JP4428322B2 - Reactor - Google Patents

Description

  The present invention relates to a reactor that generates hydrogen from liquid fuel, and more particularly to a reactor that generates hydrogen to be supplied to a fuel cell.

  In recent years, development has been progressing in order to mount a fuel cell as a clean power source with high energy conversion efficiency in an automobile or a portable device. A fuel cell is one in which electric energy is directly extracted from chemical energy by electrochemically reacting fuel and oxygen in the atmosphere.

  Although hydrogen is applied as a starting fuel used in the fuel cell, hydrogen has a problem in handling because it is a gas at normal temperature and pressure. 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, in a reformed fuel cell that generates hydrogen by reforming a hydrocarbon-based liquid fuel having hydrogen atoms such as alcohols and gasoline, the fuel can be easily stored in a liquid state. In such a fuel cell, the liquid fuel is vaporized, the vaporized liquid fuel is reformed to generate a reformed gas mainly containing hydrogen, and the hydrogen in the reformed gas is sent to the fuel cell. Is done.

In such a system, a reactor such as a reformer that reforms vaporized liquid fuel by a reforming reaction, a carbon monoxide remover that removes carbon monoxide that is a byproduct generated by the reforming reaction, and the like. Is required. In addition, in order to reduce the size of such a reforming fuel cell, a microreactor in which a reformer and a carbon monoxide remover are stacked is being developed (see, for example, Patent Document 2). . In the configuration described in Patent Document 2, each of the vaporizer, the reformer, and the carbon monoxide remover is formed by joining two metal substrates on which grooves are formed, and the grooves serve as flow paths. ing.
JP 2002-356310 A JP 2005-132712 A

  In the above reactor, the operating temperature of the carbon monoxide remover is less than 200 ° C., whereas the operating temperature of the reformer is 250 ° C. or higher, and the temperature at which the reformer and the carbon monoxide remover can operate Because the environment is different, the reformer and the carbon monoxide remover are configured separately, and the reactors are connected by connecting members, and the temperature difference is maintained by keeping the inside of the heat insulating package almost vacuum. To maintain. However, since the reformer and carbon monoxide remover are configured by joining multiple members, if there is a joint failure, the gas in the reaction section leaks from there to the vacuum layer in the heat insulation package, and the vacuum layer is insulated. Sex will not be maintained. This makes it impossible to create the optimal temperature distribution for the reaction in the reaction zone.

  An object of the present invention is to prevent leakage of a reaction product or reaction product from the reaction unit to the outside in a reaction apparatus including a reaction unit that generates a reaction product by causing reaction of the reaction product.

In order to solve the above-described problems, the invention according to claim 1 is a reaction apparatus including a reaction unit that generates a reaction product by causing a reaction of a reactant, and the reaction apparatus generates hydrogen from liquid fuel. In the reaction apparatus, the reaction unit is set to at least a first temperature and heats at least one first reactor in which a reaction channel is formed, and the first reactor. A first reaction section comprising: a heating section set to the first temperature; a first box covering the outer wall of the first reactor and the heating section; and a first reaction section that is lower than the first temperature. A second reaction section comprising: at least one second reactor having a reaction flow path formed therein, and a second box covering the outer wall of the second reactor; It comprises a plurality of reaction sections of the reactor, further wherein said first reaction unit first Is installed between the reaction region, the first reactant is a reaction raw material at a reaction unit sends to the first reaction portion, the reaction product was reacted in the first reaction unit A connecting pipe to be sent to a second reaction unit, a reactant connected to the second reaction unit and supplied to the first reaction unit, which is a reaction raw material of the first reaction unit, and the second reaction unit the reaction product of the second reaction portion is discharged from the reaction unit, which is characterized in that and an external circulation pipe circulating.

The invention according to claim 2 is the reaction apparatus according to claim 1, wherein the first and second reactors in the first and second reaction sections, the outer wall of the heating section reactor, and the first And the said reaction flow path of each of the 2nd reactor and the said 1st and 2nd box are each joined by joining plate-shaped metal material, It is characterized by the above-mentioned.

According to a third aspect of the present invention, in the reaction apparatus according to the first aspect, the heating unit includes a combustor that causes combustion of gaseous fuel flowing in a space provided therein.

According to a fourth aspect of the present invention, there is provided the reactor according to the third aspect , wherein the combustor has a combustion flow path through which the gaseous fuel is circulated, and a combustion catalyst that promotes a combustion reaction of the gaseous fuel. It is applied to the bottom and side surfaces of the combustion channel.

According to a fifth aspect of the present invention, in the reaction apparatus according to the first aspect, the reaction apparatus further covers the base plate, the first reaction section, the second reaction section, and the entire connecting pipe. The interior space is provided with a heat insulating container whose vacuum pressure is set.

The invention according to claim 6 is the reaction apparatus according to claim 1, wherein the heating unit sets the second reaction unit to the second temperature via the connection unit. .
The invention according to claim 7 is the reaction apparatus according to claim 1, wherein the first reaction product is supplied to the first reaction unit to generate the first reaction product, and the second reaction product is supplied to the second reaction unit. The first reaction product is supplied to the reaction section to generate a second reaction product, and the first reaction product is a vaporized hydrocarbon-based liquid fuel, The reaction section is a reformer that causes a reforming reaction of the first reactant, wherein the first reaction product contains carbon monoxide, and the second reaction section includes the first reaction section. It is a carbon monoxide remover that removes carbon monoxide contained in the reaction product by selective oxidation.

