JP2007070179A - Reactor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a reactor capable of reducing temperature variation by keeping uniform the temperature of a portion at which high-temperature reaction occurs. <P>SOLUTION: The reactor comprises: a high-temperature reaction part 4 at which a first reaction material initiates a reaction to generate a first reaction product; a low-temperature reaction part 6 at which the first reaction material reacts at a temperature lower than that of the reaction part 4 to generate a second reaction product; a connecting tube 8 which is installed between the high- and low-temperature reaction parts 4 and 6 and supplies the first reaction material and product to the reaction parts 4 and 6, respectively; and a supply/discharge part 2 having a plurality of flow paths for discharging the second reaction product from the reaction part 4 as well as supplying the first reaction material to the reaction part 6. Further, a second combustor is provided between the stacked first and second reformers 506 and 510 to evenly heat them, thus reducing the temperature variation of the reaction part 4. <P>COPYRIGHT: (C)2007,JPO&INPIT

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 a device that directly extracts electric energy from chemical energy by electrochemically reacting fuel and oxygen in the atmosphere.

  As a fuel used in a fuel cell, hydrogen alone can be mentioned, but there is a problem in handling due to being a gas at normal temperature and normal 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. In contrast, in a reforming 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, a vaporizer that vaporizes liquid fuel and water, a reformer that extracts hydrogen necessary for power generation by reacting the vaporized liquid fuel and high-temperature water vapor, and a secondary reaction of the reforming reaction. A carbon monoxide remover or the like that removes the product carbon monoxide may be required (see, for example, Patent Document 1).

In order to reduce the size of such a reforming fuel cell, development of a microreactor in which a vaporizer, a reformer, and a carbon monoxide remover are stacked (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 obtained by joining metal substrates on which grooves are formed, and the grooves serve as flow paths.
JP 2002-356310 A JP 2005-132712 A

  However, for example, in a reformer, the operating temperature is a relatively high temperature of 250 ° C. or higher, and in order to perform a reforming reaction that sufficiently satisfies the design value, it is necessary to uniformly set the predetermined temperature over the entire flow path. There is. However, it is difficult to maintain a plurality of reactors at a relatively high and uniform temperature in the case where a plurality of reactors that form the flow paths are provided in order to lengthen the flow paths so that the reaction can be performed satisfactorily. It was. When there is a large temperature unevenness in the reformer, there is a problem that the reforming reaction that sufficiently satisfies the design value is not performed.

  Therefore, an object of the present invention is to provide a reaction apparatus that can maintain temperature of each reactor at a uniform temperature and reduce temperature unevenness in a reaction apparatus including two reactors.

  In order to solve the above problems, the invention described in claim 1 includes at least a bottom plate, a first reaction portion provided on the bottom plate, set to a first temperature, and causing a reaction of a reactant. The second reaction part is set to a second temperature lower than the first temperature and causes reaction of the reactant, and is installed between the first reaction part and the second reaction part, And a connecting pipe for sending a reaction product and a reaction product generated by the reaction between the first reaction unit and the second reaction unit, and the first reaction unit is stacked on the bottom plate. Provided between the first reactor and the second reactor, and between the first reactor and the second reactor, the first reactor and the second reaction. And a heating unit for heating the vessel to set the first temperature.

  The invention according to claim 2 is the reaction apparatus according to claim 1, wherein the heating unit sets the second reaction unit to the second temperature via the connection pipe. .

  According to a third aspect of the present invention, in the reaction apparatus according to the first aspect, the reaction apparatus is further provided in the second reaction section, and supplies at least the reactant to the first reaction section. And a supply / discharge section having a plurality of flow paths for discharging reaction products from the second reaction section.

  According to a fourth aspect of the present invention, there is provided the reaction apparatus according to the first aspect, wherein the first reaction product is supplied to the first reaction unit to generate a first reaction product, and the second reaction product is produced. 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 a fifth aspect of the present invention, in the reaction apparatus according to the first aspect, the first reaction section and the second reaction section are flow paths through which reactants flow by providing a partition in the box. Is formed.

  A sixth aspect of the present invention is the reaction apparatus according to the fifth aspect, wherein the box and the partition are formed by joining plate-like metal materials.

  A seventh aspect of the present invention is the reaction apparatus according to the first aspect, wherein the connecting pipe is formed by joining plate-like metal materials, and the first reaction section and the second reaction section are connected to each other. It is characterized by being joined.

