JP2005306658A - Hydrogen producing apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hydrogen producing apparatus capable of effectively heating water accumulated in a water-vaporization section while simplifying a configuration of gas-flow channels. <P>SOLUTION: This hydrogen producing apparatus 10 is equipped with a first cylindrical wall member 11, a second cylindrical wall member 12 disposed outside the first cylindrical wall member 11 coaxially therewith, a cylindrical water-vaporization section 13 and a cylindrical reforming catalyst body 14 both arranged so as to be lined up in the axial direction of the first and second cylindrical wall members 11, 12 in a first cylindrical space between the first cylindrical wall member 11 and the second cylindrical wall member 12, a burner 15 generating a combustion gas through combustion of a combustible gas, a third cylindrical wall member 16 disposed inside the first cylindrical wall member 11 and arranged coaxially therewith to form a second cylindrical space to flow the combustion gas between itself and the first cylindrical wall member 11, and a heater arranged inside the second cylindrical space. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a hydrogen generation apparatus, and more particularly to a hydrogen generation apparatus that enables water accumulated in a water evaporation section to be efficiently evaporated.

  The fuel cell system supplies a hydrogen-rich gas (reformed gas) to the anode of the fuel cell, supplies an oxidant gas to the cathode of the fuel cell, and causes these gases to react electrochemically inside the fuel cell. It generates electricity and heat at the same time.

  Here, as a method for generating the reformed gas, a hydrogen generator for producing hydrogen gas from a raw material gas (for example, natural gas or city gas) and steam by a steam reforming reaction is used. It is necessary to receive the heat of evaporation that evaporates water and the heat of reaction that promotes the reforming reaction from the high-temperature combustion gas of the heating burner, so that water and the reforming catalyst body can efficiently exchange heat with the combustion gas. However, it is an important issue from the viewpoint of effective use of thermal energy.

As a report example related to this problem, hydrogen generation in which a water evaporation part is arranged so as to cover the periphery of the cylindrical reforming part containing the reforming catalyst body in the circumferential direction with the combustion gas flow path interposed therebetween An apparatus has been proposed (for example, see Patent Document 1 as a conventional example). In this hydrogen generator, a combustion gas flow path is formed by covering a combustion gas flow path and a reforming section (reforming catalyst body) with a water evaporation section. The amount of heat released from the high-temperature combustion gas flowing through the gas and the amount of heat released from the reforming catalyst body maintained at a high temperature are reduced to improve the thermal efficiency of the hydrogen generator.
JP 2003-252604 A

  However, in the above-described conventional hydrogen generator, priority has been given to improving the thermal efficiency of the hydrogen generator, so when the mixed gas containing the raw material gas and water vapor flows out from the water evaporation section toward the reforming section, this mixed gas The configuration of the mixed gas flow path is complicated by changing the flow direction from the axial direction of the water evaporation section to the circumferential direction. For example, the mixed gas supply pipe that connects the mixed gas outlet of the water evaporation section and the mixed gas inlet of the reforming section extends in the radial direction, and at the connection point between the mixed gas supply pipe and the reforming section that extends in the axial direction, It is necessary to perform piping construction such as welding, and this piping construction of the mixed gas flow path may lead to deterioration of the structure durability performance due to the cost increase of the hydrogen generator and the complexity of the structure.

  For such a configuration, the cylindrical water evaporation section and the reforming catalyst body are arranged side by side in the same axial direction, and the flow of the mixed gas is smoothly directed from the water evaporation section to the reforming catalyst body along the axial direction. Can be simplified, the mixed gas flow path can be simplified, and the above-described problems can be solved and a desirable mixed gas flow path configuration can be realized.

  However, in the configuration in which the mixed gas (water vapor) flows in the axial direction in the water evaporation unit, the heat of evaporation cannot be quickly supplied to the water accumulated at the lower end of the water evaporation unit when the hydrogen generator is started. There is a problem that it takes time to heat the accumulated water to a predetermined temperature required for evaporation, and the start-up operation of the hydrogen generator becomes slow.

  The present invention has been made in view of such circumstances, and an object of the present invention is to simplify the configuration of the mixed gas flow path and to efficiently collect water accumulated in the water evaporation section when the hydrogen generator is activated. An object of the present invention is to provide a hydrogen generator that can be heated.

  In order to solve the above-described problems, a hydrogen generator according to the present invention includes a first cylindrical wall member and a coaxial arrangement with the first cylindrical wall member outside the first cylindrical wall member. In the first cylindrical space between the second cylindrical wall member and the first cylindrical wall member and the second cylindrical wall member. A cylindrical water evaporation portion and a cylindrical reforming catalyst body provided so as to be aligned in the axial direction, a burner that generates combustion gas by combustion of combustible gas, and the inside of the first cylindrical wall member A third cylindrical wall member disposed coaxially with the first cylindrical wall member and forming a second cylindrical space for flowing the combustion gas with the first cylindrical wall member And a heating element disposed inside the second cylindrical space, and the water flowing in through the water inlet of the water evaporation unit is introduced into the water evaporation unit. The raw material gas flowing in through the raw material gas inlet of the water evaporation unit is mixed with the water vapor, and the mixed gas including the raw material gas and the water evaporation unit is supplied from the water evaporation unit to the reforming catalyst. The mixed gas that has flowed into the medium is reformed into a hydrogen-rich reformed gas by a reforming reaction while passing through the reforming catalyst body.

  The heating element is, for example, a heater for electric heating and / or a gas combustion catalyst body.

  The water flowing into the water evaporation unit through the water inlet of the water evaporation unit is heated by the heating element to evaporate into water vapor.

  Thereby, while simplifying the structure of a mixed gas flow path, the hydrogen generator which can heat the water collected in the water evaporation part at the time of starting of a hydrogen generator efficiently with a heat generating body is obtained.

  Furthermore, a water evaporation part temperature measuring means for detecting the temperature inside the water evaporation part and a heater control part are provided, and the heater control part is based on the temperature detected by the water evaporation part temperature detection means. You may comprise so that the heating to the said water of the said heater may be controlled.

  Thus, when the hydrogen generator is started, the temperature inside the water evaporation unit is detected by the water evaporation unit temperature measuring means, and the heater control unit appropriately performs the heating operation of the heater to the water based on the detected temperature. Can be controlled.

  If the temperature detected by the water evaporation unit temperature measuring means is equal to or higher than a predetermined temperature, the heater control unit controls a heater heating operation so as to stop the heating of the heater to the useless heater. Heating can be stopped to suppress energy loss.

  In addition, an example of the gas combustion catalyst body includes catalyst particles and a metal carrier that supports the catalyst particles. Alternatively, another example of the gas combustion catalyst body includes catalyst particles and a cylindrical ceramic carrier that supports the catalyst particles.

  Using the catalytic function of the catalyst particles, the unburned gas can be easily burned with the gas combustion catalyst body, thereby preventing the unburned gas from being released into the atmosphere and utilizing the heat obtained by unburned gas combustion. Water accumulated in the water evaporation section can be heated.

  The metal carrier includes, for example, a cylindrical first metal plate and a second metal plate that has a protruding portion that contacts a side surface of the first metal plate and is processed into a corrugated shape. There may be.

  By using such a metal carrier, even if the porous portion is arranged in multiple layers in a narrow flow path (for example, about 5 mm), the degree of freedom in design can be reduced without causing cracks or cracks in this portion. An excellent gas combustion catalyst body can be obtained.

  Further, the ceramic carrier may be configured such that, for example, a plurality of holes penetrating in the axial direction are formed in a honeycomb shape.

  By using such a ceramic carrier, an inexpensive gas combustion catalyst body can be obtained.

  The gas combustion catalyst body may be configured by applying catalyst particles to the inner peripheral surface of the first cylindrical wall member or the outer peripheral surface of the third cylindrical wall member.

  Thus, it is possible to easily form a gas combustion catalyst body by reducing the number of parts.

  A hydrogen generator according to the present invention includes a cylindrical water evaporation section extending in the direction of the central axis, and a cylindrical modification extending in parallel with the central axis of the water evaporation section on an extension line of the central axis of the water evaporation section. A reforming catalyst body, a burner that generates combustion gas by combustion of combustible gas, and a reformer that is disposed coaxially with the water evaporation section in a region surrounded by the water evaporation section and flows out of the reforming catalyst body A CO gas removal unit that houses a catalyst body for removing carbon monoxide gas contained in the gas, and a cylindrical combustion gas flow for flowing the combustion gas between the CO gas removal unit and the water evaporation unit A heating element disposed in the path, and evaporates water flowing through the water inlet of the water evaporation section into water vapor inside the water evaporation section and flows through the source gas inlet of the water evaporation section The raw material gas is mixed with the water vapor. The mixed gas containing the raw material gas and the water evaporating part is caused to flow from the water evaporating part into the reforming catalyst body, and the introduced mixed gas is hydrogen-rich by a reforming reaction while passing through the reforming catalyst body. It reforms to a new reformed gas.

