JP2023113226A - Method for manufacturing hydrogen generator - Google Patents

Abstract

To provide a hydrogen generator suppressing individual difference in concentration of CO included in hydrogen-containing gas after a conversion reaction by making a downstream position of a CO-reducing part constant.SOLUTION: A hydrogen generator is manufactured by first performing fixation of an upper shelf board of a CO-reducing part in assembling the CO-reducing part, performing filling of a CO-reducing catalyst under the condition where a gravity direction is inverted with respect to that when the hydrogen generator is used, and installing a lower shelf board of the CO-reducing part at an upstream position of the CO-reducing catalyst. As a result of this, variation in the cubic volume of the CO-reducing catalyst can be absorbed at a position where the lower shelf board of the CO-reducing part is fixed and thereby variation in the position of the upper shelf board of the CO-reducing part can be suppressed.SELECTED DRAWING: Figure 1

Description

The present disclosure relates to a method for manufacturing a hydrogen generator.

In Patent Document 1, a combustion exhaust gas flow path for upwardly flowing combustion exhaust gas is formed between a combustion cylinder surrounding the outer circumference of a heating part and a heating part partition wall surrounding the outer circumference of the combustion cylinder. Between the first partition surrounding the outer periphery, an evaporating section is configured on the upper side, and a reforming section is configured on the lower side, respectively, and CO reduction is provided between the first partition and the second partition surrounding the outer periphery of the first partition. A multi-cylindrical hydrogen generator is disclosed, in which a hydrogen-containing gas flowing out from the CO reduction unit is discharged to the outside.

JP 2018-118863 A

The present disclosure provides a method of manufacturing a hydrogen generator that can keep the downstream position of the CO reduction unit constant and suppress individual differences in the concentration of CO contained in the hydrogen-containing gas after passing through the CO reduction unit.

A method for manufacturing a hydrogen generator according to the present disclosure includes a heating section, a combustion cylinder, a heating section partition, a first partition, a flue gas flow path, an evaporating section, a reforming section, a heat transfer buffer, a second partition, and a CO reduction section. , a lower shelf plate of a CO reduction unit, an upper shelf plate of a CO reduction unit, a lower part of a second partition wall, and a return flow path, comprising a CO reduction catalyst filling preparation step, a CO reduction catalyst filling step, and a CO reduction catalyst It is characterized by having a sealing step, a step of introducing under the second partition wall, and a step of joining the second partition wall.

The heating unit is configured to burn the combustible gas and discharge flue gas. The combustion tube has a cylindrical shape having a central axis in the vertical direction and surrounds the outer circumference of the heating section, and is configured so that combustion exhaust gas flows downward inside the tube. The partition wall of the heating section has a bottomed tubular shape with a central axis in the vertical direction, and is configured to accommodate the combustion tube with a gap between it and the combustion tube.

The first partition has a substantially cylindrical shape having a central axis in the vertical direction, the diameter of the lower portion is larger than the diameter of the upper portion, and the first partition surrounds the outer circumference of the partition of the heating portion with a gap between it and the partition of the heating portion. The flue gas flow path is a flow path formed in a gap between the combustion cylinder and the partition wall of the heating section, through which the flue gas flows upward.

The evaporating section is formed in a gap between the heating section partition and the upper portion of the first partition, and is configured to heat the material gas and water with heat transferred through the heating section partition to evaporate the water.

The reforming section is formed by filling the gap between the partition wall of the heating section and the lower part of the first partition with a reforming catalyst. It is configured to generate a primary hydrogen-containing gas containing carbon monoxide through a reforming reaction from a mixed gas of gas and water vapor.

The heat transfer buffer cylinder has a substantially cylindrical shape with a central axis in the vertical direction, the outer diameter of the outer peripheral surface is larger than the outer diameter of the outer peripheral surface of the lower part of the first partition, and heat transfer is performed between the upper part of the first partition and the heat transfer buffer cylinder. The upper and lower ends are bent inward and fixed to the upper outer peripheral surface of the first partition so as to form a buffer space.

The second partition wall has a substantially cylindrical shape having a central axis in the vertical direction, surrounds the outer periphery of the heat transfer buffer cylinder with a gap between it and the heat transfer buffer cylinder, and the upper end portion is bent inward to form the first partition wall. It is fixed to the outer peripheral surface of the upper part of the partition.

The CO reduction section is formed by filling a gap between the heat transfer buffer cylinder and the second partition with a CO reduction catalyst, and reduces the concentration of carbon monoxide contained in the primary hydrogen-containing gas flowing out of the reforming section by a modification reaction. It is configured to be reduced and discharged as a secondary hydrogen-containing gas.

The lower shelf plate of the CO reduction unit and the upper shelf plate of the CO reduction unit are air-permeable, doughnut-shaped shelves. and the second partition wall for supporting the CO reduction catalyst from below. It is a shelf plate for covering the upper surface of the part filled with the CO reduction catalyst so that the lower surface is in contact with the CO reduction catalyst.

The lower part of the second partition wall has a bottomed cylindrical shape with a central axis in the vertical direction, the upper end abuts the outer peripheral part of the lower surface of the lower shelf plate of the CO reduction part, and the upper part of the outer peripheral surface contacts the lower part of the inner peripheral surface of the second partition wall. It is joined to the top of the second partition so as to face each other, and is configured to accommodate the first partition and the heating portion partition with a gap between them and the portion of the first partition below the CO reduction section.

The return flow path is formed in a gap between a portion of the first partition below the CO reduction section and the bottom of the second partition, and changes the flow of the primary hydrogen-containing gas that has flowed downward from the reforming section upward to increase CO It is a flow path for leading to the reduction part.

In the CO reduction catalyst filling preparation step, the lower portion of the second partition wall that has been attached to the predetermined position has not yet been arranged under the second partition wall, and the predetermined position of the gap between the second partition wall and the heat transfer buffer cylinder Although the upper shelf plate of the CO reduction unit has already been installed, the CO reduction catalyst and the lower shelf plate of the CO reduction unit have not yet been placed in the gap between the second partition wall and the heat transfer buffer cylinder. is produced, and the hydrogen generator is turned upside down in the direction of gravity during use.

In the CO reduction catalyst filling step, in a state where the CO reduction catalyst filling preparation step is completed, CO reduction of a predetermined weight is placed from above in the space surrounded by the second partition wall, the heat transfer buffer cylinder, and the CO reduction unit upper shelf plate. This is the step of filling the catalyst.

In the CO reduction catalyst sealing step, in a state where the CO reduction catalyst filling step is completed, the CO reduction section lower shelf is introduced from above toward the portion filled with the CO reduction catalyst to remove the CO in the CO reduction section lower shelf. In this step, the surface facing the CO reduction catalyst is installed at a position where the surface is evenly in contact with the CO reduction catalyst.

In the step of introducing under the second partition, in a state where the step of sealing the CO reduction catalyst is completed, the bottom of the second partition is turned upside down so that the bottom of the bottom of the second partition faces up, and the bottom of the second partition is moved from above to the lower shelf of the CO reduction unit. In this step, the second partition is introduced toward the plate and installed at a position where the bottom of the second partition abuts the bottom shelf plate of the CO reduction unit.

The second partition joining step is a step of hermetically joining the portions where the second partition bottom and the second partition top are adjacent to each other in a state where the second partition bottom introduction step is completed.

In addition, another method for manufacturing a hydrogen generator in the present disclosure includes a heating section, a combustion cylinder, a heating section partition, a first partition, a combustion exhaust gas flow path, an evaporating section, a reforming section, a heat transfer buffer, and a second partition. , a CO reduction section, a CO reduction section lower shelf, a CO reduction section upper shelf, a second partition bottom, and a return flow path, and the second partition bottom and the CO reduction section bottom shelf are integrally configured. In the manufacturing method, the step of sealing the CO reduction catalyst is omitted by integrating the bottom of the second partition and the bottom plate of the CO reduction unit in the method of manufacturing the hydrogen generator described above.

The lower portion of the second partition wall has a bottomed cylindrical shape with a central axis in the vertical direction, and is integrally formed with the lower shelf plate of the CO reduction unit, with the upper portion of the outer peripheral surface facing the lower portion of the inner peripheral surface of the second partition wall. It is joined to the top of the second partition, and is configured to accommodate the first partition and the heating portion partition with a gap between them and the portion of the first partition below the CO reduction section.

In the step of introducing under the second partition, in the state where the CO reduction catalyst filling step is completed, the CO under the second partition is turned upside down so that the lower shelf plate of the CO reduction unit is at the bottom and the bottom under the second partition is at the top. A step of introducing the lower shelf plate of the reduction section from above toward the portion filled with the CO reduction catalyst, and installing the surface of the lower shelf plate of the CO reduction section facing the CO reduction catalyst evenly in contact with the CO reduction catalyst. is.

In the method of manufacturing a hydrogen generator according to the present disclosure, the upper shelf plate of the CO reduction unit is first fixed in the assembly of the CO reduction unit, and the CO reduction catalyst is installed in a state in which the direction of gravity is reversed from when the hydrogen generation unit is used. By adopting a manufacturing method in which the filling is performed and the lower shelf plate of the CO reduction section is installed upstream of the CO reduction catalyst, the following effects can be obtained.

By fixing the upper shelf of the CO reduction section to a predetermined position in advance, it is possible to absorb variations in the volume of the filled CO reduction catalyst at the fixed position of the lower shelf of the CO reduction section. Variation in the position of the plate can be suppressed.

Therefore, since the downstream position of the CO reduction catalyst can be kept constant, the distance between the downstream position of the CO reduction catalyst and the heating section becomes constant, and the temperature of the downstream part of the CO reduction catalyst can be kept constant. Since the concentration of CO contained in the hydrogen-containing gas after passing through the CO reduction portion depends on the temperature of the downstream portion of the CO reduction catalyst, it is possible to suppress individual differences in the CO concentration in the post-shifting reaction gas.

Schematic diagram of the hydrogen generator in Embodiment 1 Schematic configuration diagram showing five manufacturing processes for assembling the CO reduction unit of the hydrogen generator according to Embodiment 1. Schematic configuration diagram of a hydrogen generator in Embodiment 2 Schematic configuration diagram showing four manufacturing processes for assembling the CO reduction unit of the hydrogen generator according to Embodiment 2 Schematic configuration diagram of a hydrogen generator in another form Schematic configuration diagram showing five manufacturing processes for assembling a CO reduction unit of a hydrogen generator in another form

(Knowledge, etc. on which this disclosure is based)
At the time when the inventors came up with the present disclosure, a combustion exhaust gas flow path for upwardly flowing combustion exhaust gas was formed between the combustion cylinder surrounding the outer circumference of the heating part and the heating part partition wall surrounding the outer circumference of the combustion cylinder. , between the heating part partition and the first partition surrounding the outer periphery of the heating part partition, the evaporating part is configured on the upper side and the reforming part is configured on the lower side, and the first partition and the first partition surrounding the outer periphery of the first partition There was a multi-cylindrical hydrogen generator in which a CO reduction section was formed between two partition walls and the hydrogen-containing gas that flowed out from the CO reduction section was discharged to the outside.

However, in the conventional hydrogen generator, the mounting position of the shelf supporting the CO reduction catalyst from below so that the CO reduction catalyst in the CO reduction unit does not drop was determined before the CO reduction catalyst was filled.

However, since the CO reduction catalyst is a spherical object, there are individual differences in the downstream position of the CO reduction section in each aircraft due to the difference in the amount of catalyst filled and the gap created by the filling of the catalyst. In addition, when a CO reduction catalyst with a low specific gravity is mixed with the CO reduction catalyst that is controlled and filled so as to have a constant weight, the volume of the CO reduction remover increases, and the downstream position of the CO reduction unit moves upward. deviate.

