reforming catalyst and the reforming section lower shelf plate have not yet been disposed between the first partition and the heating section partition, and the CO reduction section upper shelf plate has been attached between the second partition and the heat transfer buffer tube, but the CO reduction catalyst and the CO reduction section lower shelf plate have not yet been disposed between the second partition and the heat transfer buffer tube, and the hydrogen generation apparatus is then turned upside down in the direction of gravity when used; a catalyst filling step in which, in a state in which the catalyst filling preparation step is completed, a step of filling the reforming catalyst into a space surrounded by the first partition wall, the heating unit partition wall, and the reforming unit upper shelf plate, and a step of filling the CO reduction catalyst into a space surrounded by the second partition wall, the heat transfer buffer tube, and the CO reduction unit upper shelf plate, are performed; When the catalyst filling step is completed, the reforming section lower shelf is introduced vertically from above toward the portion filled with the reforming catalyst, and the upper end of the portion filled with the reforming catalyst is and a catalyst sealing step of introducing the CO reduction unit lower shelf plate vertically from above toward the portion filled with the CO reduction catalyst to place the CO reduction unit lower shelf plate in a position where it abuts against the upper end of the portion filled with the CO reduction catalyst. A method for manufacturing a hydrogen generation device.

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