JP4715405B2 - Reactor - Google Patents

Description

  The present invention relates to a reactor for reforming liquid fuel, and more particularly to a reactor for generating hydrogen to be supplied to a fuel cell.

  In recent years, fuel cells have begun to be applied to automobiles and portable devices as clean power sources with high energy conversion efficiency. A fuel cell is one in which electric energy is directly extracted from chemical energy by electrochemically reacting fuel and oxygen in the atmosphere.

  As the starting fuel used in the fuel cell, for example, hydrogen is applied. However, since the simple substance of hydrogen is a gas at normal temperature and normal pressure, it has a problem in handling. Although there is an attempt to store hydrogen using a hydrogen storage alloy, the amount of hydrogen stored per unit volume is small, and it is insufficient as a fuel storage means for a power source of a small electronic device such as a portable electronic device. On the other hand, a liquid fuel having hydrogen atoms such as alcohols is applied as a starting fuel, the liquid fuel is vaporized and reformed to generate a reformed gas, and hydrogen in the reformed gas is sent to the fuel cell. A system has also been developed.

In this system, mainly the “vaporizer” that vaporizes the liquid fuel prior to the reforming reaction, the “reformer” that uses the vaporized liquid fuel for the reforming reaction, and the by-product (carbon monoxide) generated by the reforming reaction. Therefore, a “carbon monoxide remover” that removes carbon dioxide is required (for example, see Patent Document 1).
JP 2002-356310 A

By the way, in the above system, when reforming, in order to improve reaction efficiency, the liquid fuel is once vaporized before reforming. However, the vaporization process of liquid fuel, that is, the phase change from liquid to gas, generally involves a large endotherm, so that a sufficient amount of heat that can compensate for the endotherm must be supplied to the vaporizer. The liquid fuel vaporization process cannot be accelerated. If the liquid fuel vaporization process cannot be promoted, the conversion rate to reformed gas will be low, and the amount of hydrogen fed to the fuel cell cannot be increased. As a result, the power generation amount and efficiency of the fuel cell will be reduced. It will be reduced.
An object of the present invention is to accelerate the liquid fuel vaporization process.

In order to solve the above problems, the reaction apparatus according to the first aspect of the present invention provides:
A vaporizer for vaporizing liquid fuel;
A combustor that generates heat by burning a combustion source,
The combustor is arranged around the vaporizer,
The vaporizer has a vaporization introduction path including a liquid absorbing material that absorbs the liquid fuel,
The combustor includes a high temperature reaction section for reforming the liquid fuel vaporized by the vaporizer and a low temperature reaction section for removing carbon monoxide from a product of the high temperature reaction section . The low temperature reaction part is heated.

According to the first aspect of the present invention, since the combustor is arranged so as to go around the carburetor, the combustion heat of the combustor is conducted from around the carburetor to the carburetor. Therefore, the vaporizer can be efficiently heated to such an extent that the heat absorption associated with the liquid fuel vaporization step can be compensated, the liquid fuel vaporization step in the vaporizer can be promoted, and the liquid absorbing material is provided. The liquid fuel can be stably introduced into the vaporizer, and when the proper temperature range of the vaporizer is closer to the proper temperature range of the low temperature reaction section than the proper temperature range of the high temperature reaction section, vaporization can be efficiently performed. Ru can heat the vessel and the low-temperature reaction unit.

The reactor according to claim 1,
The combustion source may be hydrogen gas.

  If the combustion source is hydrogen gas, unreacted hydrogen that could not be used in the fuel cell can be reused as a combustion source for the combustor.

The reactor according to claim 1,
The combustion source may be methanol gas.

  When the combustion source is methanol gas, when methanol is applied as the liquid fuel, the liquid fuel can be used in combination for two purposes of reforming and combustion.

  The combustor may include a combustion catalyst that promotes a combustion reaction of the combustion source.

  When the combustor has a combustion catalyst, the combustion reaction of the combustion source can be promoted, and the heat generation efficiency in the combustor can be improved.

The combustor has a combustion flow path for circulating the combustion source;
The combustion catalyst may be applied to the bottom surface and the side surface of the combustion channel.

  When the combustion catalyst is applied to the bottom surface and the side surface of the combustion channel, the combustion reaction of the combustion source flowing through the combustion channel can be greatly induced.

  The combustor may include a combustor plate in which a combustion channel for circulating the combustion source is formed, and a structure in which a plurality of the combustor plates are stacked.

  When the combustor plate is provided with a combustion catalyst, particularly around the combustion flow path, the thinner the combustor plate, that is, the narrower the combustion flow path, the more the combustion source diffuses into the combustion catalyst. It becomes easy and it becomes easy to burn efficiently. The vaporizer can be effectively heated by stacking a plurality of such thin combustor plates.

The vaporizer may include a vaporization introduction path for introducing liquid fuel and a hydrogen gas discharge path for discharging the hydrogen gas generated by the reaction path.
In this case, the waste heat from the hydrogen gas discharged from the hydrogen gas discharge passage heats the vaporizer, so that the fuel is more easily vaporized more efficiently.

The carburetor may include a combustion mixture introduction path for introducing a combustion source to the combustor and an exhaust gas discharge path for discharging exhaust gas generated when combusted in the combustor.
In this case, waste heat from the exhaust gas discharged from the exhaust gas discharge path heats the carburetor, so that the fuel is easily vaporized more efficiently.

A heating wire that generates heat when supplied with electric power may be further provided, and the heating wire may be arranged to circulate around the vaporizer.

  According to the present invention, heat can be conducted from around the vaporizer to the vaporizer, and the vaporizer is efficiently heated to such an extent that the heat of vaporization in the vaporization step (endothermic step) of the liquid fuel can be compensated. Can do. Therefore, the vaporization process of the liquid fuel in the vaporizer can be promoted.

  The best mode for carrying out the present invention will be described below with reference to the drawings. However, although various technically preferable limitations for implementing the present invention are given to the embodiments described below, the scope of the invention is not limited to the following embodiments and illustrated examples.

  FIG. 1 is a perspective view of the microreactor module 1 shown obliquely from above, FIG. 2 is a perspective view of the microreactor module 1 shown obliquely from below, and FIG. 3 is a side view of the microreactor module 1.

  The microreactor module 1 is a reaction device that generates hydrogen gas used in a fuel cell, which is built in an electronic device such as a notebook personal computer, a PDA, an electronic notebook, a digital camera, a mobile phone, a wristwatch, a register, or a projector. The microreactor module 1 is a high-temperature reaction in which a relatively high temperature reforming reaction occurs in an appropriate reaction temperature range in a supply / discharge unit 2 in which reactants are supplied and products are discharged and a low-temperature reaction unit 6 described later. Reaction product and production between the high temperature reaction part 4 and the low temperature reaction part 6 in which the selective oxidation reaction relatively low with respect to the appropriate reaction temperature range in the high temperature reaction part 4 and the high temperature reaction part 4 occurs. And a connecting pipe 8 for inflow or outflow of goods.

  FIG. 4 is a schematic side view when the microreactor module 1 is divided for each function. As shown in FIG. 4, the supply / discharge unit 2 is mainly provided with a carburetor 502 and a first combustor 504. The first combustor 504 includes a fuel that is at least partially vaporized (for example, hydrogen gas, methanol gas, and the like) and a gas that serves as an oxygen source such as air containing oxygen for burning the fuel. These gases are supplied separately or as an air-fuel mixture, and these gases are burned by the catalyst in the first combustor 504 to generate heat. The vaporizer 502 is supplied with water and liquid fuel (for example, alcohols such as methanol and ethanol, ethers such as dimethyl ether, and fossil fuels such as gasoline) from the fuel container separately or mixed. The heat of combustion in the combustor 504 is conducted into the vaporizer 502, whereby water and liquid fuel are vaporized in the vaporizer 502.

  The high temperature reaction section 4 is mainly provided with a first reformer 506, a second combustor 508, and a second reformer 510. The first reformer 506 and the second reformer 510 are both reformers that generate hydrogen by reforming the fuel, and are configured to communicate with each other. The first reformer 506 is on the lower side, the second reformer 510 is on the upper side, and the second combustor 508 is sandwiched between the first reformer 506 and the second reformer 510.

  In the second combustor 508, a fuel (for example, hydrogen gas, methanol gas, etc.) at least a part of which is vaporized and a gas serving as an oxygen source such as air containing oxygen are separately or as an air-fuel mixture. Then, these gases are burned by the catalyst in the second combustor 508 to generate heat. Note that in some cases, unreacted hydrogen gas is included in the off-gas discharged from the fuel cell after the hydrogen gas is supplied to generate an electrochemical reaction, and the first combustor 504 and the second combustor 508 At least one of them may emit heat by burning this unreacted hydrogen gas with a gas such as oxygen-containing air. Of course, at least one of the first combustor 504 and the second combustor 508 vaporizes the liquid fuel (for example, methanol, ethanol, butane, dimethyl ether, gasoline) stored in the fuel container by another vaporizer. The vaporized fuel may be combusted with a gas such as air containing oxygen.