Due to the difference in the downstream position of the CO reduction section, the distance from the high-temperature heating section varies, and the temperature of the hydrogen-containing gas downstream of the CO reduction section and the hydrogen-containing gas after the transformation reaction varies. A chemical reaction called the water-gas shift reaction takes place in the CO reduction zone, which is an exothermic chemical reaction. Therefore, when the temperature of the CO reduction catalyst portion rises, the equilibrium state is biased toward the reactants, and the concentration of CO in the generated gas increases.

As a result, there is a problem that the concentration of CO contained in the hydrogen-containing gas after the shift reaction varies among individuals due to the difference in the temperature of the hydrogen-containing gas after the shift reaction.

Under such circumstances, the inventors first fixed the upper shelf plate of the CO reduction unit, filled the CO reduction catalyst with the direction of gravity reversed from when the hydrogen generator was used, and then reduced CO. By fixing the shelf plate at the bottom of the unit at the upper end position of the CO reduction catalyst in the vertical direction in a state where the direction of gravity is reversed from when the hydrogen generator is in use, variations in the downstream position of the CO reduction unit are suppressed. I got the idea that it can be done.

However, the shelf plate at the bottom of the CO reduction section needs to be fixed by welding with the inner cylindrical member that makes up the CO reduction section, but the welding torch interferes with the outer cylindrical member that makes up the CO reduction section, and the welding torch interferes. difficult to weld.

Furthermore, the inventors believe that unlike the upper shelf plate of the CO reduction unit, the lower shelf plate bears the weight of the catalyst, so it must be securely fixed in order to prevent product defects due to falling off of the catalyst. It has been discovered that there is a problem, and the subject matter of this disclosure has been formed in order to solve that problem.

Therefore, in the present disclosure, assembly is performed in the order of fixing the upper shelf plate of the CO reduction unit, filling the CO reduction catalyst, and installing the lower shelf plate of the CO reduction unit to form a return flow path through which the gas after the reforming reaction flows. The upper end portion of the outer cylindrical member is supported in contact with the lower shelf plate of the CO reduction section, thereby fixing the lower shelf plate of the CO reduction section at the lower end position of the CO reduction catalyst and forming the return flow path. and the outer cylindrical member that constitutes the CO reduction section are welded to form a CO reduction section with a uniform upper end position in each fuselage, and individual differences in the concentration of CO contained in the hydrogen-containing gas after the metamorphic reaction are eliminated. Provided is a method for manufacturing a hydrogen generator capable of suppressing.

Hereinafter, embodiments will be described in detail with reference to the drawings. However, more detailed description than necessary may be omitted. For example, detailed descriptions of well-known matters or redundant descriptions of substantially the same configurations may be omitted.

It should be noted that the accompanying drawings and the following description are provided to allow those skilled in the art to fully understand the present disclosure and are not intended to limit the claimed subject matter thereby.

(Embodiment 1)
Embodiment 1 will be described below with reference to FIGS. 1 and 2. FIG.

[1-1. composition]
As shown in FIG. 1, the hydrogen generator 100 includes a heating unit 120, an evaporating unit 121, a reforming unit 122, a CO reducing unit 123, a CO reducing unit upper shelf 124, a CO reducing unit lower shelf 125, a combustion cylinder 130, and a heating unit. It has a partition wall 131 , a first partition wall 132 , a second upper partition wall 133 , a second lower partition wall 134 , a heat transfer buffer cylinder 135 , a flue gas flow path 140 and a return flow path 141 .

The heating unit 120 is arranged on the inner peripheral side of a combustion cylinder 130 having a central axis in the vertical direction, and includes a burner that burns combustible gas mixed with combustion air and discharges combustion exhaust gas, and a combustible gas in the burner. and a combustion air supply pipe for supplying combustion air to the burner. The burners of heating section 120 are configured to produce downward flames.

Raw material gas (city gas or LP gas) can be used as the combustible gas. In addition, when the hydrogen generator 100 supplies a hydrogen-containing gas to the fuel cell as the fuel gas, it is used in the fuel cell. A fuel gas (anode off-gas) discharged from the fuel cell can be used.

Combustion cylinder 130 has a cylindrical shape having a central axis in the vertical direction and surrounds the outer periphery of heating section 120 , and is arranged coaxially with heating section 120 . In the combustion tube 130, the combustion exhaust gas flows downward (downward in the vertical direction) on the inner peripheral side of the combustion tube 130, and the combustion gas formed between the combustion tube 130 and the heating section partition 131 on the outer peripheral side of the combustion tube 130. The exhaust gas passage 140) is a member for causing the combustion exhaust gas to flow upward (upward in the vertical direction).

The lower end of the combustion tube 130 is located vertically below the lower end of the reforming section 122, and the bottom of a bottomed cylindrical heating section partition 131 that surrounds the combustion tube 130 and is arranged coaxially with the combustion tube 130. located vertically above

In the hydrogen generator 100, after the flue gas generated by the combustion of the burner of the heating section 120 flows downward along the inner peripheral surface of the combustion tube 130 along the inner peripheral side of the combustion tube 130, it reaches the bottom portion of the heating section partition wall 131. and the lower end of the combustion cylinder 130 and flows upward, and after heat exchange with the reforming section 122 through the combustion exhaust gas flow path 140 formed between the combustion cylinder 130 and the heating section partition 131, , exchanges heat with the evaporating section 121 and is discharged to the outside of the hydrogen generator 100 from a combustion exhaust gas outlet pipe provided in the upper portion of the heating section partition 131 .

The combustion exhaust gas flow path 140 is a flow path formed in a gap between the combustion cylinder 130 and the heating section partition wall 131 and through which the combustion exhaust gas flows upward.

The heating part partition wall 131 has an inner diameter larger than the outer diameter of the combustion cylinder 130 , surrounds the outer peripheral surface of the combustion cylinder 130 , and is arranged coaxially with the combustion cylinder 130 . There is a gap between the bottom of the heating part partition 131 and the lower end of the combustion cylinder 130 through which combustion exhaust gas flows. The heating part partition 131 is configured to accommodate the combustion cylinder 130 with a gap between it and the combustion cylinder 130 .

The first partition 132 has a substantially cylindrical shape with a vertical center axis, an inner diameter larger than the outer diameter of the heating part partition 131, and a lower diameter larger than an upper diameter. The first partition 132 is a metal member that surrounds the outer peripheral surface of the heating part partition 131 with a gap between it and the heating part partition 131 and is arranged coaxially with the heating part partition 131 .

Between the upper portion of the first partition 132 and the heating section partition 131, a spirally bent bar is arranged for spirally flowing the raw material gas containing hydrocarbons and water. A reforming catalyst 150 that generates a primary hydrogen-containing gas (a hydrogen-containing gas containing carbon monoxide) by a reforming reaction from a mixed gas of raw material gas and steam is filled between the lower part and the heating part partition wall 131 . there is

A raw material gas containing hydrocarbons and water pass through while being heated by the heat transmitted from the heating part partition 131 at the place where the spiral bar is arranged between the upper part of the first partition 132 and the heating part partition 131. A portion filled with the reforming catalyst 150 between the lower portion of the first partition 132 and the heating portion partition 131 serves as the reforming portion 122 .

A supply pipe for supplying the raw material gas and water to the evaporator 121 is connected to a portion of the first partition 132 above the location where the spiral bar is arranged.

The evaporating section 121 is formed (configured) by arranging a spirally bent bar in the gap between the heating section partition 131 and the upper portion of the first partition 132 . 120 and the heat of the flue gas) to heat the raw material gas containing hydrocarbons and water to evaporate the water.

The reforming section 122 is formed by filling the gap between the heating section partition wall 131 and the lower part of the first partition wall 132 with a reforming catalyst. Heat and heat of combustion exhaust gas) are transferred, and a primary hydrogen-containing gas containing carbon monoxide is generated by a reforming reaction from the mixed gas of raw material gas and water vapor that flowed out from the evaporator 121 .

The reforming section 122 includes a reforming section lower shelf (not shown) and a reforming section upper shelf (not shown) in addition to the reforming catalyst filled between the lower portion of the first partition 132 and the heating section partition 131 . not shown).

The reforming section lower shelf is a shelf arranged between the lower part of the first partition 132 and the heating section partition 131 so as to support the reforming catalyst from below. The shelf plate is arranged between the lower part of the first partition 132 and the heating part partition 131 so as to cover the . The lower shelf plate of the reforming section and the upper shelf plate of the reforming section have an air-permeable structure, are doughnut-shaped, and have vent holes smaller than the particle size of the reforming catalyst.

The heat transfer buffer cylinder 135 has a substantially tubular shape with a central axis in the vertical direction, and the outer diameter of the outer peripheral surface is larger than the outer diameter of the lower outer peripheral surface of the first partition 132 . The upper and lower ends of the heat transfer buffer cylinder 135 are bent inward so as to form a space for heat transfer buffer between the upper portion of the first partition wall 132 and the outer peripheral surface of the upper portion of the first partition wall 132 . is fixed to

The heat transfer buffer cylinder 135 is fixed to the outer peripheral surface of the portion of the first partition 132 where the evaporator 121 is formed so as to form a space for heat transfer buffer between the evaporator 121 and the CO reduction unit 123. It is a cylindrical member that is used. The heat transfer buffer cylinder 135 is arranged so as to surround the outer peripheral surface of the portion of the first partition 132 where the evaporator 121 is formed and be coaxial with the first partition 132 .

Of the primary hydrogen-containing gas that has flowed out of the reforming unit 122, it flows between the heat transfer buffer cylinder 135 and the first partition 132 without flowing through the CO reduction unit 123, and is discharged out of the hydrogen generator 100. The upper and lower ends of the heat transfer buffer cylinder 135 are hermetically joined to the first partition wall 132 so that the amount of the primary hydrogen-containing gas that is lost does not exceed the allowable amount.

The heat transfer buffer tube 135 has an inner diameter of a portion between the upper end and the lower end larger than the outer diameter of the portion of the first partition 132 where the evaporator 121 is formed, and the inner circumference of the heat transfer buffer tube 135 A space is formed between the surface and the inner peripheral surface of the portion of the first partition 132 where the evaporator 121 is formed. Further, the outer diameter of the portion between the upper end portion and the lower end portion of the heat transfer buffer tube 135 is larger than the outer diameter of the portion of the first partition wall 132 where the reformed portion 122 is formed.

In the heat transfer buffer 135, the CO reduction catalyst of the CO reduction portion 123 adjacent to the outer peripheral side of the heat transfer buffer 135 or the gas flowing on the outer peripheral surface of the heat transfer buffer 135 locally heats through heat exchange with the evaporator 121. It is a member for forming a heat transfer buffer space that suppresses cooling to the outside.

In the heat transfer buffer cylinder 135, the CO reduction catalyst filled between the outer peripheral surface of the heat transfer buffer cylinder 135 and the inner peripheral surface of the upper second partition wall 133 is locally cooled by heat exchange with the evaporator 121. A heat transfer buffer space is formed to suppress the occurrence of temperature unevenness in the CO reduction catalyst.

The heat transfer buffer cylinder 135 forms a heat transfer buffer space between the inner peripheral surface of the heat transfer buffer cylinder 135 and the inner peripheral surface of the portion of the first partition wall 132 where the evaporator 121 is formed. The space suppresses heat transfer (heat exchange) between the evaporation section 121 and the CO reduction section 123 .

The second upper partition wall 133 has a substantially cylindrical shape having a central axis in the vertical direction, surrounds the outer circumference of the heat transfer buffer cylinder 135 with a gap between it and the heat transfer buffer cylinder 135, and the upper end portion is bent inward. is fixed to the outer peripheral surface of the upper portion of the first partition wall 132 .