According to the reaction apparatus concerning this invention, the box which covers the outer wall of a reaction part is provided, and the leakage of the reaction material or reaction product to the exterior from a reaction part can be prevented. As a result, when a heat insulating container is provided and a vacuum heat insulating structure is used, the degree of vacuum in the heat insulating container can be maintained, heat conduction from the reaction part to the outside of the heat insulating container is suppressed, and the temperature distribution in the reaction part is optimal for the reaction. It is possible to maintain a proper temperature.

  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 schematic side view when the microreactor module 1 in the embodiment of the reaction apparatus according to the present invention is divided for each function. The microreactor module 1 is a reactor that generates hydrogen gas used in a fuel cell, for example, built in an electronic device such as a notebook personal computer, PDA, electronic notebook, digital camera, mobile phone, wristwatch, register, or projector. It is. The microreactor module 1 includes a supply / exhaust unit 2 that supplies reactants and discharges products, a high-temperature reaction unit (first reaction unit) 4 that undergoes a reforming reaction at a relatively high temperature, and a high-temperature reaction Inflow of reactants and products between the low-temperature reaction part (second reaction part) 6 where the selective oxidation reaction occurs at a temperature lower than the set temperature of the part 4 and between the high-temperature reaction part 4 and the low-temperature reaction part 6 Or the connection part 8 for performing outflow is comprised.

  As shown in FIG. 1, the supply / discharge unit 2 is mainly provided with a carburetor 502 and a first combustor 504. Air and gaseous fuel (for example, hydrogen gas, methanol gas, etc.) are supplied to the first combustor 504 separately or as an air-fuel mixture, and heat is generated by the catalytic combustion. The vaporizer 502 is supplied with water and liquid fuel (for example, methanol, ethanol, dimethyl ether, butane, gasoline) from the fuel container separately or mixed, and water and liquid are generated by the combustion heat in the first combustor 504. The fuel is vaporized in the vaporizer 502.

  The high temperature reaction section 4 is mainly provided with a first reformer (first reactor) 506, a second combustor (heating section) 508, and a second reformer (second reactor) 510. . For example, 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. The first reformer 506 and the second reformer 510 are configured to communicate with each other.

  Air and gaseous fuel (for example, hydrogen gas, methanol gas, etc.) are supplied to the second combustor 508 separately or as a mixture, and heat is generated by the catalytic combustion. In the fuel cell, electricity is generated by an electrochemical reaction of hydrogen gas, and the unreacted hydrogen gas contained in the off-gas discharged from the fuel cell is mixed with air in the first combustor 504 and the second combustor 508. May be supplied. Of course, the liquid fuel (for example, methanol, ethanol, dimethyl ether, butane, gasoline) stored in the fuel container is vaporized by another vaporizer, and the vaporized fuel / air mixture becomes the first combustor 504 and It may be supplied to the second combustor 508.

The first reformer 506 and the second reformer 510 are supplied with an air-fuel mixture (first reactant) from the vaporizer 502 from which water and liquid fuel are vaporized. The mass device 510 is heated by the second combustor 508. In the first reformer 506 and the second reformer 510, hydrogen gas or the like (first reaction product) is generated by catalytic reaction from water vapor and the vaporized liquid fuel, and carbon monoxide gas is further generated in a small amount. The When the fuel is methanol, chemical reactions such as the following formulas (1) and (2) occur. The reaction for generating hydrogen 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 heated by the first combustor 504, and a small amount of carbon monoxide generated from the first reformer 506 and the second reformer 510 by the chemical reaction of (2) above. An air-fuel mixture (second reactant) containing gas or the like is supplied and air is further supplied. The carbon monoxide remover 512 selectively oxidizes carbon monoxide from the air-fuel mixture, thereby removing the carbon monoxide. An air-fuel mixture (second reaction product: 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 connection unit 8 will be described with reference to FIGS. Here, FIG. 2 is an exploded perspective view of the microreactor module 1 in the present embodiment, and FIG. 3 is a side view of the microreactor module 1 in the present embodiment. 4 and 5 are views showing the microreactor module 1 from which a gas leak prevention package (box body) to be described later is removed. FIG. 4 is a perspective view seen from the upper side, and FIG. 5 is a perspective view seen from the lower side. It is.
6 is a cross-sectional view taken along the plane direction of the combustor plate 12 to be described later from a cutting line VI-VI in FIG. 3, and FIG. 7 is a base plate to be described later from a cutting line VII-VII in FIG. 28 is a cross-sectional view taken along the plane direction of the base plate 102 and FIG. 8, and FIG. 8 is an arrow view taken along the plane direction of the lower frame 30 and the lower frame 104 described later from the cutting line VIII-VIII of FIG. 9 is a cross-sectional view taken along the plane direction of a middle frame 32 and a middle frame 106, which will be described later, from a cutting line IX-IX in FIG. 3, and FIG. 10 is a sectional line X in FIG. FIG. 11 is a cross-sectional view taken along the plane of the upper frame 34 and the upper frame 110 described later from −X, and FIG. 11 is a cross-sectional view taken along the line XI-XI in FIG. 12 is along the surface direction orthogonal to the communication direction of the connecting pipe 8 from the cutting line XII-XII of FIG. FIG.
FIG. 13 is a perspective view of a gas leak prevention package, which will be described later, as seen obliquely from below, FIG. 14 is a perspective view of a member along the cutting line VII-VII in FIG. 3, and FIG. 15 is a cutting line VIII in FIG. It is a perspective view of the member in alignment with -VIII.
FIG. 16 is a diagram showing a path from the supply of liquid fuel and water to the discharge of the product rich hydrogen gas in the microreactor module 1 of the present embodiment, and FIG. 17 shows the present embodiment. It is the figure which showed the path | route until the water etc. which are a product are discharged | emitted in the micro reactor module 1 after supplying the combustion mixture which consists of gaseous fuel and air.