When the second combustor 508 burns off-gas discharged from the fuel cell, first, at the start, the first reformer 506 and the second reformer 510 are heated by a heating wire 172 described later to generate hydrogen. When the off-gas containing hydrogen is steadily discharged from the fuel cell to which this hydrogen is supplied, the second combustor 508 burns the hydrogen in the off-gas, and the first reformer 506 and the second reformer 510. Heat. When the 2nd combustor 508 becomes a main heat source, the applied voltage with respect to the heating wire 172 will become low so that it may switch to an auxiliary heat source. In the heated first reformer 506 and second reformer 510, hydrogen gas and the like are generated from water and fuel by a catalytic reaction, and a carbon monoxide gas is further generated in a small amount. When the fuel is methanol, chemical reactions such as the following formulas (1) and (2) occur. Note that the reaction in which hydrogen is generated is an endothermic reaction, and the combustion heat of the second combustor 508 is used.
CH ₃ OH + H ₂ O → 3H ₂ + CO ₂ (1)
2CH ₃ OH + H ₂ O → 5H ₂ + CO + CO ₂ (2)

  The low temperature reaction unit 6 is mainly provided with a carbon monoxide remover 512. The carbon monoxide remover 512 is supplied with an air-fuel mixture containing hydrogen gas, carbon monoxide gas, and the like from the first reformer 506 and the second reformer 510 while being heated by the first combustor 504. Furthermore, air is supplied. The carbon monoxide remover 512 selectively oxidizes carbon monoxide from the air-fuel mixture, thereby removing the carbon monoxide. An air-fuel mixture (hydrogen-rich gas) from which carbon monoxide has been removed is supplied to the fuel electrode of the fuel cell.

  Hereinafter, specific configurations of the supply / discharge unit 2, the high temperature reaction unit 4, the low temperature reaction unit 6, and the connecting pipe 8 will be described with reference to FIGS. 3 and 5 to 15. 5 is an exploded perspective view of the microreactor module 1, FIG. 6 is a perspective view of the first combustor 504, FIG. 7 is an exploded perspective view of the first combustor 504, and FIG. FIG. 9 is a cross-sectional view taken along a plane direction of a combustor plate 12 to be described later from a cutting line VIII-VIII, and FIG. 9 is a plane direction of a base plate 28 and a base plate 102 to be described later from a cutting line IX-IX in FIG. FIG. 10 is a cross-sectional view taken along the line X-X in FIG. 3, and FIG. 10 is a cross-sectional view taken along the plane direction of the lower frame 30 and the lower frame 104, which will be described later. FIG. 12 is a cross-sectional view taken along the plane direction of the middle frame 32 and the middle frame 106, which will be described later, from the cutting line XI-XI in FIG. 3, and FIG. 12 is an upper frame, which will be described later, from the cutting line XII-XII in FIG. 34 and an arrow cut along the plane direction of the upper frame 110 FIG. 13 is a cross-sectional view taken along the plane direction of the combustor plate 108, which will be described later, from a cutting line XIII-XIII in FIG. 3. FIG. 14 is a cross-sectional view from the cutting line XIV-XIV in FIG. FIG. 6 is a cross-sectional view taken along an arrow along a surface direction orthogonal to the communication direction of the connecting pipe 8. FIG. 15 is a cross-sectional view taken along the line XV-XV in FIG. 9 along the thickness direction of the low temperature reaction part 6.

  As shown in FIGS. 3, 5, and 8, the supply / exhaust unit 2 is laminated with an external flow pipe 10 made of a metal material such as stainless steel (SUS304) having excellent corrosion resistance, and the external flow pipe 10 around the external flow pipe 10. Three combustor plates 12. The combustor plate 12 is joined to the external flow pipe 10 by hard soldering. As the wax, it is preferable to apply a wax having a melting point higher than the maximum temperature of the fluid flowing through the external flow pipe 10 and the combustor plate 12 and having a melting point of 700 degrees or more. On the other hand, a gold wax containing silver, copper, zinc and cadmium, a wax containing gold, silver, zinc and nickel as main components, or a wax containing gold, palladium and silver as main components is particularly preferable.

  The external circulation pipe 10 is a pipe having a plurality of channels through which each fluid in the microreactor module 1 is circulated to the outside of the microreactor module 1. In the external circulation pipe 10, the vaporization introduction path 14, the air introduction path 16, the combustion mixture introduction path 18, the exhaust gas discharge path 20, the combustion mixture introduction path 22 and the hydrogen gas discharge path 24 are parallel to each other. Is provided. The vaporization introduction path 14, the air introduction path 16, the combustion mixture introduction path 18, the exhaust gas discharge path 20, the combustion mixture introduction path 22 and the hydrogen gas discharge path 24 are partitioned by a partition wall 29 of the external circulation pipe 10. Yes.

  The vaporization introduction path 14, the air introduction path 16, the combustion mixture introduction path 18, the exhaust gas discharge path 20, the combustion mixture introduction path 22, and the hydrogen gas discharge path 24 are provided in one external circulation pipe 10. However, the external flow pipe 10 may be one in which these flow paths 14, 16, 18, 20, 22, 24 are provided in separate pipe materials and these pipe materials are bundled. The hydrogen gas discharge path 24 of the external flow pipe 10 is connected to a fuel electrode of a power generation module 608 described later, and the vaporization introduction path 14 of the external flow pipe 10 is connected to a fuel container 604 via a flow rate control unit 606 described later. It is connected.

  The vaporization introduction path 14 is filled with a liquid absorbing material 33 such as a felt material, a ceramic porous material, a fiber material, and a carbon porous material. The liquid absorbing material 33 absorbs liquid, and the liquid absorbing material 33 is obtained by solidifying inorganic fibers or organic fibers with a binder, sintered inorganic powder, or binding inorganic powder. It may be hardened with a material or a mixture of graphite and glassy carbon.

Here, the first combustor 504 will be described in detail.
The first combustor 504 appropriately heats the carbon monoxide remover 512 and the vaporizer 502. As shown in FIG. 6, the first combustor 504 has a structure in which three combustor plates 12 each having a square frame shape are stacked. The outer circulation pipe 10 is arranged so as to go around the outer periphery. The three combustor plates 12 are made of a metal material such as stainless steel (SUS304) having excellent corrosion resistance, like the external flow pipe 10, and the external flow pipe 10 is inserted in the state where the external flow pipe 10 is inserted. It is joined with.

  As shown in FIG. 7, the combustor plate 12 has a frame portion 12a having a rectangular frame shape, and a rectangular through hole 12b is formed therein. A side wall 12c is formed on the outer edge of the frame portion 12a, and a partition wall 12d is formed from a midway portion of the side wall 12c toward the through hole 12b. The through hole 12b has a size corresponding to the outer periphery of the external circulation pipe 10, and the external circulation pipe 10 can be inserted into the through hole 12b.

  The external circulation pipe 10 is joined in a state of being inserted through the through hole 12b. In this state, as shown in FIG. 6, the partition wall 10 a of the external circulation pipe 10 that separates the combustion mixture introduction path 22 and the exhaust gas discharge path 20 and the partition wall 12 d of the combustor plate 12 correspond to each other. In the first combustor 504, the three combustor plates 12 are joined in a stacked state, and the uppermost combustor plate 12 is joined to the lower surface of the low-temperature reaction unit 6, so that airtightness is achieved. A high combustion channel 26 is formed. As indicated by arrows in FIG. 6, the combustion flow paths 26 in each combustor plate 12 both lead from the same combustor mixture introduction path 22 to the same exhaust gas discharge path 20.

  Combustion channels for burning gaseous fuel (for example, hydrogen gas, methanol gas, etc.) as a combustion source with oxygen are formed on the bottom and side surfaces (the inner surface of the side wall 12c and both side surfaces of the partition wall 12d) of the combustion channel 26. A catalyst is applied. Examples of the combustion catalyst include platinum.

  The liquid absorbing material 33 in the external circulation pipe 10 is filled until the tip reaches the position of the combustor plate 12. Further, the proper heating temperature range of the carbon monoxide remover 512 by the first combustor 504 and the proper heating temperature range of the vaporizer 502 by the first combustor 504 are different as described later. Such a difference in the appropriate temperature range is caused by the difference in the area of the first combustor 504 facing the carbon monoxide remover 512 and the area facing the vaporizer 502. In the present embodiment, the first combustor 504 is configured by the three combustor plates 12. However, if the first combustor 504 is set to be in such an appropriate temperature range, the first combustor 504 is configured by the single combustor plate 12. Alternatively, two combustor plates 12 or four or more combustor plates 12 may be used, and the number of combustor plates 12 constituting the first combustor 504 may be changed as appropriate. May be.