The upper second partition wall 133 has an inner diameter larger than the outer diameter of the heat transfer buffer cylinder 135 , and surrounds the portion of the first partition wall 132 where the evaporator 121 is configured and the outer peripheral surface of the heat transfer buffer cylinder 135 . It is a metal member that is arranged coaxially with (the heat transfer buffer cylinder 135 ) and constitutes the CO reduction part 123 between the heat transfer buffer cylinder 135 and the heat transfer buffer cylinder 135 .

The second partition top 133 is provided with an outlet pipe for discharging (supplying) the secondary hydrogen-containing gas to the outside of the hydrogen generator 100 above the portion of the second partition top 133 where the CO reduction unit 123 is configured. there is

The second partition wall top 133 allows the primary hydrogen-containing gas that has passed through the return flow path 141 to flow between it and the heat transfer buffer cylinder 135 or between the first partition wall 132 whose outer peripheral surface is not covered with the heat transfer buffer cylinder 135. A flow path leading to the CO reduction section lower shelf 125 (CO reduction section 123) and a flow path for guiding the secondary hydrogen-containing gas flowing out from the CO reduction section upper shelf 124 (CO reduction section 123) to the outlet pipe are also formed. .

The CO reduction section 123 is formed by filling a gap between the heat transfer buffer cylinder 135 and the upper second partition wall 133 with a CO reduction catalyst, and reduces the concentration of carbon monoxide contained in the primary hydrogen-containing gas flowing out of the reforming section 122. is reduced by the modification reaction and discharged as a secondary hydrogen-containing gas.

The CO reduction catalyst is a granular Cu—Zn catalyst with a diameter of 2 to 3 mm, which is filled between the second partition wall 133 and the heat transfer buffer cylinder 135 .

The CO reduction unit lower shelf plate 125 and the CO reduction unit upper shelf plate 124 each have a ventilation structure and are doughnut-shaped shelf plates. The lower shelf plate 125 of the CO reduction unit and the upper shelf plate 124 of the CO reduction unit are formed with air holes having a diameter of 1 mm, which is smaller than the particle diameter of the CO reduction catalyst.

The CO reduction section lower shelf plate 125 is arranged in a gap between the heat transfer buffer tube 135 and the second partition wall top 133 so that the CO reduction catalyst of the CO reduction section 123 does not drop, and is a shelf for supporting the CO reduction catalyst from below. is a board.

The CO reduction unit upper shelf plate 124 is arranged in the gap between the heat transfer buffer cylinder 135 and the second partition wall upper part 133 so that the CO reduction catalyst of the CO reduction unit 123 does not flow upward from the CO reduction unit 123, and the lower surface is CO reduction. A shelf plate for covering the upper surface of the part filled with the CO reduction catalyst so as to be in contact with the catalyst.

The lower second partition wall 134 has a bottomed cylindrical shape with a central axis in the vertical direction, and the upper end of the lower second partition wall 134 abuts on the outer peripheral portion of the lower surface of the lower shelf plate 125 of the CO reduction unit. is joined to the upper second partition wall 133 in a state facing the lower portion of the inner peripheral surface of the upper second partition wall 133, and a gap is provided between the portion of the first partition wall 132 below the CO reduction portion 123 The first partition wall 132 and the heating part partition wall 131 are accommodated.

The second partition bottom 134 has an inner diameter larger than the outer diameter of the portion of the first partition 132 where the reformed portion 122 is formed, and surrounds the outer peripheral surface of the portion of the first partition 132 where the reformed portion 122 is formed. It is a bottomed cylindrical metal member that is arranged coaxially with the first partition 132 and forms a return flow path 141 between the first partition 132 and the portion of the first partition 132 where the reforming section 122 is formed. Between the bottom of the lower 134 and the lower end of the first partition 132 there is a gap through which the primary hydrogen-containing gas flows.

The bottom of the second partition bottom 134 is larger than the bottom of the heating part partition 131 , and the bottom of the second partition bottom 134 is positioned below the bottom of the heating part partition 131 . The outer diameter of the upper end portion of the second lower partition wall 134 is larger than the diameter of the portion other than the upper end portion of the second lower partition wall 134 so that the upper end portion of the second lower partition wall 134 can be joined to the lower end portion of the second upper partition wall 133. is also largely constructed.

The return flow path 141 is formed in a gap between a portion of the first partition 132 below the CO reduction section 123 and the second partition bottom 134, and receives the flow of the primary hydrogen-containing gas flowing downward from the reforming section 122. It is a flow path for turning upward and leading to the CO reduction section 123 .

(Configuration of manufacturing process of hydrogen production device)
As shown in FIG. 2, the method for manufacturing the hydrogen generator 100 includes a CO reduction catalyst filling preparation step 101, a CO reduction catalyst filling step 102, a CO reduction catalyst sealing step 103, and a second partition bottom introduction step 104. , and a second partition bonding step 105 .

In the first CO reduction catalyst filling preparation step 101, in the next CO reduction catalyst filling step 102, a CO reduction This is a step of preparing to fill the catalyst 151 .

In the CO reduction catalyst filling preparation step 101, the heat transfer buffer cylinder 135 is attached and fixed to a predetermined position on the outer peripheral surface of the portion of the first partition 132 where the evaporator 121 is configured, and is attached and fixed to a predetermined position on the first partition 132. At the lower end of the second upper partition wall 133, the lower second partition wall 134 has not yet been arranged, and the upper shelf plate 124 of the CO reduction section has already been attached between the upper second partition wall 133 and the heat transfer buffer cylinder 135. , so that the CO reduction catalyst 151 can be filled in the next CO reduction catalyst filling step 102, the hydrogen This is a step of manufacturing a hydrogen generator and turning it upside down in the direction of gravity when the hydrogen generator is in use (turning it upside down).

The second CO reduction catalyst filling step 102 is surrounded by the second partition wall upper portion 133, the heat transfer buffer cylinder 135, and the CO reduction portion upper shelf plate 124 in a state where the first CO reduction catalyst filling preparation step 101 is completed. In this step, the space is filled with a predetermined weight of the CO reduction catalyst 151 from above the upper shelf plate 124 of the CO reduction unit.

In the third CO reduction catalyst sealing step 103, in a state where the second CO reduction catalyst filling step 102 is completed, the CO reduction section lower shelf plate 125 is vertically attached to the CO reduction catalyst 151 from above.
is introduced toward the portion filled with CO, and the surface of the lower shelf plate 125 of the CO reduction section facing the CO reduction catalyst 151 is installed at a position where the CO reduction catalyst 151 evenly contacts the CO reduction catalyst 151.

In the fourth step 104 of introducing the second partition wall, the second partition wall is turned upside down so that the bottom of the second partition wall 134 faces up in the state where the third CO reduction catalyst sealing step 103 is completed. In this step, the lower part is introduced from above in the vertical direction toward the lower shelf plate 125 of the CO reduction section, and the lower second partition wall 134 is installed at a position where it contacts the lower shelf board 125 of the CO reduction section.

In the fifth step 105 for joining the second partition wall, in a state where the fourth step 104 for introducing the second partition wall bottom is completed, the portion where the upper second partition wall 133 and the lower second partition wall 134 are adjacent to each other is airtightly joined over the entire circumference. It is a process of performing the work to be done.

[1-2. motion]
The operation and function of the hydrogen generator 100 configured as described above will be described below.

(Operation of hydrogen generator)
In order to obtain the necessary amount of hydrogen in the hydrogen generator 100, the raw material gas and water are supplied to the evaporator 121 from the supply pipe at an appropriate ratio.

In the present embodiment, since city gas containing methane as a main component is used as the raw material gas, the amount of water required for the presence of 3 mol of water vapor per 1 mol of methane supplied to the evaporating section 121 is Water is supplied to the evaporator 121 . That is, the city gas and water are supplied to the evaporator 121 by adjusting the water supply flow rate with respect to the city gas supply flow rate so that the steam carbon ratio (S/C ratio) becomes 3.

The supplied water flows along the helical flow path of the evaporator 121 and becomes water vapor by the heat of the heating unit 120 (including the heat of the combustion exhaust gas) transmitted through the heating unit partition 131, and is mixed with the raw material gas. be.

The mixed gas of the raw material gas and water vapor is supplied to the reforming section 122, and the heat of the heating section 120 (including the heat of the combustion exhaust gas) transmitted through the heating section partition wall 131 reaches a temperature suitable for the reforming reaction (approximately 600°C). ), a steam reforming reaction is carried out by the reforming catalyst heated to ), resulting in a primary hydrogen-containing gas.

Note that the temperature of the reforming catalyst exemplified as 600° C. in the present embodiment is a typical temperature, and the temperature in the reforming section 122 that causes the reforming reaction depends on the structure and material of the reforming section 122, It also depends on the size. The temperature inside the reforming section 122 that causes the reforming reaction can vary, for example, in the range of 400.degree. C. to 650.degree.

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 section 123 from below. reacts to reduce the CO concentration in the primary hydrogen-containing gas to about 0.1 to 0.2%, resulting in a secondary hydrogen-containing gas.

At this time, the CO reduction catalyst 151 receives the heat of the primary hydrogen-containing gas discharged from the reforming section 122 (the reforming catalyst 150) and flowing into the CO reduction section 123, It is heated to about 250° C., which is a temperature suitable for the shift reaction, by cold heat transmitted to the CO reduction catalyst 151 through the space and the heat transfer buffer cylinder 135 .

Note that the temperature of the CO reduction catalyst 151 exemplified as 250° C. in the present embodiment is a typical temperature, and the temperature in the CO reduction section 123 causing the shift reaction varies depending on the structure and material of the CO reduction section 123, It also depends on the size. The temperature in the CO reduction section 123 where the transformation reaction occurs can vary, for example, within the range of 200°C to 300°C.

The secondary hydrogen-containing gas discharged from the CO reduction unit 123 exits the hydrogen generator 100 through the outlet pipe and is supplied to a hydrogen utilization device such as a fuel cell.

The combustion exhaust gas generated by the combustion of the burner of the heating section 120 flows downward along the inner peripheral surface of the combustion tube 130 and then flows downward along the inner peripheral side of the combustion tube 130, and then reaches the bottom of the heating section partition 131 and the lower end of the combustion tube 130. The flue gas flow path 140 formed between the combustion cylinder 130 and the heating section partition wall 131 is folded upward through the gap between and heat-exchanged with the reforming section 122, and then heat-exchanged with the evaporating section 121. Then, it is discharged to the outside of the hydrogen generator 100 from a combustion exhaust gas outlet pipe provided in the upper part of the heating part partition 131 .

(Manufacturing process related to the CO reduction part of the hydrogen generator)
In the first CO reduction catalyst filling preparation step 101, in the next CO reduction catalyst filling step 102, CO reduction is filled in the space surrounded by the second partition upper 133, the heat transfer buffer cylinder 135, and the CO reduction unit upper shelf plate 124. Preparations are made so that the catalyst 151 can be filled.

Specifically, in the first CO reduction catalyst filling preparation step 101, the heat transfer buffer cylinder 135 is attached and fixed at a predetermined position on the outer peripheral surface of the portion of the first partition 132 where the evaporator 121 is formed, and the first partition At the lower end of the upper second partition wall 133 that has already been attached and fixed to the predetermined position of 132 , the lower second partition wall 134 is not yet arranged, and the upper shelf of the CO reduction unit is placed between the upper second partition wall 133 and the heat transfer buffer cylinder 135 . Although the plate 124 has already been attached, the CO reduction section lower shelf plate 125 is still between the second bulkhead top 133 and the heat transfer buffer cylinder 135 so that the CO reduction catalyst 151 can be filled in the next CO reduction catalyst filling step 102. The hydrogen generator is manufactured until it is not placed, and the work of turning the hydrogen generator upside down in the direction of gravity when it is in use (turning it upside down) is performed.

The CO reduction unit upper shelf plate 124 is attached to the heat transfer buffer cylinder 135 before the second partition wall top 133 is attached to a predetermined position of the first partition wall 132 so that the second partition wall top 133 surrounds the outer peripheral surface of the heat transfer buffer cylinder 135 . It is fixed by welding to either a predetermined position on the outer peripheral surface or a predetermined position on the inner peripheral surface of the second partition wall 133 .