  The heating element is, for example, a heater for electric heating and / or a gas combustion catalyst body.

  The water flowing into the water evaporation unit through the water inlet of the water evaporation unit is heated by the heating element to evaporate into water vapor.

  Thereby, while simplifying the structure of a mixed gas flow path, the hydrogen generator which can heat the water collected in the water evaporation part at the time of starting of a hydrogen generator efficiently with a heat generating body is obtained. At the same time, when the hydrogen generator is started, the catalyst body incorporated in the CO gas removal unit can be quickly and efficiently heated to the catalytic reaction temperature.

  Further, the apparatus includes a water evaporation unit temperature measuring unit that detects a temperature inside the water evaporation unit, and a heater control unit, the heater control unit based on the temperature detected by the water evaporation unit temperature detection unit. You may comprise so that the heating to the said water of a heater may be controlled.

  Thus, when the hydrogen generator is started, the temperature inside the water evaporation unit is detected by the water evaporation unit temperature measuring means, and the heater control unit appropriately performs the heating operation of the heater to the water based on the detected temperature. Can be controlled.

  If the temperature detected by the water evaporation section temperature measuring means is equal to or higher than a predetermined temperature, the heater control section controls useless heating of the heater by controlling the heater heating operation so as to stop the heating of the heater to the water. Stops energy loss.

  In addition, a catalyst body temperature measuring unit for detecting the temperature of the catalyst body and a heater control unit are provided, and the heater control unit is configured to detect the catalyst body of the heater based on a temperature detected by the catalyst body temperature measuring unit. You may comprise so that the heating to may be controlled.

  As a result, when the hydrogen generator is started, the temperature inside the catalyst body is detected by the catalyst body temperature measuring means, and the heater controller appropriately controls the heating operation of the heater to the catalyst body based on the detected temperature. it can.

  The catalyst body is, for example, a shift catalyst body that shifts the carbon monoxide gas.

  In this case, when the temperature detected by the catalyst body temperature measuring means is not more than a predetermined temperature when the load of the hydrogen generator is fluctuated, the heater control unit may start heating the shift catalyst body of the heater. good. When the load fluctuates, the temperature of the catalyst body tends to decrease, and in order to compensate for this, it is effective to heat the shift catalyst body with a heater.

The catalyst body may be a selective oxidation catalyst body that selectively oxidizes the carbon monoxide gas. An example of the gas combustion catalyst body includes catalyst particles and a metal carrier that supports the catalyst particles. is there. Another example of the gas combustion catalyst body includes catalyst particles and a cylindrical ceramic carrier that supports the catalyst particles.

  Using the catalytic function of the catalyst particles, the unburned gas can be easily burned with the gas combustion catalyst body, thereby preventing the unburned gas from being released into the atmosphere and utilizing the heat obtained by unburned gas combustion. Water accumulated in the water evaporation section can be heated.

  The metal carrier includes a cylindrical first metal plate and a second metal plate that has a protruding portion that contacts a side surface of the first metal plate and is processed into a corrugated shape. Also good.

  By using such a metal carrier, even if the porous portion is arranged in multiple layers in a narrow flow path (for example, about 5 mm), the degree of freedom in design can be reduced without causing cracks or cracks in this portion. An excellent gas combustion catalyst body can be obtained.

  The ceramic carrier may be configured such that a plurality of holes penetrating in the axial direction are formed in a honeycomb shape.

  By using such a ceramic carrier, an inexpensive gas combustion catalyst body can be obtained.

  ADVANTAGE OF THE INVENTION According to this invention, while aiming at simplification of the structure of a mixed gas flow path, the hydrogen generator which can heat efficiently the water collected in the water evaporation part at the time of starting of a hydrogen generator is obtained.

  Embodiments of the present invention will be described below with reference to the drawings. In the figure, the side marked “upper” is the upper side, the side marked “lower” is the lower side, and the vertical direction of the cylindrical hydrogen generator 10 is the axial direction. Each embodiment will be described with the direction along the circumference drawn around the first central axis 110 as the circumferential direction and the direction along the radius of the circumference as the radial direction.

(Embodiment 1)
FIG. 1 is a cross-sectional view showing the internal structure of the hydrogen generator according to Embodiment 1 of the present invention.

  First, an outline of the overall configuration of the hydrogen generator 10 shown in FIG. 1 will be described.

  The hydrogen generator 10 mainly includes a first cylindrical wall member 11 and a second cylindrical wall member made of cylindrical seamless metal (stainless steel) that share a first central axis 110 to form a double pipe. 12 and the first central axis 110 of the first and second cylindrical wall members 11, 12 formed in a cylindrical region defined by the first and second cylindrical wall members 11, 12. In a region partitioned by the first and second cylindrical wall members 11 and 12, and arranged in the direction of the first central axis 110 along the water evaporation unit 13. Between the arranged cylindrical platinum-based reforming catalyst body 14 and the lower end of the first cylindrical wall member 11 to the vicinity of the upper end inside the first cylindrical wall member 11, and between the first cylindrical wall member 11 Third cylindrical seamless metal (stainless steel) forming a coaxial double tube A seamless metal (stainless steel) cylindrical cover that covers the upper half of the cylindrical wall member 16 and the second cylindrical wall member 12 and forms a double tube with the second cylindrical wall member 12 22.

  Here, the heater device for heating the water accumulated in the water evaporating unit 13 has a gap with the third cylindrical wall member 16 in the vicinity of the lower end 13 d of the water evaporating unit 13. A cylindrical heater 131 as a heating element attached to the inner peripheral surface of the cylindrical wall member 11, and the second cylindrical wall member 12 at a position above the water reservoir 38 of the water evaporation unit 13, A water evaporator temperature measuring means 64 (for example, a thermocouple) that measures the temperature inside the water evaporator 13 and a heater control that controls output to the heater 131 based on the temperature detected by the water evaporator temperature measuring means 64. Part 130. Here, as an example of the heater 131, there is a heating element constituted by a heating wire for energization.

  Moreover, according to FIG. 1, the burner 15 is arrange | positioned at the upper end of the 1st cylindrical wall member 11 so that the flame of the burner 15 may go below.

  More specifically, the combustion cylinder 50 is inserted into the third cylindrical wall member 16 from the upper end thereof, and the lower end 50A of the combustion cylinder 50 is connected to the first cylindrical wall member 11 (third cylindrical wall member 16). ) In the axial center (near the lower end 14d of the reforming catalyst body 14).

  Here, the annular flange 50S provided at the upper end 50B of the combustion cylinder 50 is brought into contact with the upper ends of the first cylindrical wall member 11 and the cylindrical cover 22 to position the combustion cylinder 50 in the axial direction. ing. At the same time, the upper end of the hydrogen generator 10 surrounded by the cylindrical cover 22 is covered by the flange 50S except for the inner region of the combustion cylinder 50, and the flange 50S serves as a lid member (first and second). And a role as a lid member provided above the third cylindrical wall members 11, 12, and 16). And the burner 15 is connected to this collar part 50S.

  Further, a disc-shaped partition member 51 faces the lower end 50A of the combustion cylinder 50 in the vicinity of the lower end 50A of the combustion cylinder 50 and blocks the lower side of the combustion cylinder 50 to partition the inside of the third cylindrical wall member 16. Are arranged as follows.

  As will be described in detail later, the cylindrical space between the combustion cylinder 50 and the third cylindrical wall member 16 is used as a second combustion gas passage 53 through which the combustion gas from the burner 15 flows. The cylindrical space between the third cylindrical wall member 16 and the first cylindrical wall member 11 is used as the first combustion gas flow path 30, and the second cylindrical wall member 12 and the cylindrical cover are used. The cylindrical space between 22 is used as a reformed gas flow path 45 through which the reformed gas flows. Then, the heater 131 extends in an annular shape over the entire circumferential direction of the inner peripheral surface of the first cylindrical wall member 11 (the surface defining the first combustion gas flow path 30), A first fuel gas flow path 30 between the cylindrical wall member 16 and the first cylindrical wall member 11 is provided.

  Further, the reforming catalyst body 14 is supported in a boundary region between the upper end 13u of the water evaporation section 13 and the lower end 14d of the reforming catalyst body 14, and has an annular shape having a plurality of mixed gas ejection holes 43h arranged uniformly in the circumferential direction. The support member 43 is provided.

  As described above, according to the hydrogen generator 10 shown in FIG. 1, the first central axis 110 of the reforming catalyst body 14 is aligned with the first central axis 110 of the water evaporation unit 13, The reforming catalyst bodies 14 are arranged side by side on the downstream side in the flow direction of the mixed gas (gas containing raw material gas and water vapor) existing inside the evaporation section 13. That is, the water evaporation unit 13 is disposed below the reforming catalyst body 14.