  As shown in FIGS. 3 and 5, the low temperature reaction unit 6 is formed by laminating a base plate 28, a lower frame 30, a middle frame 32, an upper frame 34, and a lid plate 36 in this order from the bottom, and has a rectangular parallelepiped shape. ing. The base plate 28, the lower frame 30, the middle frame 32, the upper frame 34, and the lid plate 36 are made of a metal material such as stainless steel (SUS304) having excellent corrosion resistance.

  The outer circulation pipe 10 and the uppermost combustor plate 12 are joined to the lower surface of the base plate 28 at the center in the width direction of the base plate 28. As shown in FIG. 9, by providing a partition wall 41 protruding on the upper surface of the base plate 28, a mixed gas flow path 38, a mixed flow path 40, a carbon monoxide removal flow path 42, a distorted monoxide. It is divided into a carbon removal channel 44, a U-shaped carbon monoxide removal channel 46, a combustion mixture channel 48 and an exhaust gas channel 50.

  A through hole 52 is formed at the end of the mixed gas flow path 38, and the mixed gas flow path 38 communicates with the vaporization introduction path 14 of the external flow pipe 10 through the through hole 52. The carbon monoxide removal channel 46 surrounds the through hole 52, a through hole 54 is formed at the end of the carbon monoxide removal channel 46, and the carbon monoxide removal channel 46 passes through the through hole 54. It leads to a discharge path 24 for hydrogen gas.

  A through hole 58 is formed at the end of the combustion mixture flow path 48, and the combustion mixture flow path 48 communicates with the combustion mixture introduction path 18 through the through hole 58. A through hole 56 is formed at the end of the exhaust gas channel 50, and the exhaust gas channel 50 communicates with the exhaust gas discharge channel 20 through the through hole 56. A through hole 60 is formed at the end of the mixing channel 40, and the mixing channel 40 communicates with the air introduction path 16 through the through hole 60. A bottom plate 53 is provided on the lower surface of the base plate 28 except for the through hole 52, the through hole 54, the through hole 56, the through hole 58, and the through hole 60.

  As shown in FIG. 10, the partition 43 is provided inside the lower frame 30, so that the inner side of the lower frame 30 has a twisted carbon monoxide removal channel 62 and a spiral carbon monoxide removal channel. 64, a blow-through hole 66, a combustion mixture passage 68, and an exhaust gas passage 70. A bottom plate 72 is provided in the carbon monoxide removal channel 64, the combustion mixture channel 68 and the exhaust gas channel 70. When the lower frame 30 is joined to the base plate 28 by brazing or the like, the bottom plate 72 causes the mixed gas channel to flow. 38, the mixture channel 40, the carbon monoxide removal channel 46, the combustion mixture channel 48 and the exhaust gas channel 50 are covered.

  One end portion 64 a of the carbon monoxide removal flow path 64 communicates with the carbon monoxide removal flow path 62, and the carbon monoxide removal flow path 42 of the base plate 28 in the middle of the carbon monoxide removal flow path 64. A blow-through hole 74 communicating with the exhaust gas flow path 50 of the base plate 28 is formed at the other end 64b of the carbon monoxide removal flow path 64.

The partition wall 43 overlaps with the partition wall 41 so that the carbon monoxide removal channel 62 and the carbon monoxide removal channel 44 in plan view coincide with each other, and the carbon monoxide removal channel 62 and the carbon monoxide. The removal channel 44 is blown through. The blow-through hole 66 is located on the mixing channel 40 of the base plate 28. A blow-through hole 69 is formed in the combustion mixture flow path 68, and the combustion mixture flow path 68 communicates with the combustion mixture flow path 48 of the base plate 28 via the blow-through hole 69. An exhaust hole 71 is formed in the exhaust gas flow path 70, and the exhaust gas flow path 70 communicates with the exhaust gas flow path 50 of the base plate 28 via the blow through hole 71.
When viewed from above, the external circulation pipe 10 has a structure in which the carbon monoxide removal flow path 64 overlaps with a part of the carbon monoxide removal flow path 64 and the carbon monoxide removal flow path 64 spirals around the external flow pipe 10.

  As shown in FIG. 11, the partition 45 is provided inside the middle frame 32, so that the inside of the middle frame 32 has a twisted carbon monoxide removal channel 78 and a spiral carbon monoxide removal channel. 80 and a blow-through hole 82. A part of the carbon monoxide removal channel 80 is provided with a bottom plate 83. When the middle frame 32 is joined to the lower frame 30 by brazing or the like, the bottom plate 83 causes the combustion mixture channel 68 and exhaust gas of the lower frame 30 to be joined. The upper part of the flow path 70 is covered.

  The partition wall 45 overlaps the partition wall 43 so that the carbon monoxide removal channel 78 and the carbon monoxide removal channel 62 of the lower frame 30 coincide with each other in plan view, and the carbon monoxide removal channel 78 and the monoxide are oxidized. The carbon removal channel 62 is blown through. The partition wall 45 overlaps the partition wall 43 so that the carbon monoxide removal channel 80 and the carbon monoxide removal channel 64 of the lower frame 30 coincide with each other in plan view, and the carbon monoxide removal channel 80 and the monoxide are oxidized. The carbon removal channel 64 is blown through. The blow-through hole 82 is overlapped with the blow-through hole 66 of the lower frame 30 so that the blow-through hole 82 and the blow-through hole 66 are in communication with each other.

  As shown in FIG. 12, the partition wall 47 is provided on the inner side of the upper frame 34, so that a distorted carbon monoxide removal channel 84 is formed on the inner side of the upper frame 34. Further, a bottom plate 86 is provided on the entire inner side of the upper frame 34. When the upper frame 34 is joined to the middle frame 32 by brazing or the like, the carbon monoxide removal flow path 78 and the monoxide are removed by the bottom plate 86. The upper part of the carbon removal channel 80 is covered.

  A blow-through hole 88 is formed at one end of the carbon monoxide removal flow path 84, and a blow-through hole 90 is formed at the other end of the carbon monoxide removal flow path 84. The blow-through hole 88 overlaps the blow-through hole 82 of the middle frame 32, and the carbon monoxide removal flow path 84 communicates with the mixing flow path 40 through the blow-through hole 88, the blow-through hole 82, and the blow-through hole 66. The blow-through hole 90 is positioned on the end of the carbon monoxide removal flow path 78 of the middle frame 32, and the carbon monoxide removal flow path 84 communicates with the carbon monoxide removal flow path 78 through the blow-through hole 90. .

  As shown in FIG. 5, the lid plate 36 is joined onto the upper frame 34, so that the upper side of the carbon monoxide removal channel 84 is covered with the lid plate 36. Here, a carbon monoxide selective oxidation catalyst that selectively oxidizes carbon monoxide is formed on the entire wall surfaces of the carbon monoxide removal flow paths 42, 44, 46, 46, 62, 64, 78, 80, and 84. It is supported. Here, a catalyst for selective oxidation of carbon monoxide is supported in advance at predetermined portions of the base plate 28, the lower frame 30, the middle frame 32, and the flow path upper frame 34, which are the wall surfaces, before being joined to each other. Examples of the catalyst for selective oxidation of carbon monoxide include platinum.

  As shown in FIGS. 3 and 5, the high temperature reaction unit 4 is formed by laminating a base plate 102, a lower frame 104, a middle frame 106, a combustor plate 108, an upper frame 110 and a lid plate 112 in this order from the bottom. It has a rectangular parallelepiped shape. The base plate 102, the lower frame 104, the middle frame 106, the combustor plate 108, the upper frame 110, and the lid plate 112 are made of a metal material such as stainless steel (SUS304) having excellent corrosion resistance.

  As shown in FIG. 9, the base plate 102 is provided with a bottom plate 113, and the partition wall 103 is provided on the upper surface of the bottom plate 113 so that the supply flow path 114, the distorted reforming flow is provided. It is divided into a channel 116 and a discharge channel 115. The supply flow path 114 is continuous with the reforming flow path 116, but the discharge flow path 115 is independent of the supply flow path 114 and the reforming flow path 116.

  As shown in FIG. 10, the partition wall 105 is provided inside the lower frame 104, so that the reforming channel 118, the combustion mixture channel 120, the exhaust gas channel 122, and the blow-through are formed inside the lower frame 104 in a distorted shape. It is divided into holes 124. A bottom plate 126 is provided in the combustion mixture flow channel 120 and the exhaust gas flow channel 122, and the lower frame 104 is joined to the base plate 102, so that the supply flow channel 114 and the discharge flow channel 115 of the base plate 102 are covered by the bottom plate 126. . The partition wall 105 overlaps the partition wall 103 so that the reforming channel 118 and the reforming channel 116 of the base plate 102 coincide with each other in plan view, and the reforming channel 118 and the reforming channel 116 are blown through. It is said that.

  As shown in FIG. 11, the partition wall 107 is provided inside the middle frame 106, so that the inside of the middle frame 106 has a twisted reforming flow path 128, a blow hole 130, a blow hole 132, and a blow hole 134. It is divided. The middle frame 106 is provided with a bottom plate 136, and the middle frame 106 is joined to the lower frame 104, so that the bottom plate 136 covers the combustion mixture flow path 120 and the exhaust gas flow path 122 of the lower frame 104. .