Before the first partition 132 is arranged on the outer peripheral side of the heating part partition 131 so that the first partition 132 surrounds the outer peripheral surface of the heating part partition 131 , the reforming part upper shelf is provided with a predetermined amount of pressure on the outer peripheral surface of the heating part partition 131 . It is fixed by welding to either a position or a predetermined position on the inner peripheral surface of the lower portion of the first partition wall 132 .

The reforming catalyst is placed under the first partition 132 and the heating part partition 131 after performing the work of inverting the gravity direction when the hydrogen generator is used in the CO reduction catalyst filling preparation step 101 (upside down). and the upper shelf plate of the reforming section.

The reforming section upper shelf plate is arranged between the lower part of the first partition wall 132 and the heating section partition wall 131 by the step 104 of introduction below the second partition wall after the reforming catalyst is filled, and the first partition wall 132 It is fixed by welding or the like to at least one of the inner peripheral surface of the lower portion and the outer peripheral surface of the heating portion partition wall 131 .

Before the first partition 132 is arranged on the outer peripheral side of the heating part partition 131 so that the first partition 132 surrounds the outer peripheral surface of the heating part partition 131 , the helically bent bar of the evaporating part 121 is attached to the heating part 121 . After the first partition 132 is arranged on the outer peripheral side of the heating part partition 131 so that the first partition 132 surrounds the outer peripheral surface of the heating part partition 131, the heating part partition 131 is attached. The pipe is expanded and the helically bent bar is brought into close contact with the upper inner peripheral surface of the first partition wall 132 .

In the second CO reduction catalyst filling step 102, in the state where the first CO reduction catalyst filling preparation step 101 is completed, the second partition wall upper part 133, the heat transfer buffer cylinder 135, and the CO reduction part upper shelf plate 124 A predetermined weight of the CO reduction catalyst 151 is filled into the space from above the CO reduction unit upper shelf plate 124 .

In the third CO reduction catalyst sealing step 103, in a state where the second CO reduction catalyst filling step 102 is completed, the CO reduction section lower shelf plate 125 is vertically moved from above to the portion filled with the CO reduction catalyst 151. Then, the surface of the lower shelf plate 125 of the CO reduction section facing the CO reduction catalyst 151 is installed at a position where the CO reduction catalyst 151 evenly contacts the CO reduction catalyst 151 .

Therefore, the variation in the volume of the CO reduction section 123 caused by the filling state of the CO reduction catalyst 151 can be absorbed by installing the CO reduction section lower shelf plate 125 .

Since the outer diameter of the heat transfer buffer cylinder 135 is configured to be larger than the outer diameter of the portion of the first partition 132 where the reformed portion 122 is formed (the lower part of the first partition 132), the heat transfer buffer cylinder 135 The inner diameter of the CO reduction section lower shelf plate 125 installed on the outer peripheral side of is made larger than the outer diameter of the portion of the first partition wall 132 where the reforming section 122 is formed.

Therefore, when the CO reduction section lower shelf plate 125 is installed at a predetermined position by passing through the portion of the first partition 132 where the reforming section 122 is formed, the reforming section 122 of the first partition 132 is formed. The CO reduction unit lower shelf plate 125 can be introduced to a position where it abuts on the portion filled with the CO reduction catalyst 151 without being obstructed by the portion where the CO reduction catalyst 151 is placed.

In the fourth step 104 of introducing the lower second partition wall, the second partition wall is turned upside down so that the bottom of the lower second partition wall 134 faces up in the state where the third CO reduction catalyst sealing step 103 is completed. The second partition bottom 134 is installed at a position where the second partition wall bottom 134 comes into contact with the CO reduction section bottom shelf 125 by introducing the bottom from above in the vertical direction toward the CO reduction section bottom shelf 125 .

In the fifth step 105 for joining the second partition wall, in a state where the fourth step 104 for introducing the second partition wall bottom is completed, the portion where the upper second partition wall 133 and the lower second partition wall 134 are adjacent to each other is airtightly joined over the entire circumference. work to be done.

As a result, the lower shelf plate 125 of the CO reduction unit does not need to be directly joined (welded) to at least one of the inner peripheral surface of the upper second partition wall 133 and the outer peripheral surface of the heat transfer buffer cylinder 135. A second partition bottom 134 that supports the CO reduction section bottom shelf 125 from below and is joined to the second partition top 133 causes the weight of the CO reduction catalyst 151 and the CO reduction section bottom shelf 125 to cause the CO reduction section bottom shelf 125 to fall off. The CO reduction section lower shelf 125 can be fixed so that it does not.

[1-3. effect]
As described above, the hydrogen generator 100 according to the present embodiment includes the heating section 120, the combustion cylinder 130, the heating section partition wall 131, the first partition wall 132, the flue gas flow path 140, the evaporating section 121, the reforming section 122, and the transmission. It has a heat buffer cylinder 135 , a second partition upper portion 133 , a CO reduction portion 123 , a CO reduction portion lower shelf plate 125 , a CO reduction portion upper shelf plate 124 , a second partition lower portion 134 , and a return channel 141 .

Then, the method for manufacturing the hydrogen generator 100 in the present embodiment includes a CO reduction catalyst filling preparation step 101, a CO reduction catalyst filling step 102, a CO reduction catalyst sealing step 103, a second partition under introduction step 104, and a second partition wall and a joining step 105 .

The heating unit 120 is configured to burn combustible gas and discharge flue gas. The combustion tube 130 has a tubular shape having a central axis in the vertical direction and surrounds the outer circumference of the heating section 120, and is configured so that combustion exhaust gas flows downward inside the tube. The heating section partition 131 has a bottomed tubular shape with a central axis in the vertical direction, and is configured to accommodate the combustion tube 130 with a gap between it and the combustion tube 130 .

The first partition wall 132 has a substantially cylindrical shape having a central axis in the vertical direction, and is configured such that the diameter of the lower portion is larger than the diameter of the upper portion, and the outer periphery of the heating portion partition wall 131 is provided with a gap between it and the heating portion partition wall 131 . surround. The combustion exhaust gas flow path 140 is a flow path formed in a gap between the combustion cylinder 130 and the heating section partition wall 131 and through which the combustion exhaust gas flows upward.

The evaporator 121 is formed in a gap between the heating partition wall 131 and the upper portion of the first partition wall 132, and is configured to heat the raw material gas and water by heat transmitted through the heating partition wall 131, thereby evaporating the water. It is

The reforming section 122 is formed by filling the gap between the heating section partition 131 and the lower portion of the first partition 132 with a reforming catalyst. It is configured to generate a primary hydrogen-containing gas containing carbon monoxide through a reforming reaction from the mixed gas of the raw material gas and water vapor that flowed out of the unit 121 .

The heat transfer buffer cylinder 135 has a substantially cylindrical shape with a central axis in the vertical direction, and has an outer diameter larger than that of the outer peripheral surface of the lower portion of the first partition 132 , and is spaced from the upper portion of the first partition 132 . The upper and lower ends are bent inward and fixed to the outer peripheral surface of the upper portion of the first partition wall 132 so that a space for heat transfer buffering is formed at the bottom.

The second upper partition wall 133 has a substantially cylindrical shape having a central axis in the vertical direction, surrounds the outer circumference of the heat transfer buffer cylinder 135 with a gap between it and the heat transfer buffer cylinder 135, and the upper end portion is bent inward. is fixed to the outer peripheral surface of the upper portion of the first partition wall 132 .

The CO reduction section 123 is formed by filling a gap between the heat transfer buffer cylinder 135 and the second partition wall upper portion 133 with a CO reduction catalyst 151, and reduces carbon monoxide contained in the primary hydrogen-containing gas flowing out of the reforming section 122. The concentration is reduced by a denaturation reaction and is configured to be discharged as a secondary hydrogen-containing gas.

The lower shelf plate 125 of the CO reduction section 125 is a donut disk-shaped shelf with a ventilation structure arranged in the gap between the heat transfer buffer cylinder 135 and the upper second partition wall 133 so that the CO reduction catalyst 151 of the CO reduction section 123 does not drop. It is a plate and supports the CO reduction catalyst 151 from below.

The CO reduction unit upper shelf plate 124 is arranged in a gap between the heat transfer buffer cylinder 135 and the second partition wall top 133 so that the CO reduction catalyst 151 of the CO reduction unit 123 does not flow upward from the CO reduction unit 123. It is a donut disk-shaped shelf plate in structure, and covers the upper surface of the part filled with the CO reduction catalyst 151 so that the lower surface contacts the CO reduction catalyst 151 .

The lower second partition wall 134 has a bottomed cylindrical shape with a central axis in the vertical direction. The first partition wall 132 and the heating part partition wall 131 are joined to the upper part of the second partition wall 133 in a state facing the lower part thereof, and a gap is provided between the first partition wall 132 and the portion below the CO reduction part 123 in the first partition wall 132 and the heating part partition wall 131. configured to store.

The return flow path 141 is formed in a gap between a portion of the first partition 132 below the CO reduction section 123 and the second partition bottom 134, and receives the flow of the primary hydrogen-containing gas flowing downward from the reforming section 122. It is a flow path for turning upward and leading to the CO reduction section 123 .

In the first CO reduction catalyst filling preparation step 101, the second partition wall top 133 is not yet placed below the second partition wall top 133 that has been attached to a predetermined position, and the second partition wall top 133 and the second partition wall 133 are heat transfer buffers. Although the CO reduction unit upper shelf plate 124 has already been attached to a predetermined position in the gap between the cylinder 135 and the CO reduction unit lower shelf plate 125, the CO reduction catalyst 151 and the CO reduction unit lower shelf plate 125 are still located between the second partition wall top 133 and the heat transfer buffer cylinder 135. In this process, the hydrogen generator is manufactured so that it is not placed in the gap, and the hydrogen generator is turned upside down in the direction of gravity during use.

The second CO reduction catalyst filling step 102 is surrounded by the second partition wall upper portion 133, the heat transfer buffer cylinder 135, and the CO reduction portion upper shelf plate 124 in a state where the first CO reduction catalyst filling preparation step 101 is completed. This is a step of filling the space with a predetermined weight of the CO reduction catalyst 151 from above.

In the third CO reduction catalyst sealing step 103, in a state where the second CO reduction catalyst filling step 102 is completed, the CO reduction section lower shelf plate 125 is introduced from above toward the portion filled with the CO reduction catalyst 151. Then, the surface of the lower shelf plate 125 of the CO reduction section facing the CO reduction catalyst 151 is installed at a position where the CO reduction catalyst 151 evenly contacts the CO reduction catalyst 151 .

In the fourth step 104 of introducing the second partition wall, the second partition wall is turned upside down so that the bottom of the second partition wall 134 faces up in the state where the third CO reduction catalyst sealing step 103 is completed. In this step, the lower part 134 is introduced from above toward the CO reducing part lower shelf plate 125 and installed at a position where the second partition lower part 134 comes into contact with the CO reducing part lower shelf plate 125 .

A fifth step 105 for joining the second partition wall is a step of air-tightly joining the portions where the lower second partition wall 134 and the upper second partition wall 133 are adjacent to each other in a state where the fourth step 104 for introducing below the second partition wall is completed. be.

In the method of manufacturing the hydrogen generator 100 according to the present embodiment, in the assembly of the CO reduction unit 123, the upper shelf plate 124 of the CO reduction unit is first fixed, and the direction of gravity is reversed from that when the hydrogen generation unit 100 is used. By adopting a manufacturing method in which the CO reduction catalyst 151 is filled in the state and the CO reduction section lower shelf plate 125 is installed upstream of the CO reduction catalyst 151, the following effects can be obtained.