  As shown in FIGS. 2, 3, and 6, the supply / discharge section 2 includes an external circulation pipe 10 made of a plate-like metal material such as stainless steel, and three sheets stacked around the external circulation pipe 10. Combustor plate 12 is provided and joined.

  The external circulation pipe 10 is a pipe having a plurality of channels for circulating each fluid in the microreactor module 1 to the outside of the microreactor module 1. The external circulation pipe 10 includes a vaporization introduction path 14, an air The introduction path 16, the combustion mixture introduction path 18, the exhaust gas discharge path 20, the combustion mixture introduction path 22 and the hydrogen discharge path 24 are provided in parallel to each other. 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 discharge path 24 are partitioned by a partition wall of 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 discharge path 24 are provided in one external flow pipe 10. These flow paths 14, 16, 18, 20, 22, and 24 may be provided in separate pipes, and these pipes may be bundled.

  The vaporization introduction path 14 is filled with a liquid absorbing material such as a felt material, a ceramic porous material, a fiber material, and a carbon porous material. The liquid-absorbing material absorbs liquid, and the liquid-absorbing material is, for example, an inorganic fiber or organic fiber solidified with a binder, an inorganic powder sintered, an inorganic powder solidified with a binder, It consists of a mixture of graphite and glassy carbon.

  The combustor plate 12 is also made of a plate-like metal material such as stainless steel. A through hole is formed at the center of the combustor plate 12, and the external circulation pipe 10 is fitted into the through hole, and the external circulation pipe 10 and the combustor plate 12 are joined. Here, the external circulation pipe 10 is joined to the combustor plate 12 by brazing, for example. As the wax, the melting point is higher than the highest temperature of the fluid flowing through the external flow pipe 10 and the combustor plate 12, and the melting point is 700 ° C. or more and contains silver, copper, zinc, and cadmium in gold. Particularly preferred are gold waxes, waxes based on gold, silver, zinc and nickel, or waxes based on gold, palladium and silver. Further, a partition wall is provided on one surface of the combustor plate 12 so as to protrude. A part of the partition wall is provided over the entire outer periphery of the combustor plate 12 and the other part is provided in the radial direction, and the three combustor plates 12 are laminated around the outer circulation pipe 10 by bonding. Further, when the uppermost combustor plate 12 is joined to the lower surface of the low temperature reaction section 6, a combustion flow path 26 whose upper portion is covered with another combustor 12 or a base plate 28 is formed. One end of the combustion flow path 26 communicates with the combustion mixture introduction path 22, and the other end of the combustion flow path 26 communicates with the exhaust gas discharge path 20. A combustion catalyst for burning the combustion air-fuel mixture is carried on the wall surface of the combustion channel 26. An example of the combustion catalyst is platinum. The liquid absorbing material in the external circulation pipe 10 is filled up to the position of the combustor plate 12.

  As shown in FIGS. 2 and 3, 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 is a cuboid. Present. 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 plate-like metal material such as stainless steel.

  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. 7, by providing a partition wall 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 twisted carbon monoxide. It is divided into a 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 hydrogen discharge path 24. 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.

  As shown in FIG. 8, by providing a partition wall inside the lower frame 30, the inner side of the lower frame 30 has a twisted carbon monoxide removal channel 62 and a spiral carbon monoxide removal channel 64. Are divided into 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 flow path 64, the combustion mixture flow path 68, and the exhaust gas flow path 70. When the lower frame 30 is joined to the base plate 28 by brazing or the like, the bottom plate 72 causes the upper portion to move. A capped mixed gas channel 38, a mixed channel 40, a carbon monoxide removal channel 46, a combustion mixture channel 48, and an exhaust gas channel 50 are formed. Further, one end of the carbon monoxide removal flow path 64 communicates with the carbon monoxide removal flow path 62, and the carbon monoxide removal flow path of the base plate 28 in the middle of the carbon monoxide removal flow path 64. A blow-through hole 74 that leads to the carbon monoxide removal flow path 64 is formed at the other end of the carbon monoxide removal flow path 64, and a blow-through hole 76 that leads to the carbon monoxide removal flow path 46 of the base plate 28 is formed. The carbon monoxide removing channel 62 overlaps the carbon monoxide removing channel 44 of the base plate 28, and the carbon monoxide removing channel 62 and the carbon monoxide removing channel 44 are in communication with each other. 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. In plan view, the external circulation pipe 10 is configured to overlap 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. 9, by providing a partition wall inside the middle frame 32, 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 flow path 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 combustion of the lower frame 30 whose upper portion is covered by the bottom plate 83 is burned. An air-fuel mixture channel 68 and an exhaust gas channel 70 are formed.

  The carbon monoxide removing channel 78 overlaps the carbon monoxide removing channel 62 of the lower frame 30, and the carbon monoxide removing channel 78 and the carbon monoxide removing channel 62 are in communication with each other. The carbon monoxide removal flow path 80 overlaps the carbon monoxide removal flow path 64 of the lower frame 30, and the carbon monoxide removal flow path 80 and the carbon monoxide removal flow path 64 are in communication with each other. 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.

  Here, as shown in FIG. 14, among the partition walls provided on the base plate 28, the four partition walls 29 forming the carbon monoxide removal flow path 44 are higher than the other partition walls. As shown in FIGS. 7 to 9, the partition wall 29 extends from the base plate 28 to the middle frame 32 through the lower frame 30. The base plate 28, the lower frame 30, the middle frame 32, and the upper frame 34 are joined together by brazing or the like, so that twisted carbon monoxide removal channels 44, 62, and 78 are integrally formed.