  By aligning the direction of the first central axis 110 of the water evaporation unit 13 and the reforming catalyst body 14 and arranging them side by side, the inside of the water evaporation unit 13 is directed from the water evaporation unit 13 toward the reforming catalyst body 14. Ascending mixed gas can be smoothly flowed out to the reforming catalyst body 14 in one direction (axial direction), for example, complicated gas flow paths using piping construction such as welding can be reduced, and DSS (Daily It is possible to improve the durability of the hydrogen generator 10 against a thermal cycle by Start-up & Shut-down) and to reduce the manufacturing cost of the hydrogen generator 10 by simplifying the gas flow path.

  Further, since the water evaporation unit 13 is disposed below the reforming catalyst body 14, only the water vapor can be supplied to the reforming catalyst body 14, and water droplets from the water evaporation unit 13 flow into the reforming catalyst body 14, so that the reforming catalyst. It is possible to prevent the reforming catalyst body 14 from being deteriorated due to cracking of the reforming catalyst body 14 due to evaporation of water droplets on the medium 14.

  Subsequently, a piping configuration for introducing fuel gas, raw material gas, air and water from an external device (not shown) to the hydrogen generator 10 will be described.

  In the water evaporation section 13, the source gas pipe 40 that guides the source gas supplied from the source supply means (not shown) to the source gas inlet 40 in of the water evaporation section 13 and the supply water to the water inlet 13 in of the water evaporation section 13. A leading water pipe 41 is connected.

  The burner 15 is connected to a fuel gas pipe 17 that guides the fuel gas that is recirculated as an off gas of a fuel cell (not shown) to the flame region of the burner 15 and is supplied from an air supply means (not shown). An air pipe 21 that guides air to the flame area of the burner 15 is connected via an annular air buffer 23.

Next, the configuration of the hydrogen generator 10 related to the combustion gas path will be described in more detail.
The inner diameter of the combustion cylinder 50 is smaller than the inner diameter of the third cylindrical wall member 16, whereby a second combustion gas comprising a cylindrical gap between the combustion cylinder 50 and the third cylindrical wall member 16. A flow path 53 is formed. The combustion cylinder 50 is inserted into the inside from the upper end of the third cylindrical wall member 16 with a cylindrical gap therebetween at the time of assembly. In a state where the combustion cylinder 50 is inserted into the third cylindrical wall member 16 with the directions of the first central axes 110 aligned, an annular gap is provided between the combustion cylinder 50 and the lower end 50A of the combustion cylinder 50. A disc-shaped partition member 51 is arranged. This gap corresponds to the lower combustion gas inlet 52.

  Further, the inner diameter of the third cylindrical wall member 16 is smaller than the inner diameter of the first cylindrical wall member 11, whereby the third cylindrical wall member 16 and the first cylindrical wall member 11 are interposed. A first combustion gas flow path 30 formed of a cylindrical gap is formed. The third cylindrical wall member 16 is formed with a first cylindrical shape from the lower end of the first cylindrical wall member 11 so as to form a cylindrical gap with the first cylindrical wall member 11 during assembly. It is inserted into the wall member 11. Then, in a state where the third cylindrical wall member 16 is inserted into the first cylindrical wall member 11 and the directions of the first central axes 110 are aligned and fixed, the third cylindrical wall member 16 The upper end of the first cylindrical wall member 11 is closed by the flange portion 50S so as to have an annular gap between the upper end and the upper end. This gap corresponds to the upper combustion gas inlet 31.

  Further, when the third cylindrical wall member 16 is inserted, the annular stopper portion 16a at the lower end of the third cylindrical wall member 16 is attached to the lower wall of the combustion gas exhaust portion 33 via a packing (not shown). The third cylindrical wall member 16 is positioned in the axial direction by contact.

  Further, the upper end of the first cylindrical wall member 11 abuts against the flange portion 50S, and the lower end portion thereof is brought into contact with the lower wall of the combustion gas exhaust portion 33 via a packing (not shown). One cylindrical wall member 11 is fixed.

  Both the first cylindrical wall member 11 and the third cylindrical wall member 16 are seamlessly extended from the vicinity of the upper end 14 u of the reforming catalyst body 14 to the vicinity of the lower end 13 d of the water evaporation section 13. Since it is a metal pipe, the first combustion gas flow path 30 is also formed from the vicinity of the upper end 14 u of the reforming catalyst body 14 to the vicinity of the lower end 13 d of the water evaporation section 13.

  Moreover, in order to guide the combustion gas flowing through the first combustion gas flow path 30 to the atmosphere through the combustion gas outlet 32 formed in the vicinity of the lower end of the first cylindrical wall member 11, the first cylindrical wall member A combustion gas exhaust part 33 is disposed around the vicinity of the lower end of 11, and an exhaust pipe 34 is disposed at a predetermined position of the combustion gas exhaust part 33 so as to protrude outward in the radial direction.

  More specifically, the first cylindrical wall member 11 is formed with a combustion gas outlet 32 as an opening that is uniformly arranged in the circumferential direction, and covers the combustion gas outlet 32 so as to cover the first cylindrical wall member. 11 and a combustion gas exhaust part 33 is disposed so as to extend over the entire circumference of the first cylindrical wall member 11. A cylindrical exhaust pipe 34 is disposed so as to protrude in the radial direction from the outer periphery of the combustion gas exhaust part 33.

  Thus, as shown in FIG. 1, the combustion gas flow path is formed by the third cylindrical wall member 16 inserted in the region between the combustion cylinder 50 and the first cylindrical wall member 11 so that the second combustion gas flow. From the passage 53 toward the first combustion gas passage 30, it is bent in a U shape with the upper combustion gas inlet 31 as a boundary.

  Next, the configuration of the hydrogen generator 10 related to the mixed gas flow path and the reformed gas path will be described in more detail.

  As shown in FIG. 1, the mixed gas inside the water evaporation unit 13 is disposed in a boundary region between the upper end 13 u of the water evaporation unit 13 and the lower end 14 d of the reforming catalyst body 14 to support the reforming catalyst body 14. It flows out to the reforming catalyst body 14 through a plurality of mixed gas ejection holes 43 h formed in the supporting member (partition plate) 43 to be performed. Here, the mixed gas ejection holes 43 h of the support member 43 are formed as a plurality of round holes (diameter: about 1 mm) at a predetermined interval in the circumferential direction of the support member 43. As a result, the mixed gas can be supplied uniformly in the circumferential direction of the reforming catalyst body 14.

  Moreover, the outer periphery of this support member 43 is connected to the 2nd cylindrical wall member 12 as shown in FIG. 1, and the support member 43 is supported by the 2nd cylindrical wall member 12 in the cantilever state. On the other hand, there is an annular gap between the inner periphery of the support member 43 and the first cylindrical wall member 11, and the mixed gas flows from the water evaporation section 13 toward the reforming catalyst body 14 through this annular gap. Needless to say, the support member 43 can be cantilevered by the second cylindrical wall member 12, and the support member 43 may be cantilevered by the first cylindrical wall member 11. Both members may be supported by the members 11 and 12. The shape of the mixed gas ejection hole 43h is not limited to a round hole, and may be any shape such as an oval, an ellipse, or a rectangle.

  As a modification of the support member 43, instead of forming a plurality of mixed gas ejection holes 43 h in the circumferential direction of the support member 43, a mixed gas ejection hole (not shown) is provided only at one location in the circumferential direction of the support member 43. ) May be provided. By providing a single mixed gas ejection hole in this way, when the raw material gas and water vapor inside the water evaporation section 13 flow out toward the reforming catalyst body 14, the raw material gas and water vapor enter the mixed gas ejection hole. The mixed gas can be mixed and promoted to be mixed (however, a separate measure for making the mixed gas uniform in the circumferential direction and supplying it to the reforming catalyst body is necessary).

  On the other hand, the reformed gas flowing out from the upper end in the axial direction of the reforming catalyst body 14 passes through the reformed gas inlet 44 corresponding to the annular gap between the upper end of the second cylindrical wall member 12 and the flange portion 50S. It flows out into the reformed gas channel 45 formed between the second cylindrical wall member 12 and the cylindrical cover 22. More specifically, the inner diameter of the second cylindrical wall member 12 is smaller than the inner diameter of the cylindrical cover 22, thereby causing a cylindrical gap between the second cylindrical wall member 12 and the cylindrical cover 22. A reformed gas flow path 45 is formed. The second cylindrical wall member 12 is inserted into the cylindrical cover 22 with a cylindrical gap at the time of assembly. In the state where the second cylindrical wall member 12 is inserted into the cylindrical cover 22 with the directions of the first central axes 110 aligned, a gap is formed between the second cylindrical wall member 12 and the upper end of the second cylindrical wall member 12. Thus, the upper end of the cylindrical cover 22 is closed by the flange portion 50S. Thus, an annular gap as the reformed gas inlet 44 and a cylindrical gap as the reformed gas channel 45 are formed.