  The partition wall 107 overlaps with the partition wall 105 so that the reforming channel 128 coincides with the reforming channel 118 of the lower frame 104 in plan view, and the reforming channel 128 and the reforming channel 118 are blown through. It is in a state. The blow-through hole 130 is overlapped with the blow-through hole 124 of the lower frame 104, and the blow-through hole 130 and the blow-through hole 124 are blown through. The blow-through hole 132 is located on the end of the combustion mixture flow path 120, and the blow-through hole 134 is located on the end of the exhaust gas flow path 122.

  As shown in FIGS. 3 and 5, the combustor plate 108 is joined onto the middle frame 106, whereby the reforming flow path 128 of the middle frame 106 is covered with the combustor plate 108. As shown in FIG. 13, the combustor plate 108 is provided with a bottom plate 141, and a partition wall 109 is provided on the upper surface of the bottom plate 141 so that the combustion chamber 138, the combustion chamber 140, the blow-through hole 142, and the blow-through are formed. It is divided into holes 144.

  A blow-through hole 146 is formed at the end of the combustion chamber 138, the blow-through hole 146 is positioned on the blow-through hole 132 of the middle frame 106, and the combustion chamber 138 is formed in the lower frame 104 via the blow-through hole 146 and the blow-through hole 132. It leads to the combustion mixture flow path 120. The combustion chamber 138 communicates with the combustion chamber 140.

  A blow-through hole 148 is formed at the end of the combustion chamber 140, the blow-through hole 148 is positioned on the blow-through hole 134 of the middle frame 106, and the combustion chamber 140 passes through the blow-through hole 148 and the blow-through hole 134 and the exhaust gas flow path 122. Leads to.

  The blow-through hole 142 is located on the end of the reforming flow path 128 of the middle frame 106, and the blow-through hole 142 communicates with the reforming flow path 128. The blow-through hole 144 is located on the blow-through hole 130 of the middle frame 106, and the blow-through hole 144 communicates with the blow-through hole 130. A combustion catalyst for burning the combustion mixture is carried on the wall surfaces of the combustion chamber 138 and the combustion chamber 140. Here, the combustion catalyst is supported in advance at predetermined portions of the combustor plate 108 and the upper frame 110 which are the wall surfaces before being joined to each other. An example of the combustion catalyst is platinum.

  As shown in FIG. 12, the partition wall 111 is provided on the inner side of the upper frame 110, so that a distorted reforming flow channel 150 is formed on the inner side of the upper frame 110. In addition, a bottom plate 152 is provided on the upper frame 110, and the upper frame 110 is joined to the combustor plate 108 by brazing or the like, so that the upper portions of the combustion chamber 138 and the combustion chamber 140 of the combustor plate 108 are covered. The

  A blow-through hole 154 is formed at one end of the reforming flow path 150, and a blow-through hole 156 is formed at the other end of the reforming flow path 150. The blow-through hole 154 is located on the blow-through hole 142 of the combustor plate 108, and the reforming flow path 150 communicates with the reforming flow path 128 of the middle frame 106 through the blow-through hole 154 and the blow-through hole 142. The blow-through hole 156 is located on the blow-through hole 144 of the combustor plate 108, and the reforming flow path 150 communicates with the discharge flow path 115 through the blow-through hole 156, the blow-through hole 144, the blow-through hole 130, and the blow-through hole 124. Yes.

  As illustrated in FIG. 5, the lid plate 112 is joined to the upper frame 110 by brazing or the like, so that the upper portion of the reforming flow path 150 is covered with the lid plate 112. Here, reforming catalysts for reforming the fuel to generate hydrogen are supported on the wall surfaces of the supply channel 114, the discharge channel 115, and the reforming channels 116, 118, 128, and 152. Here, a combustion catalyst is supported in advance at predetermined portions of the base plate 102, the lower frame 104, the middle frame 106, the combustor plate 108, the upper frame 110, and the lid plate 112, which are the wall surfaces, before being joined to each other. . Examples of the reforming catalyst used for reforming methanol include a Cu / ZnO-based catalyst and a Pt / ZnO-based catalyst.

  As shown in FIGS. 3 and 4, the outer shape of the connecting pipe 8 is a prismatic shape, the width of the connecting pipe 8 is narrower than the width of the high temperature reaction section 4 and the width of the low temperature reaction section 6, and the height of the connection pipe 8 is also high. It is lower than any height of the high temperature reaction part 4 and the low temperature reaction part 6. The connecting pipe 8 is installed between the high temperature reaction part 4 and the low temperature reaction part 6, and the connecting pipe 8 is joined to the high temperature reaction part 4 by brazing or the like at the center in the width direction of the high temperature reaction part 4. The low temperature reaction part 6 is joined to the low temperature reaction part 6 by brazing or the like at the center in the width direction. Further, the lower surface of the connecting pipe 8 is flush with the lower surface of the high temperature reaction unit 4, that is, the lower surface of the base plate 102, and further flush with the lower surface of the low temperature reaction unit 6, that is, the lower surface of the base plate 28. Yes.

  As shown in FIGS. 9, 10, and 14, the connecting pipe 8 is provided with a connecting channel 162, a connecting channel 164, a connecting channel 166, and a connecting channel 168 that are parallel to each other. The connection channel 162, the connection channel 164, the connection channel 166, and the connection channel 168 are partitioned by a partition wall 163 of the connection pipe 8. One end of the connection channel 162 communicates with the mixed gas channel 38, and the other end of the connection channel 162 communicates with the supply channel 114. One end of the connection channel 164 communicates with the discharge channel 115 and the other end communicates with the mixing channel 40. One end of the connection channel 166 communicates with the combustion mixture channel 68, and the other end communicates with the combustion mixture channel 120. One end of the connection channel 168 communicates with the exhaust gas channel 122 and the other end communicates with the exhaust gas channel 70.

  In addition, although the connection flow paths 162, 164, 166, and 168 are provided in one connection pipe 8, these flow paths 162, 164, 166, and 168 are provided in separate pipe materials, and these pipe materials are bundled. May be. The connecting pipe 8 is preferably made of the same material as the base plate 28, the lower frame 30, the base plate 102, and the lower frame 104 that are joined from the viewpoint of airtightness.

  As described above, the flow path is partitioned by the partition walls (including the bottom plate, the top plate, the side plate, and the outer plate) in the supply / discharge unit 2, the high temperature reaction unit 4, the low temperature reaction unit 6 and the connecting pipe 8. In this case, the thickness of the partition wall is 0.1 mm or more and 0.2 mm or less, preferably 0.1 mm.

  That is, in the high temperature reaction section 4, the partition wall 103 of the base plate 102, the partition wall 105 of the lower frame 104, and the partition wall 107 of the middle frame 106 overlap each other in the surface direction, and a meandering sidewall is formed. The reforming flow path 116, the supply flow path 114, and the discharge flow path 115 are partitioned by the upper surface of the bottom plate 113 and the lower surface of the bottom plate 141 of the combustor plate 108. The combustion chambers 138 and 140 are partitioned by the upper surface of the bottom plate 141 of the combustor plate 108, the lower surface of the partition plate 109 and the bottom plate 152 of the upper frame 110. Further, the reforming flow path 150 is partitioned by the upper surface of the bottom plate 152 of the upper frame 110, the partition wall 111, and the lower surface of the lid plate 112.

  In the low-temperature reaction part 6, the partition wall 41 of the base plate 28, the partition wall 43 of the lower frame 30, and the partition wall 45 of the middle frame 32 are formed to meander to form a meandering side wall, and in addition to this side wall, the base plate 28 Each flow path is partitioned by the upper surface of the bottom plate 53 and the bottom plate 86 of the upper frame 34. Further, the carbon monoxide removal channel 84 is partitioned by the upper surface of the bottom plate 86 of the upper frame 34, the partition wall 47, and the lower surface of the lid plate 36.

  The paths of the flow paths provided inside the supply / discharge section 2, the high temperature reaction section 4, the low temperature reaction section 6 and the connecting pipe 8 are as shown in FIGS. The correspondence relationship between FIGS. 16, 17, and 4 will be described below. The vaporization introduction path 14 corresponds to the flow path of the vaporizer 502, and the reforming flow paths 116, 118, and 128 are the first reformer 506. The reforming flow path 150 corresponds to the flow path of the second reformer 510 and extends from the start end of the carbon monoxide removal flow path 84 to the end of the carbon monoxide removal flow path 46. The carbon monoxide remover 512 corresponds to the flow path, the combustion flow path 26 corresponds to the flow path of the first combustor 504, and the combustion chambers 138 and 140 correspond to the combustion chambers of the second combustor 508.