  As shown in FIG. 15, among the partition walls provided in the lower frame 30, the partition wall 73 on the bottom plate 72 that forms the carbon monoxide removal flow path 64 is also higher than the other partition walls. As shown in FIG. 9, the partition wall 73 extends from the lower frame 30 to the middle frame 32. The base plate 28, the lower frame 30, the middle frame 32, and the upper frame 34 are joined by brazing or the like, so that spiral carbon monoxide removal channels 64 and 80 whose upper portions are covered by the upper frame 34 are integrated. Formed.

  As shown in FIG. 10, the partition wall 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 inside of the upper frame 34. When the upper frame 34 is joined to the middle frame 32 by brazing or the like, the upper portion is covered with the bottom plate 86, and carbon monoxide is removed by the middle frame 32. A flow path 78 and a carbon monoxide removal flow path 80 are formed. A blow-through hole 88 is formed at one end of the carbon monoxide removal channel 84, and a blow-through hole 90 is formed at the other end of the carbon monoxide removal channel 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. 2, the lid plate 36 is joined onto the upper frame 34 by brazing or the like, so that the upper portion is covered with the lid plate 36 and the carbon monoxide removal flow path 84 is formed.
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. An example of the catalyst for selective oxidation of carbon monoxide is platinum.

  As shown in FIG. 2 and FIG. 3, the high temperature reaction unit 4 is formed by laminating 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 in this order from below. 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 plate-like metal material such as stainless steel.

  As shown in FIG. 7, partition walls are provided on the upper surface of the base plate 102 so as to be divided into a supply flow path 114, a twisted reforming flow path 116, and a discharge flow path 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. 8, by providing a plurality of partition walls inside the lower frame 104, the inside of the lower frame 104 has a distorted reforming flow path 118, a combustion mixture flow path 120, an exhaust gas flow path 122, and It is divided into blow-through holes 124. A bottom plate 126 is provided in the combustion mixture flow path 120 and the exhaust gas flow path 122, and the lower frame 104 is joined to the base plate 102 by brazing or the like, so that the supply flow path 114 and the exhaust flow whose top is covered by the bottom plate 126 are provided. A path 115 is formed. The reforming channel 118 overlaps the reforming channel 116 of the base plate 102, and the reforming channel 118 and the reforming channel 116 are in communication with each other.

  As shown in FIG. 9, by providing a plurality of partition walls inside the middle frame 106, the inside of the middle frame 106 has a distorted reforming flow path 128, a blow hole 130, a blow hole 132, and a blow hole 134. It is divided into. Further, the middle frame 106 is provided with a bottom plate 136, and the middle frame 106 is joined to the lower frame 104 by brazing or the like, so that the combustion mixture flow path 120 and the exhaust gas of the lower frame 104 whose upper portion is covered by the bottom plate 136. A flow path 122 is formed. The reforming channel 128 overlaps the reforming channel 118 of the lower frame 104, and the reforming channel 128 and the reforming channel 118 are in communication with each other. The blow-through hole 130 overlaps with the blow-through hole 124 of the lower frame 104, and the blow-through hole 130 and the blow-through hole 124 are in communication with each other. 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.

  Here, as shown in FIG. 15, among the partition walls provided on the base plate 102, the four partition walls 117 forming the reforming flow path 116 are higher than the other partition walls. As shown in FIGS. 7 to 9, the partition wall 117 extends from the base plate 102 to the middle frame 106 through the lower frame 104. By joining the base plate 102, the lower frame 104, the middle frame 106, and the combustor plate 108, the upper portion is covered by the combustor plate 108, and the distorted reforming flow paths 116, 118, and 128 are integrated. Formed.

  As shown in FIG. 11, a partition wall is provided on the upper surface of the combustor plate 108 so as to be divided into a combustion chamber 138, a combustion chamber 140, a blow-through hole 142, and a blow-through hole 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. In addition, 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 flows through the blow-through hole 148 and the blow-through hole 134. It leads to the road 122. 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 air-fuel mixture is supported on the bottom and side surfaces of the combustion chamber 138 and the combustion chamber 140. An example of the combustion catalyst is platinum.

  As shown in FIG. 10, by providing a plurality of partition walls inside the upper frame 110, a twisted reforming flow path 150 is formed inside the upper frame 110. Further, a bottom plate 152 is provided on the upper frame 110, and the upper frame 110 is joined onto the combustor plate 108 by brazing or the like, so that the upper portion is covered by the upper frame 110, and the combustion chamber of the combustor plate 108 is provided. 138 and combustion chamber 140 are formed. 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 shown in FIG. 2, the lid plate 112 is joined onto the upper frame 110 by brazing or the like, so that the upper portion is covered by the lid plate 112 and the reforming flow path 150 is formed. Here, on the wall surfaces of the supply flow path 114, the discharge flow path 115, and the reforming flow paths 116, 118, 128, and 150, a reforming catalyst that reforms the fuel to generate hydrogen is supported. Examples of reforming catalysts used for reforming methanol include Cu / ZnO-based catalysts and Pt / ZnO-based catalysts.

  As shown in FIGS. 2, 3, and 13, the connecting portion 8 includes a first connecting portion 161, a second connecting portion 165, and a bottom plate 169. The connecting part 8 is narrower than the high temperature reaction part 4 and the low temperature reaction part 6, and is lower than the high temperature reaction part 4 and the low temperature reaction part 6.