  A round bar 46 is disposed in a gap defined by the second cylindrical wall member 12 and the cylindrical cover 22. More specifically, a flexible round bar 46 is spirally wound around the second cylindrical wall member 12, and the round bar 46 is arranged on the second cylindrical wall member 12 and the cylindrical cover 22. A reformed gas spiral channel 45 </ b> A (reformed gas circumferential direction moving means) is formed in the reformed gas channel 45.

  Further, in order to guide the reformed gas flowing through the reformed gas channel 45 to the downstream side through the reformed gas outlet 47 formed in the vicinity of the lower end of the cylindrical cover 22, A reformed gas exhaust pipe 48 is disposed so as to protrude outward in the radial direction.

  More specifically, a reformed gas outlet 47 is formed in the cylindrical cover 22, the reformed gas outlet 47 is connected to the cylindrical cover 22 so as to cover the reformed gas outlet 47, and the cylindrical modified so as to protrude in the radial direction thereof. A quality gas exhaust pipe 48 is provided.

  The area surrounded by the upper walls of the first and second cylindrical wall members 11 and 12 and the support member 43 and the combustion gas exhaust part 33 constitutes the water evaporation part 13 and encloses the mixed gas therein. It functions as a space to perform. Further, a region surrounded by the first and second cylindrical wall members 11 and 12, the support member 43, and the disc-shaped flange portion 50 </ b> S functions as a space for housing the reforming catalyst body 14.

  In the hydrogen generator 10 configured as described above, the heating operation of the heater 131 to the water accumulated in the water reservoir 38 will be described.

When the temperature of the entire hydrogen generator 10 is low, such as when the hydrogen generator 10 is activated, the heat of combustion in the burner 15 is deprived before reaching the water evaporator 13, and the water evaporator 13 itself. Since the temperature is also lowered, it is difficult to quickly heat the water supplied to the water reservoir 38 by combustion heat. In order to eliminate such problems, the heater 131 attached to the first cylindrical wall member 11 efficiently supplies heat to the supply water accumulated in the water reservoir 38.
That is, the temperature of the water evaporation unit 13 detected by the water evaporation unit temperature measuring unit 64 is output to the heater control unit 130. The heater control unit 130 controls heating of the heater 131 to the supply water based on the output signal of the water evaporation unit temperature measuring means 64. For example, when the hydrogen generator 10 is started, the supply water is supplied to the first supply water. The heater control unit 130 controls the heating operation of the heater 131 so as to quickly increase the temperature by heating the heater 131 through the cylindrical wall member 11 and the inside of the water evaporation unit 13 is set to a predetermined temperature (for example, 100 ° C.). If the temperature can be raised to a certain degree), the heater control unit 130 controls the heating operation of the heater 131 so as to stop the heating of the heater 131 to the supply water in order to stop the useless heater heating and suppress the energy loss. .

  Next, the distribution operation of the combustion gas, mixed gas, and reformed gas of the hydrogen generator 10 will be described in order.

  The fuel gas supplied from the fuel gas inlet port 17in connected to the passage (not shown) of the fuel gas (for example, the off gas of the fuel cell) is guided to the fuel gas pipe 17. Thereafter, the fuel gas descends in the direction of the burner 15 through the fuel gas pipe 17. Subsequently, the flow of the fuel gas is blocked by the fuel gas pipe lid 18 that seals the downstream end of the fuel gas pipe 17, and from there, the fuel gas is in the vicinity of the fuel gas pipe lid 18, and the fuel gas The fuel gas is ejected from a plurality of fuel gas ejection holes 19 provided on the side surface of the pipe 17 to the flame region of the burner 15.

  On the other hand, combustion air supplied from an air inlet port 21in connected to an air supply means (not shown) descends in the direction of the burner 15 through the air pipe 21, and in the vicinity of the downstream end of the fuel gas pipe 17. It is provided around the fuel gas pipe 17 and supplied to the inside of an air buffer 23 formed of an annular hollow body that is recessed in a substantially central shape. Then, the air in the air buffer 23 is ejected from the plurality of air ejection holes 20 formed on the inner surface of the concave concave portion to the flame region of the burner 15. In this way, the combustible gas concentration in the mixed gas containing the fuel gas and the air guided to the flame region of the burner 15 is maintained at the combustible concentration, and the combustible gas is burned, and a high-temperature combustion gas is generated inside the burner 15.

  The combustion gas is released to the outside (in the atmosphere) through the third cylindrical wall member 16 and the inside of the first combustion gas flow path 30 through a path indicated by a dotted line shown in FIG.

  The combustion gas generated by the combustion descends the inside of the combustion cylinder 50, and the combustion gas passes through the lower combustion gas inlet 52 as shown by the dotted line in FIG. It is formed between the third cylindrical wall member 16 and the first cylindrical wall member 11 through the second combustion gas channel 53 and the upper combustion gas inlet 31 formed between the wall members 16. The first combustion gas passage 30 is circulated.

  More specifically, the combustion gas generated in the burner 15 descends inside the combustion cylinder 50 and is prevented from descending by a partition member 51 arranged with a gap from the lower end 50A of the combustion cylinder 50. The blocked combustion gas diffuses along the partition member 51 in the radial direction of the partition member 51, passes through the annular lower combustion gas inlet 52, and is formed into a cylindrical second combustion gas flow channel 53. Led inside. Thereafter, while the high-temperature combustion gas is guided upward through the second combustion gas flow channel 53, the first cylindrical wall member 11 and the first combustion gas flow channel 30 with respect to the reforming catalyst body 14. In addition, reaction heat for the endothermic reforming reaction supplied from the combustion gas is given through the third cylindrical wall member 16 (for example, the heat is improved by radiant heat transfer of the third cylindrical wall member 16 heated by the combustion gas). The catalyst body 14 is heated.) The combustion gas rising in the second combustion gas flow channel 53 is blocked from rising by the flange portion 50 </ b> S arranged at a distance from the upper end of the third cylindrical wall member 16. The blocked combustion gas diffuses along the flange 50S in the radial direction of the flange 50S from there, passes through the annular upper combustion gas inlet 31, and the cylindrical first combustion gas flow path 30. Led inside.

  That is, the first and second combustion gas passages 30 and 53 are provided, and the combustion gas is raised in the second combustion gas passage 53 from the vicinity of the lower end 14d of the reforming catalyst body toward the vicinity of the upper end 14u. At the same time, the combustion gas is lowered in the first combustion gas flow path 30 from the vicinity of the upper end 14u of the reforming catalyst body toward the vicinity of the lower end 14d.

  Thereafter, the combustion gas gives reaction heat for a reforming reaction (endothermic reaction) by heat exchange from the combustion gas to the reforming catalyst body 14 while being guided downward through the first combustion gas passage 30. After that, evaporating heat is given to the water inside the water evaporation section 13 by heat exchange from the combustion gas. Here, the upper half portion of the third cylindrical wall member 16 also functions as a combustion cylinder, and gives heat to the reforming catalyst body 14 by its thermal radiation. The combustion gas that has exchanged heat with the water inside the water evaporation section 13 flows into the combustion gas exhaust section 33 from the combustion gas outlet 32. The inflowing combustion gas passes through the inside of the combustion gas exhaust unit 33 and is discharged from the exhaust port pipe 34 to the outside (in the atmosphere).

  As described above, by forming the flame of the burner 15 downward, the combustion product (for example, metal oxide) generated by the combustion of the mixed gas of fuel gas and air is deposited on the partition member 51. It is possible to prevent the combustion product from blocking the air ejection hole 20 and the fuel gas ejection hole 19 of the burner 15 in advance.

  Further, since the burner 15 is inverted 180 ° and installed above the reforming catalyst body, access to the burner 15 at the time of maintenance work becomes easy, and maintenance workability of the burner 15 is improved.

  Further, the combustion gas flow is divided into first and second combustion gas flow passages 30 and 53 so that the combustion gas is raised along the axial direction of the reforming catalyst body 14 and then lowered. By adopting the path, the heat transfer characteristic of the combustion gas with respect to the axial direction of the reforming catalyst body 14 (temperature gradient of the reforming catalyst body 14) can be improved.

  Specifically, the temperature of the combustion gas is highest immediately after flowing out of the combustion cylinder 50 (in the vicinity of the lower combustion gas inlet 52), and thereafter, the reaction heat necessary for the reforming reaction is converted from the combustion gas to the reforming catalyst body. As the gas passes through the first and second combustion gas paths 30 and 53 while being supplied to the fuel gas 14, the temperature of the combustion gas decreases. As an example of the change in the combustion gas temperature, the temperature of the combustion gas is 1000 ° C. at the lower combustion gas inlet 52, and the temperature of the combustion gas is 800 ° C. at the upper combustion gas inlet 31. Under such conditions, the first combustion gas passage 30 may be omitted, and the reaction heat necessary for the reforming reaction may be given to the reforming catalyst body 14 only by the second combustion gas passage 53. Assuming that the temperature difference (200 ° C.) between the combustion gases at the upper and lower combustion gas inlets 31 and 52 is directly reflected in the temperature difference between the upper end 14 u and the lower end 14 d of the reforming catalyst body 14. A temperature gradient is caused in the axial direction due to the temperature difference of the combustion gas.