By fixing the CO reduction section upper shelf plate 124 in advance at a predetermined position, it is possible to absorb variations in the volume of the filled CO reduction catalyst 151 at the fixed position of the CO reduction section lower shelf plate 125 , and the CO reduction section upper shelf plate 125 is fixed. Variation in the position of the plate 124 can be suppressed.

Therefore, since the downstream position of the CO reduction catalyst 151 can be kept constant, the distance between the downstream position of the CO reduction catalyst 151 and the heating unit 120 can be kept constant, and the temperature of the downstream part of the CO reduction catalyst 151 can be kept constant. Since the concentration of CO contained in the hydrogen-containing gas after passing through the CO reduction section 123 depends on the temperature of the downstream portion of the CO reduction catalyst 151, it is possible to suppress individual differences in the CO concentration in the post-shifting reaction gas.

In addition, for the CO reduction unit lower shelf plate 125, the work of directly joining (welding) to at least one of the inner peripheral surface of the second partition upper 133 and the outer peripheral surface of the heat transfer buffer cylinder 135 is not performed. A second partition bottom 134 that supports the reduction section lower shelf 125 from below and is joined to the second partition top 133 prevents the CO reduction section lower shelf 125 from falling off due to the weight of the CO reduction catalyst 151 and the CO reduction section lower shelf 125. The CO reduction section lower shelf plate 125 can be fixed as follows.

(Embodiment 2)
Embodiment 2 will be described below with reference to FIGS. 3 and 4. FIG.

[2-1. composition]
As shown in FIG. 3, the hydrogen generator 200 includes a heating unit 120, an evaporating unit 121, a reforming unit 122, a CO reducing unit 123, a CO reducing unit upper shelf 124, a CO reducing unit lower shelf 125, a combustion cylinder 130, and a heating unit. It has a partition wall 131 , a first partition wall 132 , a second upper partition wall 133 , a second lower partition wall 134 , a heat transfer buffer cylinder 135 , a flue gas flow path 140 and a return flow path 141 .

The heating unit 120 is arranged on the inner peripheral side of a combustion cylinder 130 having a central axis in the vertical direction, and includes a burner that burns combustible gas mixed with combustion air and discharges combustion exhaust gas, and a combustible gas in the burner. and a combustion air supply pipe for supplying combustion air to the burner. The burners of heating section 120 are configured to produce downward flames.

Raw material gas (city gas or LP gas) can be used as the combustible gas. In addition, when the hydrogen generator 200 supplies hydrogen-containing gas to the fuel cell as fuel gas, it is used in the fuel cell. A fuel gas (anode off-gas) discharged from the fuel cell can be used.

Combustion cylinder 130 has a cylindrical shape having a central axis in the vertical direction and surrounds the outer periphery of heating section 120 , and is arranged coaxially with heating section 120 . In the combustion tube 130, the combustion exhaust gas flows downward (downward in the vertical direction) on the inner peripheral side of the combustion tube 130, and the combustion gas formed between the combustion tube 130 and the heating section partition 131 on the outer peripheral side of the combustion tube 130. The exhaust gas passage 140) is a member for causing the combustion exhaust gas to flow upward (upward in the vertical direction).

The lower end of the combustion tube 130 is located vertically below the lower end of the reforming section 122, and the bottom of a bottomed cylindrical heating section partition 131 that surrounds the combustion tube 130 and is arranged coaxially with the combustion tube 130. located vertically above

In the hydrogen generator 200, after the flue gas generated by the combustion of the burner of the heating section 120 flows downward along the inner peripheral surface of the combustion tube 130 along the inner peripheral side of the combustion tube 130, it reaches the bottom portion of the heating section partition wall 131. and the lower end of the combustion cylinder 130 and flows upward, and after heat exchange with the reforming section 122 through the combustion exhaust gas flow path 140 formed between the combustion cylinder 130 and the heating section partition 131, , exchanges heat with the evaporating section 121 , and is discharged to the outside of the hydrogen generator 200 from a combustion exhaust gas outlet pipe provided in the upper portion of the heating section partition 131 .

The combustion exhaust gas flow path 140 is a flow path formed in a gap between the combustion cylinder 130 and the heating section partition wall 131 and through which the combustion exhaust gas flows upward.

The heating part partition wall 131 has an inner diameter larger than the outer diameter of the combustion cylinder 130 , surrounds the outer peripheral surface of the combustion cylinder 130 , and is arranged coaxially with the combustion cylinder 130 . There is a gap between the bottom of the heating part partition 131 and the lower end of the combustion cylinder 130 through which combustion exhaust gas flows. The heating part partition 131 is configured to accommodate the combustion cylinder 130 with a gap between it and the combustion cylinder 130 .

The first partition 132 has a substantially cylindrical shape with a vertical center axis, an inner diameter larger than the outer diameter of the heating part partition 131, and a lower diameter larger than an upper diameter. The first partition 132 surrounds the outer peripheral surface of the heating part partition 131 with a gap between it and the heating part partition 131 .
It is a metal member arranged so as to be coaxial with 31 .

Between the upper portion of the first partition 132 and the heating section partition 131, a spirally bent bar is arranged for spirally flowing the raw material gas containing hydrocarbons and water. A reforming catalyst 150 that generates a primary hydrogen-containing gas (a hydrogen-containing gas containing carbon monoxide) by a reforming reaction from a mixed gas of raw material gas and steam is filled between the lower part and the heating part partition wall 131 . there is

A raw material gas containing hydrocarbons and water pass through while being heated by the heat transmitted from the heating part partition 131 at the place where the spiral bar is arranged between the upper part of the first partition 132 and the heating part partition 131. A portion filled with the reforming catalyst 150 between the lower portion of the first partition 132 and the heating portion partition 131 serves as the reforming portion 122 .

A supply pipe for supplying the raw material gas and water to the evaporator 121 is connected to a portion of the first partition 132 above the location where the spiral bar is arranged.

The evaporating section 121 is formed (configured) by arranging a spirally bent bar in the gap between the heating section partition 131 and the upper portion of the first partition 132 . 120 and the heat of the flue gas) to heat the raw material gas containing hydrocarbons and water to evaporate the water.

The reforming section 122 is formed by filling the gap between the heating section partition wall 131 and the lower part of the first partition wall 132 with a reforming catalyst. Heat and heat of combustion exhaust gas) are transferred, and a primary hydrogen-containing gas containing carbon monoxide is generated by a reforming reaction from the mixed gas of raw material gas and water vapor that flowed out from the evaporator 121 .

The reforming section 122 includes a reforming section lower shelf (not shown) and a reforming section upper shelf (not shown) in addition to the reforming catalyst filled between the lower portion of the first partition 132 and the heating section partition 131 . not shown).

The reforming section lower shelf is a shelf arranged between the lower part of the first partition 132 and the heating section partition 131 so as to support the reforming catalyst from below. The shelf plate is arranged between the lower part of the first partition 132 and the heating part partition 131 so as to cover the . The lower shelf plate of the reforming section and the upper shelf plate of the reforming section have an air-permeable structure, are doughnut-shaped, and have vent holes smaller than the particle size of the reforming catalyst.

The heat transfer buffer cylinder 135 has a substantially tubular shape with a central axis in the vertical direction, and the outer diameter of the outer peripheral surface is larger than the outer diameter of the lower outer peripheral surface of the first partition 132 . The upper and lower ends of the heat transfer buffer cylinder 135 are bent inward so as to form a space for heat transfer buffer between the upper portion of the first partition wall 132 and the outer peripheral surface of the upper portion of the first partition wall 132 . is fixed to

The heat transfer buffer cylinder 135 is fixed to the outer peripheral surface of the portion of the first partition 132 where the evaporator 121 is formed so as to form a space for heat transfer buffer between the evaporator 121 and the CO reduction unit 123. It is a cylindrical member that is used. The heat transfer buffer cylinder 135 is arranged so as to surround the outer peripheral surface of the portion of the first partition 132 where the evaporator 121 is formed and be coaxial with the first partition 132 .

Of the primary hydrogen-containing gas that has flowed out of the reforming section 122, it flows between the heat transfer buffer tube 135 and the first partition 132 without flowing through the CO reduction section 123, and is discharged outside the hydrogen generator 200. The upper and lower ends of the heat transfer buffer cylinder 135 are hermetically joined to the first partition wall 132 so that the amount of the primary hydrogen-containing gas that is lost does not exceed the allowable amount.

The heat transfer buffer tube 135 has an inner diameter of a portion between the upper end and the lower end larger than the outer diameter of the portion of the first partition 132 where the evaporator 121 is formed, and the inner circumference of the heat transfer buffer tube 135 A space is formed between the surface and the inner peripheral surface of the portion of the first partition 132 where the evaporator 121 is formed. Further, the outer diameter of the portion between the upper end portion and the lower end portion of the heat transfer buffer tube 135 is larger than the outer diameter of the portion of the first partition wall 132 where the reformed portion 122 is formed.

In the heat transfer buffer 135, the CO reduction catalyst of the CO reduction portion 123 adjacent to the outer peripheral side of the heat transfer buffer 135 or the gas flowing on the outer peripheral surface of the heat transfer buffer 135 locally heats through heat exchange with the evaporator 121. It is a member for forming a heat transfer buffer space that suppresses cooling to the outside.

In the heat transfer buffer cylinder 135, the CO reduction catalyst filled between the outer peripheral surface of the heat transfer buffer cylinder 135 and the inner peripheral surface of the upper second partition wall 133 is locally cooled by heat exchange with the evaporator 121. A heat transfer buffer space is formed to suppress the occurrence of temperature unevenness in the CO reduction catalyst.

The heat transfer buffer cylinder 135 forms a heat transfer buffer space between the inner peripheral surface of the heat transfer buffer cylinder 135 and the inner peripheral surface of the portion of the first partition wall 132 where the evaporator 121 is formed. The space suppresses heat transfer (heat exchange) between the evaporation section 121 and the CO reduction section 123 .

The second upper partition wall 133 has a substantially cylindrical shape having a central axis in the vertical direction, surrounds the outer circumference of the heat transfer buffer cylinder 135 with a gap between it and the heat transfer buffer cylinder 135, and the upper end portion is bent inward. is fixed to the outer peripheral surface of the upper portion of the first partition wall 132 .

The upper second partition wall 133 has an inner diameter larger than the outer diameter of the heat transfer buffer cylinder 135 , and surrounds the portion of the first partition wall 132 where the evaporator 121 is configured and the outer peripheral surface of the heat transfer buffer cylinder 135 . It is a metal member that is arranged coaxially with (the heat transfer buffer cylinder 135 ) and constitutes the CO reduction part 123 between the heat transfer buffer cylinder 135 and the heat transfer buffer cylinder 135 .

The second partition wall 133 is provided with an outlet pipe for discharging (supplying) the secondary hydrogen-containing gas to the outside of the hydrogen generator 200 above the portion of the second partition wall 133 where the CO reduction unit 123 is configured. there is

The second partition wall top 133 allows the primary hydrogen-containing gas that has passed through the return flow path 141 to flow between it and the heat transfer buffer cylinder 135 or between the first partition wall 132 whose outer peripheral surface is not covered with the heat transfer buffer cylinder 135. A flow path leading to the CO reduction section lower shelf 125 (CO reduction section 123) and a flow path for guiding the secondary hydrogen-containing gas flowing out from the CO reduction section upper shelf 124 (CO reduction section 123) to the outlet pipe are also formed. .

The CO reduction section 123 is formed by filling a gap between the heat transfer buffer cylinder 135 and the upper second partition wall 133 with a CO reduction catalyst, and reduces the concentration of carbon monoxide contained in the primary hydrogen-containing gas flowing out of the reforming section 122. is reduced by the modification reaction and discharged as a secondary hydrogen-containing gas.

The CO reduction catalyst is a granular Cu—Zn catalyst with a diameter of 2 to 3 mm, which is filled between the second partition wall 133 and the heat transfer buffer cylinder 135 .