  As shown in FIGS. 2 and 5, silicon nitride, silicon oxide, or the like is illustrated on the lower surface of the low temperature reaction unit 6, that is, the lower surface of the base plate 28, the lower surface of the high temperature reaction unit 4, that is, the lower surface of the base plate 102, and the lower surface of the connecting pipe 8. An insulating film is formed on the entire surface, and the heating wire 170 meanders on the lower surface of the insulating film on the low temperature reaction portion 6 side so as to overlap with at least a part of the flow path of the carbon monoxide remover 512 in a plan view. On the lower surface of the insulating film that is patterned to the high temperature reaction section 4 from the low temperature reaction section 6 through the connecting pipe 8, the heating wire 172 is viewed in plan view in the first reformer 506 and the second reformer 510. It is patterned so as to meander so as to overlap at least a part of the flow path. An insulating film (not shown) such as silicon nitride or silicon oxide is also formed on the side surface of the external flow pipe 10 and the surface of the combustor plate 12, and the external surface passes through the surface of the combustor plate 12 from the lower surface of the low temperature reaction unit 6. A heating wire 174 is patterned over the side surface of the flow pipe 10.

  The heating wires 170, 172, and 174 are formed by laminating an adhesion layer, a diffusion prevention layer, and a heat generation layer in this order from the insulating film side. The heat generating layer is a material having the lowest resistivity among the three layers (for example, Au). When a voltage is applied to the heating wires 170, 172, and 174, a current flows intensively and heat is generated. The diffusion prevention layer is a material in which the material of the heat generation layer is not easily diffused into the diffusion prevention layer even when the heating wires 170, 172, and 174 generate heat, and the material of the diffusion prevention layer is difficult to thermally diffuse into the heat generation layer. It is preferable to use a substance (for example, W) having a high target melting point and low reactivity. The adhesion layer is a layer used when the diffusion preventing layer has low adhesion to the insulating film and is easily peeled off, and is a material having excellent adhesion to both the diffusion preventing layer and the insulating film (for example, , Ta, Mo, Ti, Cr).

  The heating wire 170 heats the low-temperature reaction unit 6 at startup, the heating wire 172 heats the high-temperature reaction unit 4 and the connecting pipe 8 at startup, and the heating wire 174 is connected to the vaporizer 502 and the first in the supply / discharge unit 2. The combustor 504 is heated. Thereafter, when the second combustor 508 is burned with off-gas containing hydrogen from the fuel cell, the heating wire 172 heats the high-temperature reaction section 4 and the connecting pipe 8 as an aid to the second combustor 508. Similarly, when the first combustor 504 is burned with off-gas containing hydrogen from the fuel cell, the heating wire 170 heats the low-temperature reaction unit 6 as an auxiliary to the first combustor 504.

  In addition, since the electric resistance of the heating wires 170, 172, and 174 changes depending on the temperature, the heating wires 170, 172, and 174 also function as temperature sensors that can read the temperature value from the resistance value with respect to a predetermined applied voltage. Specifically, the temperature of the heating wires 170, 172, and 174 is proportional to the electrical resistance.

  Any end portions of the heating wires 170, 172, and 174 are located on the lower surface of the base plate 28, and these end portions are arranged so as to surround the combustor plate 12. Lead wires 176 and 178 are connected to both ends of the heating wire 170, lead wires 180 and 182 are connected to both ends of the heating wire 172, and lead wires 184 and 186 are connected to both ends of the heating wire 174, respectively. Is connected. In FIG. 3, the heating wires 170, 172, 174 and the lead wires 176, 178, 180, 182, 184, 186 are omitted for easy understanding of the drawing.

  As shown in FIGS. 18 and 19, the reaction apparatus 1000 according to the present invention includes a heat insulation package 200 in addition to the microreactor module 1, and the high temperature reaction unit 4, the low temperature reaction unit 6, and the connecting pipe 8 are the heat insulation package 200. Is housed in. The heat insulating package 200 includes a rectangular box 202 having an open bottom surface and a base plate 204 that closes the bottom opening of the box 202. The base plate 204 is joined to the box 202 with a glass material or an insulating sealing material. ing.

  Both the box 202 and the base plate 204 are made of a heat insulating material such as glass or ceramic, and a metal reflective film such as aluminum or gold is formed on the inner surface. When such a metal reflective film is formed, it is possible to suppress the radiant heat from the supply / discharge unit 2, the high temperature reaction unit 4, the low temperature reaction unit 6, and the connection pipe 8 from being reflected and propagated outside the heat insulation package 200. To do. In the heat insulation package 200, the internal space between the microreactor module 1 is evacuated so that the internal pressure becomes 1 Torr or less.

  A part of the external circulation pipe 10 of the supply / discharge section 2 is exposed from the heat insulating package 200, and is connected to a fuel electrode of a power generation module 608 described later, and further connected to a fuel container 604 via a flow rate control unit 606. Yes. A part of the lead wires 176, 178, 180, 182, 184, 186 is exposed from the heat insulating package 200. In the external circulation pipe 10 and the lead wires 176, 178, 180, 182, 184, and 186, there is no gap that causes the outside air to enter the heat insulating package 200 from the portion exposed from the heat insulating package 200 and the internal pressure increases. In addition, the external circulation pipe 10 and the lead wires 176, 178, 180, 182, 184, and 186 are joined to the base plate 204 of the heat insulation package 200 with a glass material or an insulating sealing material. Since the internal pressure of the internal space of the heat insulation package 200 can be kept low, the medium that propagates the heat generated by the microreactor module 1 is diluted, and heat convection in the internal space can be suppressed, so that the heat retention effect of the microreactor module 1 is increased.

  In the space sealed by the heat insulating package 200, a connecting pipe 8 having a predetermined distance is interposed between the high temperature reaction part 4 and the low temperature reaction part 6 of the microreactor module 1, but the volume of the communication pipe 8 is as follows. Since the volume of the high temperature reaction part 4 and the low temperature reaction part 6 is extremely small, the propagation of heat from the high temperature reaction part 4 to the low temperature reaction part 6 by the connecting pipe 8 is suppressed, and the high temperature reaction part 4 and the low temperature reaction part 6 In the meantime, the thermal gradient required for the reaction can be maintained, the temperature in the high temperature reaction unit 4 can be easily equalized, and the temperature in the low temperature reaction unit 6 can be easily equalized.

  As shown in FIGS. 3 and 5, the surface of the low-temperature reaction unit 6 includes a fluid that can leak from the microreactor module 1 over time, a fluid that is generated from the microreactor module 1 over time, and a box 202 and a base plate 204. By adsorbing factors that increase the pressure in the internal space of the heat insulating package 200 such as a part of the remaining outside air that cannot be sufficiently evacuated at the time of joining, and outside air that enters the heat insulating package 200 over time, the heat insulating package 200 A getter material 188 to be removed from the internal space is provided, and a heater such as an electric heating material is provided in the getter material 188, and a wiring 190 is connected to the heater.

  Both ends of the wiring 190 are positioned on the lower surface of the base plate 28 around the combustor plate 12, and lead wires 192 and 194 are connected to both ends of the wiring 190, respectively. The getter material 188 is activated by being heated and has an adsorption action. Examples of the material of the getter material 188 include an alloy mainly composed of zirconium, barium, or titanium. In FIG. 3, the lead wires 192 and 194 are not shown to make the drawing easier to see.

  The lead wires 192 and 194 are partially exposed from the heat insulation package 200, and the lead wires 192 are not formed so that a gap is not generated such that outside air enters the heat insulation package 200 from the exposed portion and the internal pressure increases. , 194 are joined to the base plate 204 of the heat insulating package 200 by a glass material or an insulating sealing material. The wiring group 197 having the lead wires 176, 178, 180, 182, 184, 186, 192, and 194 is preferably separated so that the intervals between the lead wires are equal, and around the outer circulation pipe 10. It is desirable to be arranged.

  In this way, with the plurality of through holes 195 and 196 penetrating the base plate 204, the external circulation pipe 10 and the lead wires 176, 178, 180, 182, 184, 186, 192 and 194 are inserted into the respective through holes. These through holes are sealed with a glass material or an insulating sealing material. Since the internal space of the heat insulation package 200 is sealed and the internal space is at a vacuum pressure, the heat insulation effect is high. Therefore, heat loss can be suppressed.

  The external circulation pipe 10 is in a state of protruding both inside and outside the heat insulating package 200. Therefore, inside the heat insulation package 200, the external circulation pipe 10 is in a state of standing with respect to the base plate 204 as a support, and the high temperature reaction section 4, the low temperature reaction section 6 and the connection pipe 8 are supported by the external circulation pipe 10, The high temperature reaction unit 4, the low temperature reaction unit 6, and the connecting pipe 8 are separated from the inner surface of the heat insulating package 200.

  Further, it is desirable that the external circulation pipe 10 is connected to the lower surface of the low temperature reaction part 6 at the center of gravity of the high temperature reaction part 4, the low temperature reaction part 6 and the connection pipe 8 in plan view.