  In contrast, the first and second combustion gas passages 30 and 53 are provided as in the first embodiment, and the combustion gas is supplied from the lower end 14d of the reforming catalyst body in the second combustion gas passage 53. While raising toward the upper end 14u and lowering the combustion gas from the upper end 14u to the lower end 14d of the reforming catalyst body in the first combustion gas passage 30, the second combustion gas passage 53 described above. Is offset by the axial temperature gradient with respect to the reforming catalyst body 14 generated in the first combustion gas path 30. That is, in the vicinity of the lower end 14d of the reforming catalyst body 14, the temperature of the combustion gas flowing through the second combustion gas passage 53 is on the high temperature side, while the temperature of the combustion gas flowing through the first combustion gas passage 30 is high. Is on the low temperature side. On the other hand, in the vicinity of the upper end 14u of the reforming catalyst body 14, the temperature of the combustion gas flowing through the second combustion gas channel 53 is on the low temperature side, while the first combustion gas channel 30 The temperature of the combustion gas flowing through is on the high temperature side. Therefore, the difference in the temperature of the combustion gas flowing in the first combustion gas channel 30 is made uniform by the difference in the temperature of the combustion gas flowing in the second combustion gas channel 53, and the combustion gas flowing in the second combustion gas channel 53 A large amount of heat transfer to the upper end 14u of the reforming catalyst body 14 having a low temperature is supplied by the fuel gas flowing through the first fuel gas passage 30, and a small amount of heat transfer to the lower end 14d having a high temperature is supplied. Thus, the temperature gradient in the axial direction of the entire reforming catalyst body 14 can be made small and uniform. Therefore, it becomes easy to set the reforming catalyst body 14 in a desired temperature range (for example, 550 ° C. to 650 ° C.), and the entire reforming catalyst body 14 can be used effectively. Durability can be improved by reducing the amount and preventing the high temperature of the local reforming catalyst body 14.

  Further, the mixed gas containing the raw material gas and the water vapor flows out from the water evaporation section 13 to the reforming catalyst body 14 as follows.

  The source gas supplied to the source gas inlet 40in connected to the source supply means is led to the water evaporation unit 13 through the first source gas pipe 40 and supplied to the water inlet 13in connected to the reforming heat exchange unit 60. Is guided to the water evaporation unit 13 through the water pipe 41.

  And as already explained, when the hydrogen generator 10 is started, the water supplied in the water reservoir 38 of the water evaporator 13 can be quickly evaporated by heating the heater 131 via the first cylindrical wall member 11. After heating up to a certain temperature, heating to the supply water of the heater 131 is stopped, and then this heating water receives the heat of evaporation by heat exchange with the combustion gas via the first cylindrical wall member 11 and converts it into water vapor. Is evaporated.

  The water vapor thus evaporated is mixed with the raw material gas in the water evaporation section 13, rises in the axial direction of the water evaporation section 13, and passes through a plurality of mixed gas ejection holes 43 h formed in the support member (partition plate) 43. And flows out to the reforming catalyst body 14. The mixed gas is reformed into a hydrogen-rich reformed gas by a reforming reaction while passing through the reforming catalyst body 14.

  The reformed gas flows out from the reforming catalyst body 14 through the reformed gas channel 45 to the downstream side, as indicated by a thin one-dot chain line shown in FIG.

  More specifically, the reformed gas generated by reforming the mixed gas as described above in the reforming catalyst body 14 rises inside the reforming catalyst body 14 and is prevented from rising by the flange 50S. . The blocked reformed gas diffuses along the flange 50S in the radial direction of the flange 50S from there, and is guided to the reformed gas flow path 45 through the reformed gas inlet 44. Thereafter, the reformed gas is moved in the circumferential direction of the reforming catalyst body 14 along the round bar 46 (bar-shaped member) while being guided downward through the reformed gas spiral channel 45A.

  Thus, the reformed gas flowing through the reformed gas channel 45 flows out to the reformed gas exhaust pipe 48 through the reformed gas outlet 47. The outflowed reformed gas flows out downstream through the reformed gas exhaust pipe 48.

  According to such a hydrogen generator 10, since the first, second and third cylindrical wall members 11, 12, 16 and the cylindrical cover 22 are all simple cylindrical shapes, the hydrogen generator 10 Durability performance is improved. In particular, the first, second and third cylindrical wall members 11, 12, 16 and the cylindrical cover 22 are made of seamless stainless steel metal pipes having no joints such as welds in the middle of the piping. Therefore, it is possible to eliminate the influence on the weld due to the thermal cycle based on the DSS operation in which the start and stop are performed every day.

  Further, the entire circumferential surface from the upper end 14u to the lower end 14d of the reforming catalyst body 14 can be brought into contact with the combustion gas flowing through the first combustion gas flow path 30 via the first cylindrical wall member 11, The reaction heat necessary for the reforming reaction can be efficiently given to the reforming catalyst body 14 from the combustion gas, and the entire surface in the circumferential direction from the upper end 13u to the lower end 13d of the water evaporation section 13 is It is possible to make contact with the combustion gas flowing through the first combustion gas passage 30 via the cylindrical wall member 11, and to efficiently give evaporation heat from the combustion gas to the water inside the water evaporation section 13. Is possible.

  In addition, since the first combustion gas channel 30 can be disposed inside the first cylindrical wall member 11, heat radiation of the combustion gas flowing through the first combustion gas channel 30 can be suppressed.

  Further, since the reformed gas is moved in the circumferential direction of the reforming catalyst body 14, the unevenness of the reformed gas flow in the circumferential direction can be suppressed, and the heat release of the reforming catalyst body 14 kept at a high temperature is spread over the entire circumferential direction. Can be prevented evenly.

  In addition, the heater 131 is annularly attached to the inner peripheral surface of the first cylindrical wall member 11 in the vicinity of the lower end 13d of the water evaporation unit 13, so that the supply accumulated in the water reservoir 38 when the hydrogen generator 10 is started up. Water can be quickly heated by the heater 131, and the startup time of the hydrogen generator 10 can be shortened.

  Here, the modification which further improves the heat-transfer characteristic with respect to the supply water of the heater 131 is demonstrated with reference to FIG. 2 below.

  As shown in FIG. 2, in this modification, a thin film 37 (a porous metal film having a thickness of about 0.5 mm) made of a porous material is formed on the outer peripheral surface of the first cylindrical wall member 11 located in the water reservoir 38. 37). Specifically, FIG. 2 is an enlarged cross-sectional view of the vicinity of the lower end 13d of the water evaporation unit 13 in FIG. The porous metal film 37 extends from the lower end of the water reservoir 38 upward by a fixed distance and over the entire circumferential direction of the outer peripheral surface of the first cylindrical wall member 11 (the surface defining the water evaporation portion 13). Is provided on the outer peripheral surface of the first cylindrical wall member 11. That is, the porous metal film 37 is disposed so as to face the heater portion 131 with the first cylindrical wall member 11 interposed therebetween. As a result, a water reservoir 38 is formed between the porous metal film 37 and the inner peripheral surface of the second cylindrical wall member 12.

  With such a configuration, the porous metal film 37 can be soaked in the water supplied from the water supply means and accumulated in the water reservoir 38 of the water evaporation unit 13 to suck up the water. The porous metal film 37 can increase the evaporation area of water. Then, the entire surface of the porous metal film 37 is heated by the heater 131, and the water that has penetrated into the porous metal film 37 can be efficiently heated.

(Embodiment 2)
FIG. 3 is a cross-sectional view showing the internal structure of the hydrogen generator according to Embodiment 2 of the present invention.

  The main difference between FIG. 3 and FIG. 1 (Embodiment 1) is that the carbon monoxide gas (CO gas) contained in the reformed gas flowing out from the reforming catalyst body 14 is removed. This is because the shift catalyst body 74 and the CO gas removing unit 100 are added downstream of the catalyst body 14 in the reformed gas flow direction.

  Note that a CO gas removing unit 100 is provided in a space surrounded by the water evaporation unit 13 (dead space shown in FIG. 1) to simplify the overall configuration of the hydrogen generator 10.

  Hereinafter, the configuration of the third embodiment will be described focusing on this difference, and the description of the same configuration and operation as those in FIG. 1 will be omitted.