The CO reduction unit lower shelf plate 125 and the CO reduction unit upper shelf plate 124 each have a ventilation structure and are doughnut-shaped shelf plates. The lower shelf plate 125 of the CO reduction unit and the upper shelf plate 124 of the CO reduction unit are formed with air holes having a diameter of 1 mm, which is smaller than the particle diameter of the CO reduction catalyst.

The CO reduction section lower shelf plate 125 is arranged in a gap between the heat transfer buffer tube 135 and the second partition wall top 133 so that the CO reduction catalyst of the CO reduction section 123 does not drop, and is a shelf for supporting the CO reduction catalyst from below. is a board. In addition, the CO reduction section lower shelf 125 of the present embodiment is configured integrally with the second partition wall lower 134 .

The CO reduction unit upper shelf plate 124 is arranged in the gap between the heat transfer buffer cylinder 135 and the second partition wall upper part 133 so that the CO reduction catalyst of the CO reduction unit 123 does not flow upward from the CO reduction unit 123, and the lower surface is CO reduction. A shelf plate for covering the upper surface of the part filled with the CO reduction catalyst so as to be in contact with the catalyst.

The second partition bottom 134 has a bottomed tubular shape with a central axis in the vertical direction, and is integrally formed with the CO reduction unit lower shelf plate 125 . The first partition wall 132 and the heating part partition wall 131 are joined to the upper part of the second partition wall 133 so as to face the lower part of the peripheral surface, and the first partition wall 132 and the heating part partition wall 131 are separated from the part of the first partition wall 132 below the CO reduction part 123 with a gap therebetween. It is configured to accommodate the

The second partition bottom 134 has an inner diameter larger than the outer diameter of the portion of the first partition 132 where the reformed portion 122 is formed, and surrounds the outer peripheral surface of the portion of the first partition 132 where the reformed portion 122 is formed. It is a bottomed cylindrical metal member that is arranged coaxially with the first partition 132 and forms a return flow path 141 between the first partition 132 and the portion of the first partition 132 where the reforming section 122 is formed. Between the bottom of the lower 134 and the lower end of the first partition 132 there is a gap through which the primary hydrogen-containing gas flows.

The bottom of the second partition bottom 134 is larger than the bottom of the heating part partition 131 , and the bottom of the second partition bottom 134 is positioned below the bottom of the heating part partition 131 . The outer diameter of the upper end portion of the second lower partition wall 134 is larger than the diameter of the portion other than the upper end portion of the second lower partition wall 134 so that the upper end portion of the second lower partition wall 134 can be joined to the lower end portion of the second upper partition wall 133. is also largely constructed.

The return flow path 141 is formed in a gap between a portion of the first partition 132 below the CO reduction section 123 and the second partition bottom 134, and receives the flow of the primary hydrogen-containing gas flowing downward from the reforming section 122. It is a flow path for turning upward and leading to the CO reduction section 123 .

(Configuration of manufacturing process of hydrogen production device)
As shown in FIG. 4, the method for manufacturing the hydrogen generator 200 includes a CO reduction catalyst filling preparation step 201, a CO reduction catalyst filling step 202, a second partition under introduction step 203, a second partition wall joining step 204, have

The first CO reduction catalyst filling preparation step 201 is the following CO reduction catalyst filling step 202. In the space surrounded by the second partition upper part 133, the heat transfer buffer cylinder 135, and the CO reduction part upper shelf plate 124, CO reduction This is a step of preparing to fill the catalyst 151 .

In the CO reduction catalyst filling preparation step 201, the heat transfer buffer cylinder 135 is attached and fixed to a predetermined position on the outer peripheral surface of the portion of the first partition 132 where the evaporator 121 is configured, and is attached and fixed to a predetermined position on the first partition 132. At the lower end of the second upper partition wall 133, the lower second partition wall 134 has not yet been arranged, and the upper shelf plate 124 of the CO reduction section has already been attached between the upper second partition wall 133 and the heat transfer buffer cylinder 135. , so that the CO reduction catalyst 151 can be filled in the next CO reduction catalyst filling step 202, the CO reduction catalyst 151 and the CO reduction unit lower shelf plate 125 integrated with the second partition bottom 134 are still in the second partition top 133 and the heat transfer buffer cylinder 135, and then turn the hydrogen generator upside down in the direction of gravity when it is in use (upside down).

The second CO reduction catalyst filling process 202 is surrounded by the second partition upper part 133, the heat transfer buffer cylinder 135, and the CO reduction part upper shelf plate 124 in the state where the first CO reduction catalyst filling preparation process 201 is completed. In this step, the space is filled with a predetermined weight of the CO reduction catalyst 151 from above the upper shelf plate 124 of the CO reduction unit.

In the third second partition bottom introduction step 203, in a state where the second CO reduction catalyst filling step 202 is completed, the CO reduction section lower shelf plate 125 is at the bottom and the bottom of the second partition bottom 134 is at the top. is introduced from above toward the portion filled with the CO reduction catalyst 151 to face the CO reduction catalyst 151 on the CO reduction section lower shelf 125. In this step, the surface is installed at a position where it evenly abuts on the CO reduction catalyst 151 .

In the fourth step 204 for joining the second partition wall, in a state where the third step 203 for introducing the second partition wall below is completed, the portion where the upper second partition wall 133 and the lower second partition wall 134 are adjacent to each other is airtightly joined over the entire circumference. It is a process of performing the work to be done.

[2-2. motion]
The operation and function of the hydrogen generator 200 configured as described above will be described below.

(Operation of hydrogen generator)
In order to obtain the necessary amount of hydrogen in the hydrogen generator 200, the material gas and water are supplied to the evaporation section 121 from the supply pipe in a proper ratio.

The supplied water flows along the helical flow path of the evaporator 121 and becomes water vapor by the heat of the heating unit 120 (including the heat of the combustion exhaust gas) transmitted through the heating unit partition 131, and is mixed with the raw material gas. be.

The mixed gas of the raw material gas and water vapor is supplied to the reforming section 122 and 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 wall 131. A steam reforming reaction is performed by the reforming catalyst to produce a primary hydrogen-containing gas.

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 section 123 from below. reacts to reduce the CO concentration in the primary hydrogen-containing gas to about 0.1 to 0.2%, resulting in a secondary hydrogen-containing gas.

At this time, the CO reduction catalyst 151 receives the heat of the primary hydrogen-containing gas discharged from the reforming section 122 (the reforming catalyst 150) and flowing into the CO reduction section 123, It is heated to a temperature suitable for the shift reaction by cold heat transmitted to the CO reduction catalyst 151 through the space and the heat transfer buffer cylinder 135 .

The secondary hydrogen-containing gas discharged from the CO reduction unit 123 exits the hydrogen generator 200 through the outlet pipe and is supplied to a hydrogen utilization device such as a fuel cell.

The combustion exhaust gas generated by the combustion of the burner of the heating section 120 flows downward along the inner peripheral surface of the combustion tube 130 and then flows downward along the inner peripheral side of the combustion tube 130, and then reaches the bottom of the heating section partition 131 and the lower end of the combustion tube 130. The flue gas flow path 140 formed between the combustion cylinder 130 and the heating section partition wall 131 is folded upward through the gap between and heat-exchanged with the reforming section 122, and then heat-exchanged with the evaporating section 121. Then, it is discharged to the outside of the hydrogen generator 200 from a combustion exhaust gas outlet pipe provided in the upper part of the heating part partition 131 .

(Manufacturing process related to the CO reduction part of the hydrogen generator)
In the first CO reduction catalyst filling preparation step 201, in the next CO reduction catalyst filling step 202, CO reduction is filled in the space surrounded by the second partition upper 133, the heat transfer buffer cylinder 135, and the CO reduction unit upper shelf plate 124. Preparations are made so that the catalyst 151 can be filled.

Specifically, in the first CO reduction catalyst filling preparation step 201, the heat transfer buffer cylinder 135 is attached and fixed to a predetermined position on the outer peripheral surface of the portion of the first partition 132 where the evaporator 121 is formed, and the first partition At the lower end of the upper second partition wall 133 that has already been attached and fixed to the predetermined position of 132 , the lower second partition wall 134 is not yet arranged, and the upper shelf of the CO reduction unit is placed between the upper second partition wall 133 and the heat transfer buffer cylinder 135 . Although the plate 124 has been attached, the CO reduction catalyst 151 and the CO reduction section lower shelf plate 125 integrated with the second partition wall lower 134 are added so that the CO reduction catalyst 151 can be filled in the next CO reduction catalyst filling step 202. is to manufacture the hydrogen generator until it is not yet placed between the second partition top 133 and the heat transfer buffer cylinder 135, and turn the hydrogen generator upside down in the direction of gravity during use (upside down work).

The CO reduction unit upper shelf plate 124 is attached to the heat transfer buffer cylinder 135 before the second partition wall top 133 is attached to a predetermined position of the first partition wall 132 so that the second partition wall top 133 surrounds the outer peripheral surface of the heat transfer buffer cylinder 135 . It is fixed by welding to either a predetermined position on the outer peripheral surface or a predetermined position on the inner peripheral surface of the second partition wall 133 .

Before the first partition 132 is arranged on the outer peripheral side of the heating part partition 131 so that the first partition 132 surrounds the outer peripheral surface of the heating part partition 131 , the reforming part upper shelf is provided with a predetermined amount of pressure on the outer peripheral surface of the heating part partition 131 . It is fixed by welding to either a position or a predetermined position on the inner peripheral surface of the lower portion of the first partition wall 132 .

The reforming catalyst is placed under the first partition 132 and the heating part partition 131 after performing the work of inverting the gravity direction when the hydrogen generator is used in the CO reduction catalyst filling preparation step 101 (upside down). and the upper shelf plate of the reforming section.

After the reforming catalyst is filled, the reforming section upper shelf plate is arranged between the lower part of the first partition wall 132 and the heating section partition wall 131 by the step 203 of introduction below the second partition wall. It is fixed by welding or the like to at least one of the inner peripheral surface of the lower portion and the outer peripheral surface of the heating portion partition wall 131 .

Before the first partition 132 is arranged on the outer peripheral side of the heating part partition 131 so that the first partition 132 surrounds the outer peripheral surface of the heating part partition 131 , the helically bent bar of the evaporating part 121 is attached to the heating part 121 . After the first partition 132 is arranged on the outer peripheral side of the heating part partition 131 so that the first partition 132 surrounds the outer peripheral surface of the heating part partition 131, the heating part partition 131 is attached. The pipe is expanded and the helically bent bar is brought into close contact with the upper inner peripheral surface of the first partition wall 132 .

In the second CO reduction catalyst filling step 202, in the state where the first CO reduction catalyst filling preparation step 201 is completed, the second partition wall upper part 133, the heat transfer buffer cylinder 135, and the CO reduction part upper shelf plate 124 A predetermined weight of the CO reduction catalyst 151 is filled into the space from above the CO reduction unit upper shelf plate 124 .

In the third step 203 of introducing under the second partition, in the state where the second CO reduction catalyst filling step 202 is completed, the lower shelf plate 125 of the CO reduction section is lowered and the bottom of the lower second partition 134 is raised. is introduced from above toward the portion filled with the CO reduction catalyst 151 to face the CO reduction catalyst 151 on the CO reduction section lower shelf 125. The work is carried out so that the surface is evenly in contact with the CO reduction catalyst 151 .

In the fourth second partition wall joining step 204, in a state where the third second partition bottom introduction step 203 is completed, the portion where the second partition wall top 133 and the second partition bottom 134 are close to each other is airtightly bonded over the entire circumference. work to be done.