  The first connecting portion 161 is installed between the high temperature reaction portion 4 and the low temperature reaction portion 6, and as shown in FIGS. 2, 7, and 14, for example, the high temperature reaction portion 4 and the low temperature reaction portion 6 are connected. It is integrally formed with base plates 28 and 102 as a base at each width direction center. The lower surface of the first connecting portion 161 is flush with the lower surface of the high temperature reaction portion 4, that is, the lower surface of the base plate 102, and further flush with the lower surface of the low temperature reaction portion 6, that is, the lower surface of the base plate 28. Yes.

  The second connecting portion 165 is also installed between the high temperature reaction portion 4 and the low temperature reaction portion 6. As shown in FIGS. 2, 8, and 15, for example, the high temperature reaction portion 4 and the low temperature reaction portion 6 are connected. It is integrally formed with the lower frames 30 and 104 as frame bodies at the center in each width direction.

As shown in FIG. 7, the first connection portion 161 is provided with a connection channel 162 and a connection channel 164 so as to be parallel to each other. The connection flow path 162 and the connection flow path 164 are partitioned by the partition wall of the first connection portion 161, and the partition wall is formed by joining to the second connection portion 165.
As shown in FIG. 8, a connection channel 166 and a connection channel 168 are provided in the second connection part 165 so as to be parallel to each other. The connection channel 166 and the connection channel 168 are partitioned by a partition wall of the second connection part 165, and the partition wall is formed by joining to the bottom plate 169 by brazing or the like. ing.
As shown in FIG. 9, the middle frame 32 and the middle frame 106 are connected by, for example, a bottom plate 169 formed integrally with the bottom plate 136.

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 the above-described configuration, the first connecting portion 161 forming the connecting portion 8 is formed integrally with the base plates 28 and 102, the second connecting portion 165 is formed integrally with the lower frames 30 and 104, and the bottom plate 169 is the middle frame. However, the present invention is not limited to this, and the connecting portion 8 is formed separately from the high-temperature reaction portion 4 and the low-temperature reaction portion 6, for example, in the shape of a prism, so that the high-temperature reaction is performed. It may be joined to the high temperature reaction part 4 at the center part in the width direction of the part 4 and joined to the low temperature reaction part 6 at the center part in the width direction of the low temperature reaction part 6.

  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 connection section 8 are as shown in FIGS. The correspondence relationship between FIGS. 16, 17, and FIG. 1 will be described. 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 flow path of the second combustor 508.

  As shown in FIGS. 2 and 5, 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 are, for example, An insulating film (not shown) is formed on the entire surface, and the heating wire 170 is patterned in a meandering manner on the lower surface of the insulating film on the low temperature reaction part 6 side. In addition, the heating wire 172 is patterned in a meandering manner on the lower surface of the insulating film that extends from the low temperature reaction portion 6 through the connecting portion 8 to the high temperature reaction portion 4. 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 laminated in the order of the diffusion prevention layer and the heat generation layer 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. Further, when the diffusion preventing layer has low adhesion to the insulating film and is easily peeled off, an adhesion layer may be further provided between the insulating film and the diffusion preventing layer. In addition, it is made of a material (for example, Ta, Mo, Ti, Cr) having excellent adhesion to the insulating film. 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.

  Further, 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 read the change in temperature from the change in resistance value. 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.

  In the microreactor module 1 according to this embodiment, the high temperature reaction unit 4 and the low temperature reaction unit 6 are covered with gas leak prevention packages (boxes) 3 and 5 as shown in FIGS. 2, 3, and 6 to 12. It has been. As shown in FIG. 13, the gas leak prevention packages 3 and 5 are box bodies made of a plate-like metal material such as stainless steel, and have openings 7 and 9 in the lower part. A space having the same shape and size as the reaction section 6 is provided. The gas leak prevention packages 3 and 5 are covered with the high temperature reaction part 4 and the low temperature reaction part 6 of the microreactor module 1 through the openings 7 and 9, respectively. Note that notches 11 and 13 that are continuous with the openings 7 and 9 are provided on the side surfaces of the gas leak prevention packages 3 and 5. The notches 11 and 13 correspond to the positions of the connecting portions 8. When the gas leak prevention packages 3 and 5 are covered with the high temperature reaction portion 4 and the low temperature reaction portion 6, the connecting portions 8 are not separated from the notches 11 and 13 portions. Protruding.

  The inner peripheral surfaces along the openings 7 and 9 of the gas leak prevention packages 3 and 5 are joined to the outer peripheral surfaces of the base plates 102 and 28, respectively. Further, the inner peripheral surfaces along the notches 11 and 13 of the gas leak prevention packages 3 and 5 are joined to both end portions of the first connecting portion 161, the second connecting portion 165, and the bottom plate 169, respectively.

  As a result, in the unlikely event that 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 poorly joined, or the base plate 28, the lower frame 30, the middle frame 32, the upper frame. Even in the unlikely event of a joint failure between the lid 34 and the lid plate 36, the gas leak prevention packages 3 and 5 more reliably prevent the reaction gas inside the high temperature reaction section 4 or the low temperature reaction section 6 from leaking to the outside. be able to.

  Further, as shown in FIGS. 2 and 3, a getter material 188 may be provided on the surface of the gas leak prevention package 5 covering the low temperature reaction part 6. The getter material 188 is provided with a heater such as an electric heating material, 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, such as a gas remaining in the inner space of the heat insulating package 200 described later, a gas leaked from the microreactor module 1 to the inner space of the heat insulating package 200, By adsorbing the gas that has entered the heat insulation package 200 from the outside, the gas enters the internal space of the heat insulation package 200 and suppresses the deterioration of the heat insulation effect due to deterioration of the degree of vacuum. Examples of the material of the getter material 188 include an alloy mainly composed of zirconium, barium, or thianium. In FIG. 3, the wiring 190 and the lead wires 192 and 194 are not shown for easy viewing of the drawing.