  As shown in FIG. 3, the peripheral structure of the shift catalyst body of the hydrogen generator 10 is mainly a cylindrical seamless metal (stainless steel) shift having a second central axis 120 extending in parallel with the first central axis 110. It has a catalyst body pipe 73 and a cylindrical platinum-type shift catalyst body 74 that is arranged inside the shift catalyst body pipe 73 and removes CO gas in the reformed gas by a shift reaction. Further, both ends of the shift catalyst body 74 in the axial direction of the shift catalyst body 74 disposed inside the shift catalyst body pipe 73 are disc-shaped first and second shift contacts in which a large number of punch holes 76h and 77h for the flow of reformed gas are formed. It is supported by medium punch metals 76 and 77. Furthermore, the inside of the shift catalyst internal pipe 73 in the vicinity of the upper end is connected to the reformed gas outlet 47 via the reformed gas exhaust pipe 48. Further, the lower end of the shift catalyst body pipe 73 is connected to the vicinity of the lower end of the CO gas removal portion outer pipe 92 described later via the shift exhaust pipe 78, and the reformed gas flowing out from the shift catalyst body pipe 73 is converted. The gas can be introduced into the CO gas removing unit 100 through the exhaust pipe 78.

  The CO gas removing unit 100 is disposed inside the third cylindrical wall member 16 so that both first central axes 110 coincide with each other from the lower end thereof. A cylindrical CO gas removing unit inner pipe 93 that forms a heavy pipe, a cylindrical CO gas removing unit outer tube 92 that covers the CO gas removing unit inner tube 93, and an area partitioned by these inner and outer tubes 93 and 92 are arranged. In order to measure the temperature of the lower end of the cylindrical CO gas removal portion catalyst body 98 and the CO gas removal portion catalyst body 98, the catalyst body temperature measuring means 132 (located on the side wall of the CO gas removal portion outer pipe 92) For example, a thermocouple), and annular first and second CO gas removal unit punch metals 96, 97 that support both ends in the axial direction of the CO gas removal unit catalyst body 98 and have a number of punch holes 96h, 97h, CO gas removal It has a CO gas removal unit vertical lid 95, 94 for closing the axial ends of the outer tube 92, the. And the inner pipe 93 has penetrated the center part of the CO gas removal part lower cover 94 to the up-down direction.

  In addition, a disk-shaped first CO gas removal unit heat insulating member 90 covers the surface of the CO gas removal unit upper cover 95 between the partition member 51 and the CO gas removal unit upper cover 95 (the end wall of the CO gas removal unit). The cylindrical second CO gas removal unit heat insulation member 91 is CO between the CO gas removal unit outer tube 92 (the surrounding wall of the CO gas removal unit) and the third cylindrical wall member 16. The gas removal portion outer tube 92 is filled so as to cover the outer peripheral surface. In this way, the first CO gas removal unit heat insulating member 90 prevents the CO gas removal unit 100 from being overheated by the high-temperature (about 1000 ° C.) combustion gas inside the burner 15. In addition, by changing the heat insulation condition of the second CO gas removal section heat insulation member 91, heat exchange between the combustion gas / heater 131 of the first combustion gas flow path 30 and the CO gas removal section catalyst body 98 is performed. The amount of heat generated can be appropriately controlled, and the CO gas removal unit catalyst body 98 can be maintained at a desired temperature.

  The temperature of the water evaporation section 13 detected by the water evaporation section temperature measuring means 64 and the temperature of the CO gas removal section catalyst body 98 detected by the catalyst body temperature measuring means 132 are output to the heater control section 130. The heater control unit 130 controls the heating of the supply water of the heater 131 and the CO gas removal unit catalyst body 98 based on the output signals of these temperature measuring means 64 and 132. For example, when the hydrogen generator 10 is started, the heater control unit 130 controls the heating operation of the heater 131 so as to quickly raise the temperature of the supplied water by heating the heater 131 via the first cylindrical wall member 11. At the same time, the heater control unit 130 may control the heating operation of the heater 131 so as to stop the heating of the heater 131 to the supply water when the temperature inside the water evaporation unit 13 can be raised to a predetermined temperature.

  Alternatively, when the hydrogen generator 10 is started, the second CO gas is provided at the lower end portion of the CO gas removal unit catalyst body 98 that is difficult to be heated by the combustion gas due to proximity to the supply water accumulated in the water reservoir 38. The heater control unit 130 controls the heating operation of the heater 131 so as to quickly increase the temperature by heating the heater 131 via the removal unit heat insulating member 91 and the CO gas removal unit outer tube 92, and also the temperature necessary for the catalytic reaction. When the temperature of the CO gas removal unit catalyst body 98 can be increased, the heater control unit 130 may control the heating operation of the heater 131 so that heating of the CO gas removal unit catalyst body 98 of the heater 131 is stopped.

  Of course, if the supply water and the CO gas removal unit catalyst body 98 can be heated to an appropriate temperature by the heater 131, the waste water heating is stopped and the energy loss is suppressed, so that the supply water and CO gas removal unit catalyst body 98 of the heater 131 is suppressed. After that, the supply water is evaporated so as to receive the heat of vaporization by the heat exchange with the combustion gas via the first cylindrical wall member 11 so as to become water vapor. The removal portion catalyst body 98 receives reaction heat by heat exchange with the combustion gas via the second CO gas removal portion heat insulating member 91 and the CO gas removal portion outer pipe 92 and is maintained at a temperature necessary for the catalytic reaction. .

  In such a configuration, the reformed gas flowing out from the reformed gas outlet 47 circulates inside the shift catalyst body 74 as shown by a thin dashed-dotted path shown in FIG.

  The reformed gas guided from the reformed gas exhaust pipe 48 to the inside of the shift catalyst inner pipe 73 is directed downward by the upper lid of the shift catalyst inner pipe 73 to punch the first shift catalyst body punch metal 76. It flows through the hole 76h and flows into the shift catalyst body 74 maintained at a temperature of 300 ° C to 350 ° C. Then, during the period in which the reformed gas passes through the inside of the shift catalyst body 74, a shift reaction (exothermic reaction) that generates carbon dioxide gas and hydrogen gas from the CO gas and water contained in the reformed gas by the shift catalyst body 74. ) To remove CO gas. Thereafter, the reformed gas after the removal of the CO gas flows out from the shift exhaust pipe 78 downstream through the punch holes 77h of the second shift catalyst body punch metal 77.

  Further, in order to further remove the CO gas in the reformed gas flowing out from the shift catalyst body 74 to the shift exhaust pipe 78, the reformed gas is guided into the CO gas removal section inner pipe 92, and the flow direction is directed upward. To be directed to. The reformed gas is contained in the reformed gas while passing through the inside of the CO gas removing unit catalyst body 98 through the punch hole 97h of the second CO gas removing unit punch metal 97 upward. CO gas is removed.

  After that, the reformed gas after passing through the punch hole 96h of the first CO gas removal unit punch metal 96 is directed downward by the CO gas removal unit upper lid 95, and the inside of the CO gas removal unit inner pipe 93 Flows downward and flows downstream.

  Specific examples of the CO gas removal unit catalyst body 98 may be the platinum-based shift catalyst for shift reaction described above, or a copper-zinc shift catalyst, and a small amount of oxygen gas ( A platinum-based CO selective oxidation catalyst body that mixes the oxygen gas inflow path with the reformed gas and converts the CO gas in the reformed gas into carbon dioxide gas may be used.

  However, when a platinum-based shift catalyst is used as the CO gas removal part catalyst 98, the catalyst temperature (catalyst reaction temperature) is maintained at 150 to 200 ° C., and when a copper-zinc shift catalyst is used, The medium temperature is maintained at 300 to 350 ° C., and when using the CO selective oxidation catalyst body, the catalyst body temperature needs to be maintained at 100 to 150 ° C. Therefore, when the hydrogen generator 10 is started, the heater control unit 130 controls the heating operation of the heater 131 so that the heater 131 can quickly raise the temperature to the catalytic action temperature in accordance with the type of catalyst body to be used. Yes.

  Further, if the load is suddenly changed in the direction of increasing the output during the operation of the hydrogen generator 10, the flow rate of the reformed gas flowing through the CO gas removal unit catalyst body 98 suddenly increases, which increases the flow rate of the reformed gas. When the temperature of the catalyst portion on the upstream side of the reformed gas is lowered by the reformed gas having a low temperature without using the reforming catalyst body 98 as the CO gas removing portion catalyst body 98, There is concern that the site may not exhibit sufficient catalytic properties.

  For this reason, the temperature in the vicinity of the lower end portion of the CO gas removal unit catalyst body 98 is detected by the catalyst body temperature measuring means 132 when the load of the hydrogen generator 10 is changed, and the heater control unit is based on the detected temperature. 130 may control the heating operation of the heater 131 to the CO gas removal unit catalyst body 98. That is, if the temperature detected by the catalyst body temperature measuring means 132 becomes equal to or lower than the reaction temperature of the shift catalyst body (150 ° C. or less for a platinum shift catalyst) as the load of the hydrogen generator 10 changes, the heater controller 130 controls the heater 131 to start heating the shift catalyst body.

  Note that the reformed gas that has flowed out of the shift exhaust pipe 78 from the CO gas removal unit 100 is first guided to the CO gas removal unit inner pipe 93 and flows upward, and then around the CO gas removal unit inner pipe 93. You may let the inside of the installed CO gas removal part catalyst body 98 pass below. Depending on the temperature conditions of the CO gas removal unit catalyst body 98, this may facilitate heat exchange between the heater 131 and the CO gas removal unit catalyst body 98.