  If the external flow pipe 10 and the lead wires 176, 178, 180, 182, 184, 186, 192, 194 are provided in the high temperature reaction section 4, the high temperature reaction section 4 needs to be kept at a high temperature during operation. Therefore, the external flow pipe 10 and the lead wires 176, 178, 180, 182, 184, 186, 192, and 194 become high temperature, and the external flow pipe 10 and the lead wires 176, 178, 180, 182, 184, and 186 are heated. , 192, 194 heat transfer to the heat insulation package 200 increases, but the external flow pipe 10 and the lead wires 176, 178, 180, 182, 184, 186, 192, 194 are provided in the low temperature reaction section 6. The external flow pipe 10 and the lead wires 176, 178, 180, 182, 184, 186, 192, 194 The amount of heat that is transferred to the heat insulation package 200 and escapes is small, and heat is radiated from the portions of the external circulation pipe 10 and the lead wires 176, 178, 180, 182, 184, 186, 192, and 194 exposed to the outside of the heat insulation package 200. The amount of heat generated can be small, the high-temperature reaction section 4 and the low-temperature reaction section 6 can be quickly heated, and the heating temperature can be easily maintained stably.

  The getter material 188 is provided on the surface of the low temperature reaction part 6, but the position where the getter material 188 is provided is not particularly limited as long as it is inside the heat insulating package 200.

  Next, the operation of the reaction apparatus 1000 including the microreactor module 1 will be described.

  First, when a voltage is applied between the lead wires 192 and 194, the getter material 188 is heated by the heater, and the getter material 188 is activated. Thereby, the factor which raises the pressure in the heat insulation package 200 is adsorbed by the getter material 188, the degree of vacuum in the heat insulation package 200 increases, and the heat insulation efficiency increases.

  Further, when a voltage is applied between the lead wires 176 and 178, the heating wire 170 generates heat and the low temperature reaction part 6 is heated. When a voltage is applied between the lead wires 180 and 182, the heating wire 172 generates heat and the high temperature reaction unit 4 is heated. When a voltage is applied between the lead wires 184 and 186, the heating wire 174 generates heat, and the upper part of the external circulation pipe 10 is heated mainly in the supply / discharge section 2. Since the supply / discharge part 2, the high temperature reaction part 4, the low temperature reaction part 6 and the connecting pipe 8 are made of a metal material, heat conduction between them is easy.

  In addition, the electric potential or electric current by each voltage drop of the heating wires 170, 172, and 174 as the resistors whose resistance value depends on the temperature is measured by the control device, so that the supply / discharge unit 2, the high temperature reaction unit 4 and The temperature of the low-temperature reaction unit 6 is measured, the measured temperature is fed back to the control device, and the output voltage of the heating wires 170, 172, 174 is controlled by the control device so that the measured temperature is within the desired temperature range. Temperature control of the supply / discharge unit 2, the high temperature reaction unit 4, and the low temperature reaction unit 6 is performed.

  In a state where the supply / discharge section 2, the high temperature reaction section 4 and the low temperature reaction section 6 are heated by the heating wires 170, 172 and 174, the liquid mixture of liquid fuel and water is continuously or intermittently supplied to the vaporization introduction path 14 by a pump or the like. When the liquid is supplied, the liquid mixture is absorbed by the liquid absorbing material 33, and the liquid mixture permeates toward the vaporization introduction path 14 by capillary action. Since the liquid absorbing material 33 is filled up to the height of the combustor plate 12, the mixed liquid in the liquid absorbing material 33 is vaporized due to heat generation in the combustor plate 12, and the mixture of fuel and water is the liquid absorbing material. Evaporate from 33. Since the liquid-absorbing material 33 is porous, the liquid mixture is vaporized in each of the chambers partitioned into a large number of fine spaces, so that bumping that occurs in a relatively large space can be suppressed and stable. And can be vaporized.

  Then, the air-fuel mixture evaporated from the liquid absorbing material 33 passes through the through-hole 52, the mixed gas flow path 38, the connection flow path 162, and the supply flow path 114, and the first reformer 506 (reforming flow paths 116, 118, 128). Thereafter, the air-fuel mixture flows into the second reformer 510 (reforming channel 150). When the air-fuel mixture flows through the reforming channels 116, 118, 128, and 150, the air-fuel mixture is heated and undergoes a catalytic reaction to generate hydrogen gas or the like (when the fuel is methanol). , See the chemical reaction formulas (1) and (2) above).

  The air-fuel mixture (including hydrogen gas, carbon dioxide gas, carbon monoxide gas, etc.) generated by the first reformer 506 and the second reformer 510 is blown through holes 156, 144, 130, and 124, and discharge channels. It flows into the mixing channel 40 through 115 and the connecting channel 164. On the other hand, air is supplied from the air introduction path 16 to the through-hole 60 by a pump or the like provided outside the microreactor module 1, flows into the mixing flow path 40, and the air-fuel mixture such as hydrogen gas is mixed with air.

  An air-fuel mixture containing air, hydrogen gas, carbon monoxide gas, carbon dioxide gas, etc. passes through the blowout holes 66, 82, 88 from the mixing flow path 40, and the carbon monoxide remover 512 (the carbon monoxide removal flow path). 84 to the carbon monoxide removal channel 46). When the air-fuel mixture flows from the carbon monoxide removal flow path 84 to the carbon monoxide removal flow path 46, the carbon monoxide gas in the air-fuel mixture is selectively oxidized and the carbon monoxide gas is removed.

  Here, the carbon monoxide gas does not react uniformly between the carbon monoxide removal flow path 84 and the carbon monoxide removal flow path 46, but from the carbon monoxide removal flow path 84. The reaction rate of the carbon monoxide gas is increased downstream (mainly from the carbon monoxide removal flow path 80 to the carbon monoxide removal flow path 46) in the path to the removal flow path 46. Since the oxidation reaction of the carbon monoxide gas is an exothermic reaction, heat is generated mainly from the carbon monoxide removal channel 80 to the carbon monoxide removal channel 46. Since the external circulation pipe 10 is located under this portion, the heat generated by the oxidation reaction of the carbon monoxide gas is combined with the heat of the first combustor 504 and is efficiently used for the heat of vaporization of water and fuel in the vaporizer 502. .

  Then, the air-fuel mixture from which carbon monoxide has been removed is supplied to the fuel electrode of the fuel cell through the through hole 54 and the hydrogen gas discharge passage 24. In the fuel cell, electricity is generated by the electrochemical reaction of hydrogen gas from the hydrogen gas discharge passage 24, but off-gas including unreacted hydrogen gas and the like is discharged from the fuel cell.

  The above operation is an initial operation, and the mixed liquid continues to be supplied to the vaporization introduction path 14 during power generation. Then, air is mixed with the off-gas discharged from the fuel cell, and the mixture (hereinafter referred to as combustion mixture) is supplied to the combustion mixture introduction path 22 and the combustion mixture introduction path 18. The combustion mixture supplied to the combustion mixture introduction path 22 flows into the combustion channel 26 of the first combustor 504, and the combustion mixture burns. As a result, the first combustor 504 circulating around the external flow pipe 10 below the low temperature reaction section 6 heats the external flow pipe 10 and heats the low temperature reaction section 6 to a low temperature. Therefore, the power consumption of the heating wires 170 and 174 can be reduced, and the energy utilization efficiency is increased.

  As shown in FIG. 6, the combustion mixture supplied to the combustion mixture introduction passage 22 is branched into the combustion passages 26 of the three combustor plates 12 so as to go around the outer periphery of the external circulation pipe 10. To the exhaust gas discharge path 20. At this time, the combustion component in the combustion mixture is burned by oxygen in the combustion mixture under the catalytic effect of the combustion catalyst applied to the combustor plate 12 and generates heat. Then, as shown by the arrows in FIG. 20, the combustion heat propagates directly from the combustor plate 12 to the carbon monoxide remover 512, or is directly conducted to the external circulation pipe 10, and the external circulation pipe 10 Or the mixture of liquid fuel and water evaporates from the liquid absorbing material 33 and then propagates to the carbon monoxide remover 512.

  At this time, since the area of the first combustor 504 (combustor plate 12) facing the carbon monoxide remover 512 (base plate 28) is larger than the area facing the vaporizer 502 (external flow pipe 10), monoxide is oxidized. It is possible to provide a temperature gradient so that the carbon remover 512 can be heated to a higher temperature than the vaporizer 502. While the first combustor 504 is operating, the power consumption of the heating wires 170 and 174 can be reduced, and the energy utilization efficiency is increased.

  On the other hand, the combustion mixture supplied to the combustion mixture introduction path 18 flows into the combustion chambers 138 and 140 of the second combustor 508, and the combustion mixture burns. As a result, combustion heat is generated, and the first reformer 506 below the second combustor 508 and the second reformer 510 above the second combustor 508 are heated to a high temperature. Since the second combustor 508 is vertically sandwiched between the first reformer 506 and the second reformer 510, heat can be efficiently propagated in the surface direction and exposed to the space sealed by the heat insulating package 200. Since there are few parts, there is little heat loss, the power consumption of the heating wire 172 can be made small, and the utilization efficiency of energy increases. Further, since hydrogen having combustibility is not discharged at a high concentration outside the power generation unit including the microreactor module 1 and the fuel cell, safety can be improved.