  Next, a heat insulating structure for suppressing heat loss of the microreactor module 1 will be described. FIG. 18 is an exploded perspective view of a heat insulation package (heat insulation container) 200 that covers the microreactor module 1 in the present embodiment, and FIG. 19 is a perspective view showing the heat insulation package 200 obliquely from below. As shown in FIG. 18, the heat insulation package 200 is configured to cover the entire microreactor module 1, and the high temperature reaction unit 4, the low temperature reaction unit 6, and the connection unit 8 are accommodated in the heat insulation package 200.

  The heat insulation package 200 includes a rectangular box 202 having a lower surface opened and a closing plate 204 for closing the lower surface opening of the box 202. As shown in FIG. Joined and sealed with, for example, a glass material or an insulating sealing material. The box 202 and the closing plate 204 are made of a plate-like metal material such as stainless steel. Further, a metal reflection film made of aluminum, gold, silver, or the like may be formed on the inner surfaces of the box 202 and the closing plate 204. When such a metal reflective film is formed, heat loss due to radiation from the supply / discharge unit 2, the high temperature reaction unit 4, the low temperature reaction unit 6 and the connection unit 8 can be suppressed.

  A plurality of through holes penetrate through the blocking plate 204, and a part of the heat insulating package is in a state where the external circulation pipe 10 and the lead wires 176, 178, 180, 182, 184, 186, 192, 194 are inserted into the respective through holes. 200 is exposed to the outside. The external circulation pipe 10, the lead wires 176, 178, 180, 182, 184, and 186 and the through-holes of the closing plate 204 are, for example, such that the outside air does not enter the heat insulating package 200 from the part exposed to the outside. Bonded and sealed with glass material or insulating sealing material. The internal space of the heat insulation package 200 is sealed and evacuated so that the internal pressure becomes 1 Torr or less, and the internal space is made a vacuum pressure to form a vacuum heat insulation structure. Thereby, it is possible to suppress the heat of each part of the microreactor module 1 from being propagated to the outside, and to reduce the heat loss.

  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 against the closing plate 204 as a support, and the high temperature reaction section 4, the low temperature reaction section 6 and the connection section 8 are supported by the external circulation pipe 10. The high temperature reaction part 4, the low temperature reaction part 6 and the connection part 8 are separated from the inner surface of the heat insulation package 200.

In addition, it is desirable that the external flow 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 part 8 in plan view.
As described above, when the heat loss of the microreactor module 1 is suppressed as a vacuum heat insulating structure, when the reaction gas inside the high temperature reaction unit 4 or the low temperature reaction unit 6 leaks and enters the internal space of the heat insulation package 200, this As the degree of vacuum in the internal space is reduced, heat insulation is reduced and heat loss is increased, and heat of the high temperature reaction unit 4 and the low temperature reaction unit 6 leaks to the outside. By providing the gas leak prevention packages 3 and 5, the reaction gas inside the high temperature reaction unit 4 or the low temperature reaction unit 6 is prevented from leaking into the internal space of the heat insulation package 200 to maintain the degree of vacuum and increase heat loss. It can prevent that the heat of the high temperature reaction part 4 or the low temperature reaction part 6 leaks outside.

  In the above description, the getter material 188 is provided on the surface of the gas leak prevention package 5 covered with the low-temperature reaction section 6. However, the getter material 188 is provided outside the gas leak prevention packages 3 and 5 and is insulated. There is no particular limitation as long as it is inside the package 200.

  Next, the operation of 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 residual gas in the heat insulation package 200 is adsorbed by the getter material 188, the degree of vacuum in the heat insulation package 200 is increased, and the heat insulation efficiency is increased.

  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 / exhaust part 2, the high temperature reaction part 4, the low temperature reaction part 6 and the connection part 8 are made of a metal material, heat conduction is easy between them. Note that the current and voltage of the heating wires 170, 172, and 174 are measured by the control device, whereby the temperatures of the supply / discharge unit 2, the high temperature reaction unit 4 and the low temperature reaction unit 6 are measured, and the measured temperature is fed back to the control device. Then, the voltage of the heating wires 170, 172, 174 is controlled by the control device, whereby the 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, a mixture of liquid fuel and water is continuously supplied to the vaporization introduction path 14 by an external pump or the like. Alternatively, when supplied intermittently, the liquid mixture is absorbed by the liquid absorbing material, and the liquid mixture penetrates toward the vaporization introduction path 14 by capillary action. Since the liquid absorbing material is filled up to the height of the combustor plate 12, the liquid mixture in the liquid absorbing material is vaporized, and the mixture of fuel and water evaporates from the liquid absorbing material. Since the liquid mixture is vaporized in the liquid absorbing material, bumping can be suppressed and vaporization can be stably performed.

  Then, the air-fuel mixture evaporated from the liquid absorbing material 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 to the air introduction passage 16 by a pump or the like, flows into the mixing passage 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 discharge passage 24. In the fuel cell, electricity is generated by an electrochemical reaction of hydrogen gas supplied from the hydrogen discharge path 24, and off-gas containing unreacted hydrogen gas and the like is discharged from the fuel cell.

  The above operation is an initial stage operation, and the mixed liquid continues to be supplied to the vaporization introduction path 14 during the subsequent power generation operation. 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, the combustion mixture burns, and combustion heat is generated. Since the combustion channel 26 circulates around the external flow pipe 10 below the low temperature reaction section 6, the external flow pipe 10 is heated by the combustion heat and the low temperature reaction section 6 is heated. Therefore, the electric power supplied to the heating wires 170 and 174 can be reduced, and the energy use 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, and the combustion mixture burns. As a result, combustion heat is generated, but the first reformer 506 is disposed below the combustion chambers 138, 140 and the second reformer 510 is disposed above the combustion chambers 138, 140. The first reformer 506 and the second reformer 510 are heated. 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. Less heat loss due to fewer parts. Thereby, the electric power supplied to the heating wire 172 can be reduced, and the energy use efficiency is increased.