(Embodiment 3)
FIG. 4 is a cross-sectional view showing the internal structure of the hydrogen generator according to Embodiment 3 of the present invention.

In the first and second embodiments, the heater 131 is disposed in the first combustion gas flow path 30 and the heater control unit 130 for controlling the heater 131 is provided (see FIG. 1 or FIG. 3). In the third embodiment, the heater control unit 130 and the heater 131 are removed, and a gas combustion catalyst body 133 as a heating element is separately disposed in the first combustion gas flow path 30, whereby the hydrogen generator 10 is started up. As will be described in detail later, unburned gas generated by the burner 15 (gas containing a combustible component such as CO, HC, H ₂ ) and remaining unburned gas in the combustion gas are appropriately treated with an exhaust gas. It is possible to effectively use the heat obtained from the combustion of the fuel gas.

  Since the configuration of the hydrogen generator 10 excluding the gas combustion catalyst body 133 is the same as that described in the second embodiment (see FIG. 3), the description thereof is omitted.

  As shown in FIG. 4, the cylindrical gas combustion catalyst body 133 having a plurality of through holes (described later) for passage of combustion gas in the axial direction has a width substantially the same as the width of the first combustion gas flow path 30. The gas combustion catalyst body 133 is inserted into the first combustion gas passage 30 and fixed at a predetermined position (in the vicinity of the water reservoir 38 of the water evaporation section 13) by an appropriate fixing means.

  As shown in FIG. 5, an example of the cylindrical gas combustion catalyst body 133 is a metal made up of a large number of platinum-based catalyst particles 134 and a thin metal plate carrying these catalyst particles 134, as can be understood in detail from the axial direction. It is constituted by a carrier.

  In detail, this metal carrier is formed in a corrugated shape by forming a first tubular metal plate 133a made of a metal thin plate and a metal thin plate into a corrugated shape by bending it into a corrugated shape. The first corrugated metal plate 133b that abuts the first protrusion 137a on the outer peripheral surface (outer side surface) of the first tubular metal plate 133a, and the second protrusion of the first corrugated metal plate 133b 137b is formed in the same manner as the second circular metal plate 133c contacting the inner peripheral surface (inner side surface) and the first corrugated metal plate 133b, and the third protrusion 137c is formed in the second circle. A second corrugated metal plate 133d that abuts on the outer peripheral surface of the tubular metal plate 133c, and a third circular tubular metal plate that abuts the fourth protrusion 137d of the second corrugated metal plate 133d on the inner peripheral surface thereof. 133e

  That is, in order to increase the contact area between the metal carrier and the unburned gas and promote the combustion reaction of the unburned gas, the first and second corrugated metal plates 133b and 133d are provided with the first, second and third It is sandwiched between circular metal plates 133a, 133c, 133e and laminated in two layers. Of course, such a corrugated metal plate is not limited to two layers, and may be one layer or multiple layers (three layers or more) depending on the combustion conditions of unburned gas.

  Thus, a plurality of first semicircular cross sections formed in the axial direction between the corrugated metal plates 133b and 133d and the first, second and third circular metal plates 133a, 133c and 133e. The unburned gas can pass through the through holes 135 of the catalyst, and the catalyst particles 134 having a small particle diameter are dispersed and supported on the metal carrier while the unburned gas flows through the first through holes 135. Can effectively exhibit its catalytic function, whereby the combustion reaction of the unburned gas is promoted, and the unburned gas can be appropriately burned.

  By using such a metal carrier, even if a porous member is arranged in multiple layers in a narrow channel (for example, about 5 mm), the design is free without causing cracks or cracks in this part. A gas combustion catalyst body excellent in degree can be obtained.

  In addition, as shown in FIG. 6, another example of the cylindrical gas combustion catalyst body 133 is a ceramic that supports a large number of platinum-based catalyst particles 134 and these catalyst particles 134, as can be understood in detail from the axial direction. It is constituted by a carrier.

  Specifically, this ceramic carrier has a cylindrical ceramic body 133f, and a plurality of second through holes 136 having a substantially hexagonal cross section in the axial direction with respect to the wall portion of the ceramic body are formed in a honeycomb shape (honeycomb). Is a porous body formed. The cross section of the second through hole 136 is not limited to a hexagon, and may be a triangle or a quadrangle.

  Thus, while the unburned gas flows through the second through-hole 136, the catalyst particles having a small particle diameter dispersed and supported on the ceramic carrier can effectively exhibit their catalytic functions, thereby causing the combustion reaction of the unburned gas. And the unburned gas can be appropriately combusted.

  In addition, an inexpensive gas combustion catalyst body can be obtained by using such a ceramic carrier.

  So far, the example in which the separate gas combustion catalyst body 133 is inserted into the first combustion gas flow path 30 has been described, but as a modification of this, the first cylinder that partitions the first combustion gas flow path 30 Catalyst particles are applied to the inner peripheral surface of the wall member 11 and / or the outer peripheral surface of the third cylindrical wall member 16, whereby the catalyst particles are applied to the first and / or third cylindrical wall members 11, 16. You may comprise a gas combustion catalyst body by making it adhere to. In this way, the parts for supporting the catalyst particles can be omitted, and the gas combustion catalyst body can be configured simply by reducing the cost. In this case, small catalyst particles dispersed and supported on the first and / or third cylindrical wall members 11 and 16 while the unburned gas flows through the first combustion gas flow path 30 The catalytic function can be effectively expressed, thereby promoting the combustion reaction of the unburned gas, and the unburned gas can be appropriately burned.

  In the hydrogen generator 10 configured as described above, an unburned gas combustion processing operation based on the gas combustion catalyst body 133 will be described.

  The range of the amount of air required for burning the combustible gas in the burner 15 with good exhaust gas characteristics (a state in which almost no unburned gas is discharged) is determined according to the amount of combustion. For this reason, if the amount of air sent from an air fan (not shown) is increased, it deviates from the region of good exhaust gas characteristics, and combustion gas containing unburned gas is generated.

  Here, when the hydrogen generator 10 is started, each part of the hydrogen generator 10 is not in an appropriate temperature state, and the reformed gas flowing out of the hydrogen generator 10 contains 20 ppm or more of CO gas. The battery cannot be supplied. Therefore, the fuel gas of the burner 15 of the hydrogen generator 10 is supplied to the fuel gas inlet port 17in. By doing so, the effective use of energy at the time of startup is realized. However, since the temperature state of the hydrogen generator 10 at the time of start-up changes, the reaction state of each catalyst also changes. Therefore, the flow rate and components of the reformed gas that flows out of the hydrogen generator 10 and is supplied to the burner 15 change drastically within a short time. Therefore, in the burner 15, the amount of air with respect to the reformed gas that is the fuel gas is out of the range having good exhaust gas characteristics, and unburned gas is easily generated.

  On the other hand, the gas combustion catalyst body 133 is in a state where it can be completely burned by the burner 15 even with an air amount outside the range of good exhaust gas characteristics by the burner 15.

  In such a situation, when the hydrogen generator 10 is started, the unburned gas flowing out from the burner 15 is not completely burned inside the burner 15, and the gas combustion catalyst disposed in the first combustion gas flow path 30 is used. The medium 133 can be surely combusted, thereby preventing the unburned gas from being released into the atmosphere, and the heat obtained by the unburned gas combustion is accumulated in the water reservoir 38 of the water evaporation unit 13. It can be effectively used for heating the feed water and heating the CO gas removal unit catalyst body 98 built in the CO gas removal unit 100.

(Embodiment 4)
FIG. 7 is a cross-sectional view showing the internal structure of the hydrogen generator according to Embodiment 4 of the present invention.

  The hydrogen generator 10 of FIG. 7 uses both the heater 131 shown in the second embodiment (FIG. 3) and the gas combustion catalyst body 133 shown in the third embodiment (FIG. 4) as the first combustion gas flow path. 30 is arranged inside.

  According to such a hydrogen generator 10, when the hydrogen generator 10 is started, the heater 131 can appropriately heat the supply water and the CO gas removal unit catalyst body 98 accumulated in the water reservoir 38 of the water evaporator 13. While the unburned gas is prevented from being released into the atmosphere by the gas combustion catalyst body 133, the supply water and the CO gas removal unit catalyst body 98 can be appropriately heated by the unburned gas combustion here as in the heater 131. It is possible to maximize the thermal efficiency of the hydrogen generator 10.

  The hydrogen generator according to the present invention simplifies the configuration of the gas flow path, and can efficiently heat the water in the water evaporation section when the hydrogen generator is activated, thereby performing household fuel cell power generation that performs DSS operation. It can be applied to applications such as devices.