  In addition, the liquid fuel (for example, methanol) stored in the fuel container is vaporized, and the combustion mixture mixture obtained by mixing the vaporized liquid fuel with oxygen (air) as a combustion source is the combustion mixture introduction paths 18 and 22. You may make it supply to.

  In a state where the mixed liquid is supplied to the vaporization introduction passage 14 and the combustion mixture is supplied to the combustion mixture introduction passages 18 and 22, the controller controls the temperature by the resistance of the heating wires 170, 172 and 174. The voltage applied to the heating wires 170, 172, and 174 is controlled while the pump is controlled. When the pump is controlled by the control device, the flow rate of the combustion mixture supplied to the combustion mixture introduction passages 18 and 22 is controlled, whereby the amount of combustion heat of the combustors 504 and 508 is controlled. As described above, the control device controls the heating wires 170, 172, 174 and the pump, thereby controlling the temperatures of the high temperature reaction section 4, the low temperature reaction section 6 and the supply / discharge section 2, respectively.

  Here, the high temperature reaction part 4 is 250 ° C. to 400 ° C., preferably 300 ° C. to 380 ° C., and the low temperature reaction part 6 is lower than the high temperature reaction part 4, specifically 120 ° C. to 200 ° C., more preferably 140 ° C. Temperature control is performed so as to be ˜180 ° C. More specifically, as shown in FIG. 15, the line L1 located near the bottom plate 53 of the low temperature reaction unit 6 is 150 ° C., the line L2 located at the upper end of the liquid absorbent 33 is 120 ° C., and the outer surface of the base plate 204 is It is preferable that the temperature distribution be such that the position line L3 is 80 ° C. and the line L4 positioned below the liquid absorbing material 33 is 65 ° C.

  That is, while keeping the inside of the heat insulation package 200 at a high temperature, the external flow pipe 10 and the wiring group 197 exposed from the heat insulation package 200 in order to suppress the amount of heat dissipated to the outside of the heat insulation package 200 is not the high temperature reaction section 4 side. It is provided on the low temperature reaction part 6 side. Further, the combustion heat of the first combustor 504 propagates to the external flow pipe 10, and the temperature is gradually increased from the bottom to the top of the liquid absorbing material 33 in the vaporization introduction path 14, thereby efficiently vaporizing the fuel. The first combustor 504 is disposed only around the upper part of the liquid absorbing material 33 so as to be able to do so.

  Further, the fuel sucked into the liquid absorbing material 33 in the vaporization introduction path 14 and the air introduced from the air introduction path 16 are first combusted before reaching the high temperature reaction section 4 and the low temperature reaction section 6, respectively. Not only the combustion heat of the vessel 504 but also the heat of the gas discharged from the exhaust gas discharge path 20 and the hydrogen gas discharge path 24 in advance. Similarly, the air-fuel mixtures introduced from the combustion mixture introduction path 18 and the combustion mixture introduction path 22 are preliminarily exhaust gas discharge path 20 and hydrogen gas before reaching the second combustor 508 and the first combustor 504. The gas is heated by the heat of the gas discharged from the discharge path 24.

  Accordingly, while heating the fluid in the vaporization introduction path 14, the air introduction path 16, the combustion mixture introduction path 18, and the combustion mixture introduction path 22 with the heat of the fluid in the exhaust gas discharge path 20 and the hydrogen gas discharge path 24, The fluid in the exhaust gas discharge path 20 and the hydrogen gas discharge path 24 is cooled by the fluid in the vaporization introduction path 14, the air introduction path 16, the combustion mixture introduction path 18, and the combustion mixture introduction path 22. Heat exchange can be performed. For this reason, it is not necessary to separately use cooling means for cooling the fluid in the exhaust gas discharge path 20 and the hydrogen gas discharge path 24, or the cooling means can be reduced in size.

  As shown in FIG. 21, the reaction apparatus 1000 as described above can be used by being assembled in the power generation unit 601. The power generation unit 601 includes a frame 602, a fuel container 604 that can be attached to and detached from the frame 602, a flow rate control unit 606 having a flow path, a pump, a flow rate sensor, a valve, and the like, and a state in which the heat generation unit 601 is accommodated in the heat insulation package 200. A power generation module 608 having a microreactor module 1 (reaction apparatus 1000), a fuel cell, a humidifier for humidifying the fuel cell, a recovery unit for recovering by-products generated in the fuel cell, and the like, and the microreactor module 1 and the power generation module 608 A power source having an air pump 610 for supplying air (oxygen) to the battery, an external interface for electrically connecting a secondary battery, a DC-DC converter, and an external device that the power generation unit 601 drives with the output of the power generation unit 601 A unit 612. By supplying the mixture of water and liquid fuel in the fuel container 604 to the microreactor module 1 by the flow rate control unit 606, hydrogen rich gas is generated as described above, and the hydrogen rich gas is the fuel of the power generation module 608 that is a fuel cell. The electricity generated and supplied to the electrodes is stored in the secondary battery of the power supply unit 612.

  FIG. 22 is a perspective view of an electronic device 701 using the power generation unit 601 as a power source. As shown in FIG. 22, the electronic device 701 is a portable electronic device, particularly a notebook personal computer. The electronic device 701 includes a lower housing 704 that includes an arithmetic processing circuit composed of a CPU, a RAM, a ROM, and other electronic components and includes a keyboard 702, and an upper housing 708 that includes a liquid crystal display 706. Prepare. The lower casing 704 and the upper casing 708 are connected by a hinge portion 712, and the upper casing 708 is overlapped with the lower casing 704 and can be folded with the liquid crystal display 706 facing the keyboard 702. Has been. A mounting portion 710 for mounting the power generation unit 601 is recessed from the right side surface to the bottom surface of the lower housing 704, and when the power generation unit 601 is mounted on the mounting portion 710, the electronic device 701 operates by electricity of the power generation unit 601. .

  As described above, according to the present embodiment, when the liquid mixture in the liquid absorbing material 33 filled in the external flow pipe 10 evaporates, heat of vaporization is required in the vaporization step of the liquid mixture. Since the first combustor 504 is arranged so as to circulate around the outer periphery of the external circulation pipe 10 and the first combustor 504 burns the combustion mixture in the combustion flow path 26 and generates heat, the combustion heat is generated. The liquid fuel and water which are propagated to the vicinity of the tip of the liquid absorbing material 33 through the external circulation pipe 10 and adsorbed by the liquid absorbing material 33 are vaporized. In the vaporized portion, that is, the tip portion of the liquid absorbing material 33, the lower liquid fuel and water are sucked up and can be continuously vaporized. At this time, the liquid fuel and water sucked up are gradually heated and vaporized as shown in FIG. 15, so that bumping in the liquid absorbing material 33 does not occur and is vaporized quantitatively. It becomes possible.

  Further, since the combustor plate 12 is provided around the external circulation pipe 10 at the upper end portion of the external circulation pipe 10, the liquid absorbing material 33 in the vaporization introduction path 14 is further positioned at the height of the combustor plate 12. Therefore, the combustion heat in the first combustor 504 can be efficiently used for vaporizing the mixed liquid.

  Furthermore, according to the present embodiment, the internal space of the heat insulation package 200 is a heat insulation space, the high temperature reaction part 4 is separated from the low temperature reaction part 6, and the interval from the high temperature reaction part 4 to the low temperature reaction part 6 is connected. This is the length of the tube 8. Therefore, the heat transfer path from the high temperature reaction section 4 to the low temperature reaction section 6 is limited to the connecting pipe 8, and the heat transfer to the low temperature reaction section 6 that does not require high temperature is limited. In particular, since the height and width of the connecting pipe 8 are smaller than the height and width of the high temperature reaction section 4 and the low temperature reaction section 6, heat conduction through the connecting pipe 8 is suppressed as much as possible. Therefore, the heat loss of the high temperature reaction part 4 can be suppressed, and the temperature increase of the low temperature reaction part 6 above the set temperature can be suppressed. That is, even when the high temperature reaction unit 4 and the low temperature reaction unit 6 are accommodated in one heat insulating package 200, a temperature difference can be generated between the high temperature reaction unit 4 and the low temperature reaction unit 6.