  A part of the liquid fuel stored in the fuel container may be vaporized, and the vaporized fuel / air combustion mixture may be supplied to the combustion mixture introduction paths 18 and 22.

  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 control device controls the resistance values of the heating wires 170, 172 and 174. While measuring the temperature, the voltage applied to the heating wires 170, 172, and 174 is controlled, and the pump and the like are 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 supply / discharge section 2, the high temperature reaction section 4 and the low temperature reaction section 6, 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.

  Next, specific dimensions and examples of constituent materials of each part of the reaction apparatus in the present invention will be described. The high temperature reaction part 4 is formed to have a size of, for example, a width of 16 mm, a length of 10 mm, and a height of about 6 mm. Here, the height of the second combustor combustor is formed to about 0.3 mm, for example. For example, the connecting pipe 8 is formed in a size of about 3 mm in length and about 1 mm in height and width. The low temperature reaction part 6 is formed, for example, in a size having a width of 16 mm, a length of 23 mm, and a height of about 6 mm. The external circulation pipe 10 in the supply / discharge section 2 is formed with a length of 7 to 8 mm and a length and width of 2 to 3 mm, for example. And the gas leak prevention packages 3 and 5 are formed in the box which has the space of the substantially same size as the high temperature reaction part 4 and the low temperature reaction part 6, respectively. Moreover, the heat insulation package 200 is formed to have a height of 9 to 10 mm, a width of 20 mm, and a length of about 40 mm, for example. And the metal material which forms the high temperature reaction part 4, the low temperature reaction part 6, the connection pipe | tube 8, the external distribution pipe | tube 10, the combustor plate 12, the gas leak prevention packages 3 and 5 etc. has thickness of 0.1 mm-0, for example. It is made of stainless steel SUS304 of about 2 mm. The heat insulation package 200 is made of, for example, stainless steel SUS304 having a thickness of about 0.5 mm. In this case, when the power of the heating wire 170 is 15 W and the power of the heating wire 172 is 25 W, the high temperature reaction part 4 is set to 375 ° C. and the low temperature reaction part 6 is set to 150 ° C. in about 9 to 10 seconds. Can be started in a relatively short time.

  Next, a schematic configuration of the power generation unit 601 including the microreactor module 1 in the present embodiment will be described. FIG. 20 is a perspective view showing an example of a power generation unit 601 including the microreactor module 1 in the present embodiment. As shown in FIG. 20, the microreactor module 1 as described above can be used by being assembled in the power generation unit 601. The power generation unit 601 is housed in, for example, 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 heat insulation package 200. The microreactor module 1 in a state, a fuel cell, a humidifier that humidifies the fuel cell, a recovery unit that recovers by-products generated in the fuel cell, and the like, and the microreactor module 1 and the power generation module 608 include air ( An air pump 610 for supplying oxygen), and a power supply unit 612 having an external interface and the like for electrical connection with a secondary battery, a DC-DC converter and an external device driven by the output of the power generation unit 601. Composed. 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 supplied to the fuel cell of the power generation module 608. The generated electricity is stored in the secondary battery of the power supply unit 612.

  FIG. 21 is a perspective view illustrating an example of an electronic device 701 that uses the power generation unit 601 as a power source. As shown in FIG. 21, the electronic device 701 is a portable electronic device, for example, 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 coupled by a hinge portion, and are configured so that the upper casing 708 can be folded with the liquid crystal display 706 facing the keyboard 702 by overlapping the lower casing 704. ing. 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, the internal space of the heat insulation package 200 is a heat insulation space, the high temperature reaction unit 4 is separated from the low temperature reaction unit 6, and the distance from the high temperature reaction unit 4 to the low temperature reaction unit 6 is. Is the length of the connecting portion 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 section 8, and 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 portion 8 are smaller than the height and width of the high temperature reaction portion 4 and the low temperature reaction portion 6, heat conduction through the connecting portion 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.

  Further, since the connecting flow paths 162, 164, 166, and 168 are combined into one connecting portion 8, the notches 11 and 13 provided in the gas leak prevention packages 3 and 5 are only required at one place, Can be reduced. That is, the openings 7 and 9 are joined to the base plates 102 and 28, and the notches 11 and 13 are joined to both ends of the connecting portion 8, so that leakage of the reaction gas can be prevented more reliably. Therefore, the degree of vacuum in the heat insulation package 200 can be maintained, and the temperature difference between the high temperature reaction part 4 and the low temperature reaction part 6 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 transfer from the high temperature reaction unit 4 to the outside of the heat insulation package 200 can be suppressed, and heat loss of the high temperature reaction unit 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 discharge path 24 are provided in one external circulation pipe 10. Therefore, heat transfer from the high temperature reaction part 4 to the outside of the heat insulating package 200 can be suppressed, and heat loss can be suppressed.

  The present invention is not limited to the above embodiment, and various improvements and design changes may be made without departing from the spirit of the present invention. For example, only one of the gas leak prevention packages 3 and 5 may be used. Further, another gas leak prevention package that covers the first combustor 504 may be provided on the outer periphery of the first combustor 504. Thereby, the leakage of the combustion gas from the combustor plate 12 can be reliably prevented.