It is sectional drawing which shows the internal structure of the hydrogen generator which concerns on Embodiment 1 of this invention. It is an expanded sectional view of the vicinity of the lower end of a water evaporation part. It is sectional drawing which shows the internal structure of the hydrogen generator which concerns on Embodiment 2 of this invention. It is sectional drawing which shows the internal structure of the hydrogen generator which concerns on Embodiment 3 of this invention. It is sectional drawing which looked at the gas combustion catalyst body which consists of metal carriers from the axial direction. It is sectional drawing which looked at the gas combustion catalyst body which consists of ceramic carriers from the axial direction. It is sectional drawing which shows the internal structure of the hydrogen generator which concerns on Embodiment 4 of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Hydrogen generator 11 1st cylindrical wall member 12 2nd cylindrical wall member 13 Water evaporation part 13in Water inlet 14 Reforming catalyst body 15 Burner 16 Third cylindrical wall member 17 Fuel gas piping 17in Fuel gas inlet Port 18 Fuel gas piping lid 19 Fuel gas ejection hole 20 Air ejection hole 21 Air piping 21 in Air inlet port 22 Cylindrical cover 23 Air buffer 30 First combustion gas flow path 31 Upper combustion gas inlet 32 Combustion gas outlet 33 Combustion Gas exhaust part 34 Exhaust port pipe 38 Reservoir part 40 First raw material gas pipe 40in Raw material gas inlet 41 Water pipe 43 Support member 43h Mixed gas injection hole 44 Reformed gas inlet 45 Reformed gas flow path 45A Reformed gas spiral Shaped channel 46 round bar 47 reformed gas outlet 48 reformed gas exhaust pipe 50 combustion cylinder 50A lower end 50B of combustion cylinder upper end 50S of combustion cylinder flange 51 partition 52 lower combustion gas inlet 53 second combustion gas flow path
64 Water Evaporating Section Temperature Measuring Means 74 Transformation Catalyst Body 76 First Transformation Catalyst Body Punch Metal 76h First Transformation Catalyst Body Punch Metal Punch Hole 77 Second Transformation Catalyst Body Punch Metal
77h Punch hole 78 of the second shift catalyst body punch metal 78 Shift exhaust pipe 90 First CO gas removal portion heat insulation member 91 Second CO gas removal portion heat insulation member 92 CO gas removal portion outer pipe 93 CO gas removal portion inner pipe 94 CO gas removal part lower lid 95 CO gas removal part upper lid 96 First CO gas removal part punch metal 96h First CO gas removal part punch metal punch hole 97 Second CO gas removal part punch metal 97h Second CO gas Punch hole 98 of the removal portion punch metal CO gas removal portion catalyst body 100 CO gas removal portion 110 first central shaft 120 second central shaft 130 heater control portion 131 heater 132 catalyst body temperature measuring means 133 cylindrical gas combustion contact Medium 133a First tubular metal plate 133b First corrugated metal plate 133c Second tubular metal plate 133d Second corrugated Metal plate 133e Third tubular metal plate 133f Ceramic body 134 Catalyst particles 135 First through hole 136 Second through hole 137a First protrusion 137b Second protrusion 137c Third protrusion 137d Fourth Protrusion

Claims (23)

A first cylindrical wall member; a second cylindrical wall member disposed coaxially with the first cylindrical wall member outside the first cylindrical wall member; and the first cylindrical wall A cylindrical water evaporation section and a cylinder provided so as to be aligned in the axial direction of the first and second cylindrical wall members in a first cylindrical space between the member and the second cylindrical wall member A reforming catalyst body in the form of a gas, a burner that generates combustion gas by combustion of combustible gas, and the first cylindrical wall member disposed inside the first cylindrical wall member and coaxially with the combustion A third cylindrical wall member that forms a second cylindrical space for flowing a gas with the first cylindrical wall member; and a heating element disposed inside the second cylindrical space; With
The water flowing in through the water inlet of the water evaporating part is evaporated into water vapor inside the water evaporating part, and the raw material gas flowing in through the raw material gas inlet of the water evaporating part is mixed with the water vapor, and the raw material gas and The mixed gas including the water evaporation section is caused to flow from the water evaporation section into the reforming catalyst body, and the mixed gas thus flowed into the hydrogen-rich reformed gas by a reforming reaction while passing through the reforming catalyst body. Reforming hydrogen generator.   The hydrogen generating apparatus according to claim 1, wherein the heating element is a heater and / or a gas combustion catalyst body.   The hydrogen generator according to claim 1, wherein water flowing into the water evaporation section through the water inlet of the water evaporation section is heated by the heating element to evaporate into water vapor.   A water evaporation unit temperature measuring means for detecting a temperature inside the water evaporation unit; and a heater control unit, wherein the heater control unit is configured to control the heater based on the temperature detected by the water evaporation unit temperature detection unit. The hydrogen generator according to claim 2 which controls heating to said water.   The hydrogen generator according to claim 4, wherein the heater control unit stops heating the water to the water when the temperature detected by the water evaporation unit temperature measuring unit is equal to or higher than a predetermined temperature.   The hydrogen generating apparatus according to claim 2, wherein the gas combustion catalyst body includes catalyst particles and a metal carrier that supports the catalyst particles.   The said metal support | carrier was equipped with the cylindrical 1st metal plate and the 2nd metal plate which has a protrusion part which contacts the side surface of the said 1st metal plate, and is processed into a corrugated shape. Hydrogen generator.   The hydrogen generating apparatus according to claim 2, wherein the gas combustion catalyst body includes catalyst particles and a cylindrical ceramic carrier that supports the catalyst particles.   The hydrogen generating apparatus according to claim 8, wherein a plurality of holes penetrating in the axial direction are formed in the ceramic support in a honeycomb shape.   The hydrogen generating apparatus according to claim 2, wherein the gas combustion catalyst body is configured by applying catalyst particles to an inner peripheral surface of the first cylindrical wall member or an outer peripheral surface of the third cylindrical wall member. . A cylindrical water evaporation portion extending in the direction of the central axis, a cylindrical reforming catalyst body extending in parallel with the central axis of the water evaporation portion on an extension line of the central axis of the water evaporation portion, and combustion of combustible gas And a carbon monoxide gas contained in the reformed gas that is disposed coaxially with the water evaporating unit in a region surrounded by the water evaporating unit and flows out of the reforming catalyst body. A CO gas removal unit that houses a catalyst body that removes gas, and a heating element that is disposed in a cylindrical combustion gas flow path for flowing the combustion gas between the CO gas removal unit and the water evaporation unit, With
The water flowing in through the water inlet of the water evaporating part is evaporated into water vapor inside the water evaporating part, and the raw material gas flowing in through the raw material gas inlet of the water evaporating part is mixed with the water vapor, and the raw material gas and The mixed gas including the water evaporation section is caused to flow from the water evaporation section into the reforming catalyst body, and the mixed gas thus flowed into the hydrogen-rich reformed gas by a reforming reaction while passing through the reforming catalyst body. Reforming hydrogen generator.   The hydrogen generator according to claim 11, wherein the heating element is a heater and / or a gas combustion catalyst body.   The hydrogen generating apparatus according to claim 11, wherein water flowing into the water evaporation unit through the water inlet of the water evaporation unit is heated by the heating element to evaporate into water vapor.   A water evaporation unit temperature measuring means for detecting a temperature inside the water evaporation unit; and a heater control unit, wherein the heater control unit is configured to control the heater based on the temperature detected by the water evaporation unit temperature detection unit. The hydrogen generator according to claim 12, wherein heating to the water is controlled.   The hydrogen generation apparatus according to claim 14, wherein the heater control unit stops heating the water by the heater when the temperature detected by the water evaporation unit temperature measuring unit is equal to or higher than a predetermined temperature.   A catalyst body temperature measuring means for detecting the temperature of the catalyst body; and a heater control section, wherein the heater control section applies the heater to the catalyst body based on the temperature detected by the catalyst body temperature measurement means. The hydrogen generator according to claim 12, which controls heating.   The hydrogen generator according to claim 16, wherein the catalyst body is a shift catalyst body that shifts the carbon monoxide gas.   18. The heater control unit starts heating the shift catalyst body of the heater when a temperature detected by the catalyst body temperature measurement unit is equal to or lower than a predetermined temperature when the load of the hydrogen generator is fluctuated. Hydrogen generator.   The hydrogen generator according to claim 16, wherein the catalyst body is a selective oxidation catalyst body that selectively oxidizes the carbon monoxide gas.   The hydrogen generating apparatus according to claim 12, wherein the gas combustion catalyst body includes catalyst particles and a metal carrier that supports the catalyst particles.   The said metal support | carrier was equipped with the cylindrical 1st metal plate and the 2nd metal plate which has a protrusion part which contacts the side surface of the said 1st metal plate, and is processed into a corrugated shape. Hydrogen generator.   The hydrogen generating apparatus according to claim 12, wherein the gas combustion catalyst body includes catalyst particles and a cylindrical ceramic carrier that supports the catalyst particles.   23. The hydrogen generator according to claim 22, wherein the ceramic carrier has a plurality of holes penetrating in the axial direction formed in a honeycomb shape.

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