As described above, in the present embodiment, since the lower shelf plate 125 of the CO reduction unit is integrated with the lower second partition wall 134, the lower shelf plate 125 of the CO reduction unit and the inner peripheral surface of the upper second partition wall 133 are heat-transferable. By joining the lower second partition wall 134 to the upper second partition wall 133 without directly joining (welding) to at least one of the outer peripheral surfaces of the buffer cylinder 135, the weight of the CO reduction catalyst 151 reduces CO. The CO reduction subordinate shelf 125 can be fixed so that the subordinate shelf 125 does not fall off.

[2-3. effect]
As described above, the hydrogen generator 200 according to the present embodiment includes the heating section 120, the combustion cylinder 130, the heating section partition wall 131, the first partition wall 132, the flue gas flow path 140, the evaporating section 121, the reforming section 122, and the transmission. It has a heat buffer cylinder 135, a second partition upper part 133, a CO reduction part 123, a CO reduction part lower shelf plate 125, a CO reduction part upper shelf plate 124, a second partition lower part 134, and a return channel 141, and a CO reduction part lower part. It differs from the hydrogen generator 100 of Embodiment 1 shown in FIG.

The method for manufacturing the hydrogen generator 200 according to the present embodiment includes a CO reduction catalyst filling preparation step 201 , a CO reduction catalyst filling step 202 , a second partition bottom introduction step 203 , and a second partition wall bonding step 204 .

The heating unit 120 is configured to burn combustible gas and discharge flue gas. The combustion tube 130 has a tubular shape having a central axis in the vertical direction and surrounds the outer circumference of the heating section 120, and is configured so that combustion exhaust gas flows downward inside the tube. The heating section partition 131 has a bottomed tubular shape with a central axis in the vertical direction, and is configured to accommodate the combustion tube 130 with a gap between it and the combustion tube 130 .

The first partition wall 132 has a substantially cylindrical shape having a central axis in the vertical direction, and is configured such that the diameter of the lower portion is larger than the diameter of the upper portion, and the outer periphery of the heating portion partition wall 131 is provided with a gap between it and the heating portion partition wall 131 . surround. The combustion exhaust gas flow path 140 is a flow path formed in a gap between the combustion cylinder 130 and the heating section partition wall 131 and through which the combustion exhaust gas flows upward.

The evaporator 121 is formed in a gap between the heating partition wall 131 and the upper portion of the first partition wall 132, and is configured to heat the raw material gas and water by heat transmitted through the heating partition wall 131, thereby evaporating the water. It is

The reforming section 122 is formed by filling the gap between the heating section partition 131 and the lower portion of the first partition 132 with a reforming catalyst. It is configured to generate a primary hydrogen-containing gas containing carbon monoxide through a reforming reaction from the mixed gas of the raw material gas and water vapor that flowed out of the unit 121 .

The heat transfer buffer cylinder 135 has a substantially cylindrical shape with a central axis in the vertical direction, and has an outer diameter larger than that of the outer peripheral surface of the lower portion of the first partition 132 , and is spaced from the upper portion of the first partition 132 . The upper and lower ends are bent inward and fixed to the outer peripheral surface of the upper portion of the first partition wall 132 so that a space for heat transfer buffering is formed at the bottom.

The second upper partition wall 133 has a substantially cylindrical shape having a central axis in the vertical direction, surrounds the outer circumference of the heat transfer buffer cylinder 135 with a gap between it and the heat transfer buffer cylinder 135, and the upper end portion is bent inward. is fixed to the outer peripheral surface of the upper portion of the first partition wall 132 .

The CO reduction section 123 is formed by filling a gap between the heat transfer buffer cylinder 135 and the second partition wall upper portion 133 with a CO reduction catalyst 151, and reduces carbon monoxide contained in the primary hydrogen-containing gas flowing out of the reforming section 122. The concentration is reduced by a denaturation reaction and is configured to be discharged as a secondary hydrogen-containing gas.

The lower shelf plate 125 of the CO reduction section 125 is a donut disk-shaped shelf with a ventilation structure arranged in the gap between the heat transfer buffer cylinder 135 and the upper second partition wall 133 so that the CO reduction catalyst 151 of the CO reduction section 123 does not drop. It is a plate and supports the CO reduction catalyst 151 from below.

The CO reduction unit upper shelf plate 124 is arranged in a gap between the heat transfer buffer cylinder 135 and the second partition wall top 133 so that the CO reduction catalyst 151 of the CO reduction unit 123 does not flow upward from the CO reduction unit 123. It is a donut disk-shaped shelf plate in structure, and covers the upper surface of the part filled with the CO reduction catalyst 151 so that the lower surface contacts the CO reduction catalyst 151 .

The second partition bottom 134 has a bottomed tubular shape with a central axis in the vertical direction, and is integrally formed with the CO reduction unit lower shelf plate 125 . The first partition wall 132 and the heating part partition wall are joined to the upper part of the second partition wall 133 in a state facing the lower part of the peripheral surface, and the first partition wall 132 and the heating part partition wall are separated from each other with a gap between them and the portion of the first partition wall 132 below the CO reduction part 123. 131.

The return flow path 141 is formed in a gap between a portion of the first partition 132 below the CO reduction section 123 and the second partition bottom 134, and receives the flow of the primary hydrogen-containing gas flowing downward from the reforming section 122. It is a flow path for turning upward and leading to the CO reduction section 123 .

In the first CO reduction catalyst filling preparation step 201, the second partition wall top 133 is not yet placed below the second partition wall top 133 that has been attached to a predetermined position, and the second partition wall top 133 and the second partition wall 133 are heat transfer buffers. The CO reduction unit upper shelf plate 124 has already been attached to a predetermined position in the gap between the cylinder 135, but the CO reduction catalyst 151 has not yet been placed in the gap between the second partition wall 133 and the heat transfer buffer cylinder 135. It is a step of manufacturing a hydrogen generator up to and inverting the direction of gravity when the hydrogen generator is in use.

The second CO reduction catalyst filling process 202 is surrounded by the second partition upper part 133, the heat transfer buffer cylinder 135, and the CO reduction part upper shelf plate 124 in the state where the first CO reduction catalyst filling preparation process 201 is completed. In this step, the space is filled with a predetermined weight of the CO reduction catalyst 151 from above the upper shelf plate 124 of the CO reduction unit.

In the third second partition bottom introduction step 203, in a state where the second CO reduction catalyst filling step 202 is completed, the CO reduction section lower shelf plate 125 is at the bottom and the bottom of the second partition bottom 134 is at the top. is introduced from above toward the portion filled with the CO reduction catalyst 151 to face the CO reduction catalyst 151 on the CO reduction section lower shelf 125. In this step, the surface is installed at a position where it evenly abuts on the CO reduction catalyst 151 .

In the fourth step 204 for joining the second partition wall, in a state where the third step 203 for introducing the second partition wall below is completed, the portion where the upper second partition wall 133 and the lower second partition wall 134 are adjacent to each other is airtightly joined over the entire circumference. It is a process of performing the work to be done.

In the method for manufacturing the hydrogen generator 200 according to the present embodiment, in the assembly of the CO reduction unit 123, the upper shelf plate 124 of the CO reduction unit is first fixed, and the direction of gravity is reversed from that when the hydrogen generation unit 200 is used. By adopting a manufacturing method in which the CO reduction catalyst 151 is filled in the state and the CO reduction section lower shelf plate 125 is installed upstream of the CO reduction catalyst 151, the following effects can be obtained.

By fixing the CO reduction section upper shelf plate 124 in advance at a predetermined position, it is possible to absorb variations in the volume of the filled CO reduction catalyst 151 at the fixed position of the CO reduction section lower shelf plate 125 , and the CO reduction section upper shelf plate 125 is fixed. Variation in the position of the plate 124 can be suppressed.

Therefore, since the downstream position of the CO reduction catalyst 151 can be kept constant, the distance between the downstream position of the CO reduction catalyst 151 and the heating unit 120 can be kept constant, and the temperature of the downstream part of the CO reduction catalyst 151 can be kept constant. Since the concentration of CO contained in the hydrogen-containing gas after passing through the CO reduction section 123 depends on the temperature of the downstream portion of the CO reduction catalyst 151, it is possible to suppress individual differences in the CO concentration in the post-shifting reaction gas.

In addition, in the present embodiment, since the lower shelf plate 125 of the CO reduction unit is integrated with the lower second partition wall 134 , the lower shelf plate 125 of the CO reduction unit is integrated with the inner peripheral surface of the upper second partition wall 133 and the heat transfer buffer cylinder 135 . By joining the lower second partition wall 134 to the upper second partition wall 133 without directly joining (welding) to at least one of the outer peripheral surfaces of the CO reduction part lower shelf plate due to the weight of the CO reduction catalyst 151 The lower CO reduction shelf 125 can be fixed so that 125 does not fall off.

In addition, by integrating the lower shelf plate 125 of the CO reduction unit and the lower second partition wall 134, the number of parts can be reduced, and the assembly process can be simplified.

(Other embodiments)
As described above, Embodiment 1 and Embodiment 2 have been described as examples of the technology disclosed in the present application. However, the technology in the present disclosure is not limited to this, and can also be applied to embodiments with modifications, replacements, additions, omissions, and the like. Also, it is possible to combine the components described in the first and second embodiments to form a new embodiment.

Therefore, another embodiment will be illustrated below with reference to FIG. In Embodiments 1 and 2, a configuration including reforming catalyst 150 and CO reduction catalyst 151 as catalysts has been described.

As shown in FIG. 5, the hydrogen generator 300 further reduces the concentration of carbon monoxide contained in the secondary hydrogen-containing gas that has flowed out of the CO reduction unit 123 to the downstream (upper) side of the CO reduction catalyst 151 through a selective oxidation reaction. A CO removal section 142 filled with a CO removal catalyst that produces a tertiary hydrogen-containing gas may be provided.

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

Both the lower shelf plate 144 of the CO removal part and the upper shelf plate 143 of the CO removal part are doughnut-shaped plates in which vent holes having a diameter of 1 mm smaller than the particle diameter of the CO removal catalyst are formed.

As a result, the CO removal catalyst can further reduce the concentration of carbon monoxide contained in the hydrogen-containing gas discharged (supplied) from the hydrogen generator 300 compared to the hydrogen generator 100 of the first embodiment. Therefore, a highly reliable hydrogen generator 300 can be provided.

Before filling the CO removal catalyst, the lower shelf plate 144 of the CO removal part is installed, and the hydrogen generator is oriented in use (vertical normal state). By installing the plate 143 , 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 .

In addition, when the CO removal catalyst is charged in order to install the CO removal unit upper shelf plate 143 after the CO removal catalyst is charged in the normal state, the upper second partition wall 133 and the heat transfer buffer cylinder 135 Above the upper shelf plate 143 of the CO removal part installed therebetween, the upper part of the second partition wall 133 is arranged so that there is no obstacle that prevents the installation of the upper shelf plate 143 of the CO removal part by filling the CO removal catalyst from above. etc. must be configured.

Note that the above-described embodiment is for illustrating the technology in the present disclosure, and various changes, replacements, additions, omissions, etc. can be made within the scope of the claims or equivalents thereof.

Another embodiment will be illustrated below with reference to FIG.

In Embodiments 1 and 2, in the CO reduction catalyst filling preparation step 101 and the CO reduction catalyst filling preparation step 201, the reforming catalyst 150 is filled in advance and the reforming section 122 is formed. explained.

As shown in FIG. 6, the hydrogen generator 300 may be manufactured by filling the reforming catalyst at substantially the same time as the CO reduction catalyst (substantially in the same process).

In the CO reduction catalyst filling steps 102 and 202, the reforming catalyst 150 is filled on the reforming section upper shelf plate 126 at the same time as the CO reduction catalyst 151 is filled, or the reforming catalyst 150 is filled immediately before or after the CO reduction catalyst 151 is filled. A reforming catalyst 150 may be packed on the quality section upper shelf 126 .