  Further, another gas leak prevention package that covers the connecting portion 8 may be provided on the outer peripheral portion of the connecting portion 8 to prevent leakage of gas from the connecting portion 8. Alternatively, the connecting portion 8 may be an integral connecting tube, and the notches 11 and 13 of the gas leak prevention packages 3 and 5 may be joined to both ends of the connecting tube. By making the connecting part 8 an integral connecting pipe, leakage of gas from the connecting part 8 can be reliably prevented.

It is a schematic side view at the time of dividing the micro reactor module in embodiment of the reaction apparatus concerning this invention for every function. It is a disassembled perspective view of the micro reactor module in this embodiment. It is a side view of the micro reactor module in this embodiment. It is the perspective view which showed the microreactor module which removed the gas leak prevention package from diagonally upward. It is the perspective view which showed the microreactor module which removed the gas leak prevention package from diagonally downward. It is arrow sectional drawing of the surface along the cutting line VI-VI of FIG. It is arrow sectional drawing of the surface along the cutting line VII-VII of 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 the perspective view which showed the gas leak prevention package from diagonally lower. It is a perspective view of the member which follows the cutting line VII-VII of FIG. It is a perspective view of the member which follows the cutting line VIII-VIII of FIG. It is the figure in the microreactor module of this embodiment which showed the path | route after supplying liquid fuel and water until the hydrogen rich gas which is a product is discharged | emitted. It is the figure in the microreactor module of this embodiment which showed the path | route from the combustion air-fuel | gaseous mixture being supplied until the water etc. which are products are discharged | emitted. It is a disassembled perspective view of the heat insulation package which covers the micro reactor module in this embodiment. It is the perspective view which showed the heat insulation package from diagonally downward. It is a perspective view which shows an example of an electric power generation unit provided with the micro reactor module in this embodiment. It is a perspective view which shows an example of the electronic device which uses a power generation unit as a power supply.

Explanation of symbols

1 Microreactor module 2 Supply / discharge section 3, 5 Gas leak prevention package (sealing material)
4 High temperature reaction part 6 Low temperature reaction part 8 Connection part 10 External flow pipe (flow path)
12 Combustor plate (member)
14 Introduction path (flow path) for vaporization
16 Air introduction path (flow path)
18,22 Combustion mixture introduction path (flow path)
20 Exhaust gas discharge path (flow path)
24 Hydrogen discharge path (flow path)
26 Combustion flow path (flow path)
28,102 Base plate (member)
30,104 Lower frame (member)
32,106 Middle frame (member)
34,110 Upper frame (member)
36,112 Lid plate (member)
38 Mixed gas channel (reaction channel)
40 Mixing channel (reaction channel)
42, 44, 46, 62, 64, 78, 80, 84 Carbon monoxide removal flow path (reaction flow path)
48, 68 Combustion mixture flow path (reaction flow path)
50, 70 Exhaust gas channel (reaction channel)
108 Combustor plate (member)
114 Supply channel (reaction channel)
115 discharge channel (reaction channel)
116, 118, 128, 150 Reforming channel (reaction channel)
120 Combustion gas mixture channel (reaction channel)
122 Exhaust gas channel (reaction channel)
138,140 Combustion chamber (reaction channel)

Claims (7)

In a reaction apparatus including a reaction unit that causes a reaction of a reactant to generate a reaction product,
The reactor is a reactor that generates hydrogen from liquid fuel,
The reaction unit is set to at least a first temperature, and at least one first reactor in which a reaction channel is formed, and the first reactor is heated to the first temperature. A first reaction section comprising a heating section to be set, a first box covering the outer wall of the first reactor and the heating section, and a second temperature lower than the first temperature. A plurality of reaction units comprising: a second reaction unit including at least one second reactor in which a reaction channel is formed; and a second box covering an outer wall of the second reactor. Comprising
The reactor further includes:
A reaction material that is installed between the first reaction unit and the second reaction unit and is reacted in the first reaction unit is sent to the first reaction unit. A connecting pipe for sending the reaction product reacted in the reaction section to the second reaction section;
A reactant which is connected to the second reaction section and is supplied to the first reaction section and which is a reaction raw material of the first reaction section; and the second reaction discharged from the second reaction section. an external circulation pipe and a reaction product of parts, flows,
A reaction apparatus comprising: Each of said reaction channel of said first and second first and second in the reaction section of the reactor and the outer wall of the heating unit reactor and the first and second reactor, wherein the first and and the second box body, a reaction apparatus according to claim 1, characterized in that, each of which is formed by joining the plate-shaped metal material.   The reaction apparatus according to claim 1, wherein the heating unit includes a combustor that causes combustion of gaseous fuel flowing in a space provided therein. The combustor has a combustion flow path for circulating the gaseous fuel,
The reaction apparatus according to claim 3 , wherein a combustion catalyst for promoting a combustion reaction of the gaseous fuel is applied to a bottom surface and a side surface of the combustion channel.   The reaction apparatus further includes a heat insulating container that covers the base plate, the first reaction unit, the second reaction unit, and the connection pipe, and that has an internal space at a vacuum pressure. Item 4. The reaction apparatus according to Item 1.   The reaction apparatus according to claim 1, wherein the heating unit sets the second reaction unit to the second temperature via the connection unit.   A first reaction product is supplied to the first reaction unit to generate a first reaction product, and a second reaction unit is supplied with the first reaction product to generate a second reaction product. The first reactant is a vaporized hydrocarbon-based liquid fuel, and the first reaction section is a reformer that causes a reforming reaction of the first reactant. Carbon monoxide is contained in the first reaction product, and the second reaction unit removes carbon monoxide contained in the first reaction product by selective oxidation. The reactor according to claim 1, wherein the reactor is a reactor.

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