In addition, since the connecting flow paths 162, 164, 166, and 168 are combined into one connecting pipe 8, the stress generated in the connecting pipe 8 and the like can be reduced. That is, since there is a temperature difference between the high temperature reaction unit 4 and the low temperature reaction unit 6, the high temperature reaction unit 4 expands more than the low temperature reaction unit 6, but the high temperature reaction unit 4 is connected to the connection pipe 8. Since the portion other than the portion is a free end, the stress generated in the connecting pipe 8 or the like can be suppressed. In particular, the connecting pipe 8 is smaller in height and width than the high temperature reaction part 4 and the low temperature reaction part 6, and the connecting pipe 8 further includes the high temperature reaction part 4 and the low temperature reaction at the center in the width direction of the high temperature reaction part 4 and the low temperature reaction part 6. Since it is connected to the part 6, it is possible to suppress the generation of stress in the connecting pipe 8, the high temperature reaction part 4 and the low temperature reaction part 6.
Since the single external circulation pipe 10 is connected between the low temperature reaction part 6 and the heat insulation package 200, the stress generated in the external circulation pipe 10 and the like can be reduced.

  In addition, if the flow paths 162, 164, 166, and 168 are provided in separate connecting pipe materials and are installed between the high temperature reaction section 4 and the low temperature reaction section 6 in a state where the connection pipe materials are separated, the low temperature reaction section 6 and the high temperature reaction section 6 Due to the difference in displacement of the reaction part 4, stress is generated in the connecting pipe material, the low temperature reaction part 6, and the high temperature reaction part 4. Moreover, since the temperature difference between the high temperature and the low temperature of the high temperature reaction part 4 is larger than the temperature difference between the high temperature and the low temperature of the low temperature reaction part 6, when an external circulation pipe is arranged on the high temperature reaction part 4 side, Since the thermal expansion and contraction of the pipe material is larger than the thermal expansion and contraction of the pipe material when the external circulation pipe material is arranged on the low temperature reaction part 6 side, the airtightness in the heat insulating package 200 is easily impaired. In the present embodiment, the generation of such stress can be suppressed and the airtightness can be maintained.

  The external circulation pipe 10 and the lead wires 176, 178, 180, 182, 184, 186, 192, and 194 extend to the outside of the heat insulation package 200, but they are all connected to the low temperature reaction unit 6. Therefore, direct heat radiation from the high temperature reaction part 4 to the outside of the heat insulation package 200 can be suppressed, and heat loss of the high temperature reaction part 4 can be suppressed. Therefore, even when the high temperature reaction unit 4 and the low temperature reaction unit 6 are accommodated in one heat insulating package 200, a temperature difference can be generated between the high temperature reaction unit 4 and the low temperature reaction unit 6. In particular, the vaporization introduction path 14, the air introduction path 16, the combustion mixture introduction path 18, the exhaust gas discharge path 20, the combustion mixture introduction path 22, and the hydrogen gas discharge path 24 are combined into one external circulation pipe 10. Since it is provided, the area of the exposed surface of the tube can be suppressed, heat radiation from the surface of the tube to the outside of the heat insulating package 200 can be suppressed, and heat loss can be suppressed.

  Since the lower surface of the connecting pipe 8, the lower surface of the high temperature reaction unit 4, and the lower surface of the low temperature reaction unit 6 are flush with each other and there is no step, the heating wire 172 can be patterned relatively easily, and the heating wire 172 is disconnected. Can be suppressed.

  In addition, since the vaporization introduction path 14 of the external flow pipe 10 is filled with the liquid absorbing material 33 and the vaporization introduction path 14 is used as the vaporizer 502, the liquid mixture can be obtained while miniaturizing and simplifying the microreactor module 1. It is possible to achieve a temperature state necessary for vaporization (a state where the upper portion of the vaporization introduction path 14 is 120 ° C.).

  Further, since the second combustor 508 is sandwiched between the first reformer 506 and the second reformer 510, the combustion heat of the second combustor 508 is changed between the first reformer 506 and the second reformer 506. Conducted uniformly to the reformer 510, and no temperature difference occurs between the first reformer 506 and the second reformer 510.

  In any part of the supply / discharge section 2, the high temperature reaction section 4, the low temperature reaction section 6 and the connecting pipe 8, the partition walls partitioning the flow path are made thin, so that these heat capacities can be reduced, and the initial stage of operation. The heating / discharging part 2, the high temperature reaction part 4, the low temperature reaction part 6 and the connecting pipe 8 can be immediately heated from room temperature to high temperature. Furthermore, the power consumption of the heating wires 170, 172, and 174 can be reduced.

  In addition, this invention is not limited to said embodiment, You may make various improvement and design change in the range which does not deviate from the main point of this invention.

  For example, as one improvement / design change matter, instead of the first combustor 504 and the heating wire 174, as shown in FIG. 23, the outer circulation pipe 10 is slightly separated from the outer circumference so as to go around. Alternatively, the heating wire 175 may be patterned in such a state that lead wires 184 and 186 are connected to both ends of the heating wire 175, respectively. In this case, when a voltage is applied between the lead wires 184 and 186, the heating wire 175 generates heat, and the heat is transmitted from the periphery of the external circulation pipe 10 via a member such as the base plate 28 of the low-temperature reaction unit 6. Similar to the case where the first combustor 504 is arranged around the external circulation pipe 10 through the external circulation pipe 10, the external circulation pipe 10 can be efficiently heated.

  As another improvement / design change matter, in addition to arranging the heating wire 175 as described above, the first combustor 504 is arranged so as to cover the heating wire 175, and the heating wire 175 and the first combustor 504 are arranged. It is good also as a structure which heats the external distribution pipe | tube 10 using two heating sources.

It is a perspective view of the micro reactor module 1 shown diagonally from the top. It is a perspective view of the micro reactor module 1 shown from diagonally below. 1 is a side view of a microreactor module 1. FIG. It is a schematic side view at the time of dividing the micro reactor module 1 for every function. 1 is an exploded perspective view of a microreactor module 1. FIG. 2 is a perspective view showing a first combustor 504. FIG. 2 is an exploded perspective view of a first combustor 504. FIG. It is arrow sectional drawing of the surface along the cutting line VIII-VIII of FIG. It is arrow sectional drawing of the surface along the cutting line IX-IX of FIG. It is arrow sectional drawing of the surface along the cutting line XX of FIG. It is arrow sectional drawing of the surface along the cutting line XI-XI of FIG. It is arrow sectional drawing of the surface along the cutting line XII-XII of FIG. It is arrow sectional drawing of the surface along the cutting line XIII-XIII of FIG. It is arrow sectional drawing of the surface along the cutting line XIV-XIV of FIG. It is arrow sectional drawing of the surface along the cutting line XV-XV of FIG. It is drawing which showed the path | route from liquid fuel and water being supplied until the hydrogen rich gas which is a product is discharged | emitted. It is drawing which showed the path | route until a water etc. which are a product are discharged | emitted after a combustion air-fuel mixture is supplied. It is a disassembled perspective view of the reaction apparatus 1000. FIG. It is a perspective view of the reaction apparatus 1000 shown from diagonally below. 4 is a side cross-sectional view showing a state where heat is conducted from the first combustor 504 through the external circulation pipe 10. FIG. 3 is a perspective view of a power generation unit 601. FIG. 2 is a perspective view of an electronic device 701. FIG. 2 is a view showing a modification of the microreactor module 1.

Explanation of symbols

1000 reactor 4 high temperature reaction section 6 low temperature reaction section 502 vaporizer 14 vaporization introduction path 20 exhaust gas discharge path 22 combustion mixture introduction path 24 hydrogen gas discharge path 504 first combustor (combustor)
12 Combustor plate 26 Combustion flow path 175 Heating wire

Claims (7)

A vaporizer for vaporizing liquid fuel;
A combustor that generates heat by burning a combustion source,
The combustor is arranged around the vaporizer,
The vaporizer has a vaporization introduction path including a liquid absorbing material that absorbs the liquid fuel,
The combustor includes a high temperature reaction section for reforming the liquid fuel vaporized by the vaporizer and a low temperature reaction section for removing carbon monoxide from a product of the high temperature reaction section . A reactor characterized by heating the low-temperature reaction section. The reactor according to claim 1,
The reaction apparatus, wherein the combustor includes a combustion catalyst for promoting a combustion reaction of the combustion source. The reactor according to claim 2,
The combustor has a combustion flow path for circulating the combustion source;
The reaction apparatus, wherein the combustion catalyst is applied to a bottom surface and a side surface of the combustion channel. In the reaction apparatus according to any one of claims 1 to 3,
The reactor according to claim 1, wherein the combustor includes a combustor plate in which a combustion channel through which the combustion source is circulated is formed and a plurality of the combustor plates are stacked. The reactor according to claim 1 ,
The vaporizer includes a vaporization introduction path for introducing liquid fuel and a hydrogen gas discharge path for discharging hydrogen gas generated by the reaction path. In the reaction apparatus according to any one of claims 1 to 5 ,
The reactor includes a combustion mixture introduction path for introducing a combustion source into the combustor and an exhaust gas discharge path for discharging exhaust gas generated when the combustion is performed in the combustor. In the reaction apparatus as described in any one of Claims 1-6 ,
It further comprises a heating wire that generates heat when supplied with power,
The reaction apparatus, wherein the heating wire is arranged so as to go around the vaporizer.

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