In the CO reduction catalyst sealing step 103, the reforming catalyst is sealed by the reformer lower shelf plate 127 at the same time as the CO reduction catalyst is sealed, or immediately before or immediately before the CO reduction catalyst is sealed. You can go right after.

However, when the CO reduction section lower shelf 125 is configured integrally with the second partition lower 134, the reforming catalyst is sealed by the reforming section lower shelf 127 after the CO reduction catalyst filling step 202. It must be done before the under-septum introduction step 203 .

As a result, the man-hours required for manufacturing the reforming section and the CO reduction section can be reduced, and the manufacturing process can be simplified.

Note that the above-described embodiment is for illustrating the technology in the present disclosure, and various changes, replacements, additions, omissions, etc. can be made within the scope of the claims or equivalents thereof.

In the present disclosure, an evaporating section and a reforming section are arranged between a heating section partition and a first partition surrounding the heating section partition, a portion of the first partition where the evaporating section is configured, and a first partition surrounding the portion. The CO reduction section is arranged between the two partition walls, 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. Applicable to hydrogen generators.

100 Hydrogen Generator 101 CO Reduction Catalyst Filling Preparatory Step 102 CO Reduction Catalyst Filling Step 103 CO Reduction Catalyst Sealing Step 104 Second Partition Below Introduction Step 105 Second Partition Wall Joining Step 120 Heating Section 121 Evaporating Section 122 Reforming Section 123 CO Reduction Part 124 CO reduction section upper shelf 125 CO reduction section lower shelf 126 reforming section upper shelf 127 reforming section lower shelf 130 combustion tube 131 heating section partition 132 first partition 133 second partition upper 134 second partition lower 135 heat transfer buffer Cylinder 140 flue gas flow path 141 return flow path 142 CO removal section 143 CO removal section upper shelf plate 144 CO removal section lower shelf plate 150 reforming catalyst 151 CO reduction catalyst 200 hydrogen generator 201 CO reduction catalyst filling preparation step 202 CO reduction catalyst filling Step 203 Step of introduction below second partition wall 204 Step of joining second partition wall 300 Hydrogen generator

Claims (2)

a heating unit that burns combustible gas and discharges combustion exhaust gas;
a cylindrical combustion cylinder having a central axis in the vertical direction and surrounding the outer periphery of the heating part so that the combustion exhaust gas flows downward inside the cylinder;
a heating part partition having a bottomed tubular shape having a central axis in a vertical direction and accommodating the combustion cylinder with a gap between it and the combustion cylinder;
a first partition having a substantially cylindrical shape having a central axis in the vertical direction, having a lower diameter larger than an upper diameter, and surrounding the outer periphery of the heating part partition with a gap between it and the heating part partition;
a flue gas flow path formed in a gap between the combustion cylinder and the partition wall of the heating section for upwardly flowing the flue gas;
an evaporator that is formed in a gap between the heating part partition and the upper part of the first partition, heats a source gas and water with heat transmitted through the heating part partition, and evaporates the water;
A reforming catalyst is formed by filling a gap between the heating part partition wall and the lower part of the first partition wall, and heat is transmitted through the heating part partition below the evaporating part and flows out from the evaporating part. a reforming unit for generating a primary hydrogen-containing gas containing carbon monoxide by a reforming reaction from the mixed gas of the raw material gas and water vapor;
It has a substantially cylindrical shape with a central axis in the vertical direction, the outer diameter of the outer peripheral surface thereof is larger than the outer diameter of the outer peripheral surface of the lower portion of the first partition wall, and is for heat transfer buffering between the upper portion of the first partition wall and the lower portion of the first partition wall. a heat transfer buffer cylinder having upper and lower ends bent inward and fixed to the outer peripheral surface of the upper portion of the first partition wall so as to form a space of
It has a substantially cylindrical shape having a central axis in the vertical direction, surrounds the outer circumference of the heat transfer buffer cylinder with a gap between it and the heat transfer buffer cylinder, and has an upper end portion bent inward to form the first partition wall. on the second partition fixed to the outer peripheral surface of the upper part;
The gap between the heat transfer buffer cylinder and the second partition is filled with a CO reduction catalyst, and the concentration of carbon monoxide contained in the primary hydrogen-containing gas flowing out of the reforming section is reduced by a modification reaction. and a CO reduction unit that discharges as a secondary hydrogen-containing gas;
It is arranged in the gap between the heat transfer buffer cylinder and the second partition so that the CO reduction catalyst of the CO reduction part does not fall, and has a ventilation structure that supports the CO reduction catalyst from below and has a donut-shaped CO reduction. subordinate shelf board,
The CO reduction catalyst of the CO reduction portion is arranged in a gap between the heat transfer buffer cylinder and the second partition so that the CO reduction catalyst does not flow upward from the CO reduction portion, and the lower surface is in contact with the CO reduction catalyst. a donut disk-shaped CO reduction unit upper shelf plate having a ventilation structure covering the upper surface of the portion filled with the CO reduction catalyst;
It has a bottomed cylindrical shape with a central axis in the vertical direction, the upper end is in contact with the outer peripheral portion of the lower surface of the lower shelf plate of the CO reduction section, and the upper portion of the outer peripheral surface is opposed to the lower portion of the inner peripheral surface on the second partition wall. a second partition bottom that is joined to the top of the second partition and accommodates the first partition and the heating part partition with a gap between a portion of the first partition that is below the CO reduction unit;
Formed in a gap between a portion of the first partition below the CO reduction portion and the bottom of the second partition, the flow of the primary hydrogen-containing gas that has flowed downward from the reforming portion is changed upward, and the A method for manufacturing a hydrogen generator having a return flow path leading to a CO reduction unit,
The bottom of the second partition is not yet arranged at the lower part of the second partition that has been attached to a predetermined position, and the CO Although the upper shelf plate of the reduction section has been installed, the CO reduction catalyst and the lower shelf board of the CO reduction section are not yet arranged in the gap between the second partition wall and the heat transfer buffer cylinder. A CO reduction catalyst filling preparation step of manufacturing a device and inverting the direction of gravity when the hydrogen generator is in use;
In a state where the CO reduction catalyst filling preparation step is completed, a predetermined weight of the CO reduction catalyst is placed from above in the space surrounded by the second partition wall, the heat transfer buffer cylinder, and the CO reduction unit upper shelf plate. a filling CO reduction catalyst filling step;
In a state where the CO reduction catalyst filling step is completed, the CO reduction section lower shelf is introduced from above toward the portion filled with the CO reduction catalyst, and the CO reduction catalyst in the CO reduction section lower shelf is introduced from above. a CO reduction catalyst sealing step in which the opposing surfaces are installed at positions where they evenly abut against the CO reduction catalyst;
In a state where the CO reduction catalyst sealing step is completed, the bottom of the second partition, which is turned upside down so that the bottom of the bottom of the second partition faces upward, is introduced from above toward the lower shelf plate of the CO reduction unit. Then, a second partition lower introduction step of installing at a position where the lower of the second partition is in contact with the lower shelf plate of the CO reduction unit;
a second partition bonding step of air-tightly joining a portion where the bottom of the second partition and the top of the second partition are close to each other in a state where the step of introducing below the second partition is completed. . a heating unit that burns combustible gas and discharges combustion exhaust gas;
a cylindrical combustion cylinder having a central axis in the vertical direction and surrounding the outer periphery of the heating part so that the combustion exhaust gas flows downward inside the cylinder;
a heating part partition having a bottomed tubular shape having a central axis in a vertical direction and accommodating the combustion cylinder with a gap between it and the combustion cylinder;
a first partition having a substantially cylindrical shape having a central axis in the vertical direction, having a lower diameter larger than an upper diameter, and surrounding the outer periphery of the heating part partition with a gap between it and the heating part partition;
a flue gas flow path formed in a gap between the combustion cylinder and the partition wall of the heating section for upwardly flowing the flue gas;
an evaporator that is formed in a gap between the heating part partition and the upper part of the first partition, heats a source gas and water with heat transmitted through the heating part partition, and evaporates the water;
A reforming catalyst is formed by filling a gap between the heating part partition wall and the lower part of the first partition wall, and heat is transmitted through the heating part partition below the evaporating part and flows out from the evaporating part. a reforming unit for generating a primary hydrogen-containing gas containing carbon monoxide by a reforming reaction from the mixed gas of the raw material gas and water vapor;
It has a substantially cylindrical shape with a central axis in the vertical direction, the outer diameter of the outer peripheral surface thereof is larger than the outer diameter of the outer peripheral surface of the lower portion of the first partition wall, and is for heat transfer buffering between the upper portion of the first partition wall and the lower portion of the first partition wall. a heat transfer buffer cylinder having upper and lower ends bent inward and fixed to the outer peripheral surface of the upper portion of the first partition wall so as to form a space of
It has a substantially cylindrical shape having a central axis in the vertical direction, surrounds the outer circumference of the heat transfer buffer cylinder with a gap between it and the heat transfer buffer cylinder, and has an upper end portion bent inward to form the first partition wall. on the second partition fixed to the outer peripheral surface of the upper part;
The gap between the heat transfer buffer cylinder and the second partition is filled with a CO reduction catalyst, and the concentration of carbon monoxide contained in the primary hydrogen-containing gas flowing out of the reforming section is reduced by a modification reaction. and a CO reduction unit that discharges as a secondary hydrogen-containing gas;
It is arranged in the gap between the heat transfer buffer cylinder and the second partition so that the CO reduction catalyst of the CO reduction part does not fall, and has a ventilation structure that supports the CO reduction catalyst from below and has a donut-shaped CO reduction. subordinate shelf board,
The CO reduction catalyst of the CO reduction portion is arranged in a gap between the heat transfer buffer cylinder and the second partition so that the CO reduction catalyst does not flow upward from the CO reduction portion, and the lower surface is in contact with the CO reduction catalyst. a donut disk-shaped CO reduction unit upper shelf plate having a ventilation structure covering the upper surface of the portion filled with the CO reduction catalyst;
The second partition wall has a bottomed cylindrical shape with a central axis in the vertical direction, and is integrally formed with the lower shelf plate of the CO reduction unit, and the upper portion of the outer peripheral surface faces the lower portion of the inner peripheral surface of the second partition wall. a second partition bottom that is joined to the top and accommodates the first partition and the heating part partition with a gap between the portion of the first partition that is below the CO reduction unit;
Formed in a gap between a portion of the first partition below the CO reduction portion and the bottom of the second partition, the flow of the primary hydrogen-containing gas that has flowed downward from the reforming portion is changed upward, and the A method for manufacturing a hydrogen generator having a return flow path leading to a CO reduction unit,
The bottom of the second partition is not yet arranged at the lower part of the second partition that has been attached to a predetermined position, and the CO The hydrogen generator is manufactured so that the reducing part upper shelf plate is already attached, but the CO reduction catalyst is not yet arranged in the gap between the second partition wall and the heat transfer buffer cylinder, and hydrogen generation is performed. A CO reduction catalyst filling preparation step of turning the apparatus upside down in the direction of gravity during use;
In a state where the CO reduction catalyst filling preparation step is completed, a predetermined weight of the CO reduction catalyst is placed from above in the space surrounded by the second partition wall, the heat transfer buffer cylinder, and the CO reduction unit upper shelf plate. a filling CO reduction catalyst filling step;
In a state in which the CO reduction catalyst filling step is completed, the CO reduction section lower shelf under the second partition is turned upside down so that the CO reduction section lower shelf is at the bottom and the bottom under the second partition is at the top. A plate is introduced from above toward the portion filled with the CO reduction catalyst, and installed at a position where the surface of the CO reduction unit lower shelf plate facing the CO reduction catalyst evenly abuts the CO reduction catalyst. a step of introducing under the second partition;
a second partition bonding step of air-tightly joining a portion where the bottom of the second partition and the top of the second partition are close to each other in a state where the step of introducing below the second partition is completed. .

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