  The invention according to claim 8 is the reaction apparatus according to claim 1, wherein the reaction apparatus further includes the bottom plate, the first reaction part, the second reaction part, and the connecting pipe. A heat insulating container is provided that covers and has an internal space at a vacuum pressure.

  The invention according to claim 9 is the reaction apparatus according to claim 8, wherein the heat insulating container is formed of a box formed by joining plate-like metal materials.

  A tenth aspect of the present invention is the reaction apparatus according to the first aspect, wherein the heating unit includes a combustor that burns gaseous fuel.

  The invention according to claim 11 is the reaction apparatus according to claim 10, wherein the combustor includes a combustion catalyst for promoting a combustion reaction of the gaseous fuel.

  A twelfth aspect of the present invention is the reaction apparatus according to the eleventh aspect, wherein the combustor has a combustion channel through which the gaseous fuel is circulated, and the combustion catalyst is a bottom surface of the combustion channel. It is applied to the side surface.

  A thirteenth aspect of the invention is characterized in that, in the reaction apparatus according to the first aspect, the heating section is a heating wire that generates heat when supplied with electric power.

  According to the present invention, in a reaction apparatus provided with two reactors, each reactor is uniformly heated from a heating unit provided between the reactors, so that temperature unevenness of each reactor can be reduced. .

  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 showing the microreactor module 1 in the embodiment of the reaction apparatus according to the present invention obliquely from above, and FIG. 2 is a perspective view showing the microreactor module 1 in this embodiment obliquely from below. FIG. 3 is a side view of the microreactor module 1 in the present embodiment.

  The microreactor module 1 is a reaction device that 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 and generates hydrogen gas used in a fuel cell. 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 a connecting pipe 8 for carrying out outflow.

  FIG. 4 is a schematic side view when the microreactor module 1 in the present embodiment 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. 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. . 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 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 liquid 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 connecting pipe 8 will be described with reference to FIGS. 3 and 5 to 12. Here, FIG. 5 is an exploded perspective view of the microreactor module 1 in the present embodiment, and FIG. 6 is a cross-sectional view taken along the plane direction of the combustor plate 12 described later along the cutting line VI-VI in FIG. 7 is a cross-sectional view taken along the plane direction of the base plate 28 and the base plate 102, which will be described later, from a cutting line VII-VII in FIG. 3, and FIG. 8 will be described later from the cutting line VIII-VIII in FIG. FIG. 9 is a cross-sectional view taken along the plane direction of the lower frame 30 and the lower frame 104, and FIG. 9 is along the plane direction of the middle frame 32 and the middle frame 106, which will be described later, from the section line IX-IX in FIG. FIG. 10 is a cross-sectional view taken along the arrow, and FIG. 10 is a cross-sectional view taken along the plane direction of the upper frame 34 and the upper frame 110, which will be described later, from the cutting line XX in FIG. Combustor plate to be described later from cutting line XI-XI FIG. 12 is a cross-sectional view taken along the plane direction 108, and FIG. 12 is a cross-sectional view taken along the plane direction perpendicular to the communication direction of the connecting pipe 8 from the cutting line XII-XII in FIG. .
FIG. 13 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. 14 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. 3, 5, and 6, the supply / discharge unit 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. And a combustor plate 12.

  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, the uppermost combustor plate 12 is joined to the lower surface of the low-temperature reaction section 6, whereby a combustion flow path 26 is formed on these joined surfaces. 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. 3 and 5, the low temperature reaction unit 6 includes a base plate (bottom plate) 28, a lower frame 30, a middle frame 32, an upper frame 34, and a lid plate 36 that are stacked in this order from the bottom. 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 plurality of partition walls inside the lower frame 30, the inner side of the lower frame 30 has a twisted carbon monoxide removal flow path 62 and a spiral carbon monoxide removal flow. It is divided into a passage 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 mixes the mixed gas. The upper part of the flow path 38, the mixing flow path 40, the carbon monoxide removal flow path 46, the combustion mixture flow path 48 and the exhaust gas flow path 50 is covered. 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 exhaust gas flow path 50 of the base plate 28 is formed at the other end of the carbon monoxide removal flow path 64. 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 plurality of partition walls inside the middle frame 32, the inside of the middle frame 32 has a twisted carbon monoxide removal flow path 78 and a spiral carbon monoxide removal flow. It is divided into a path 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 flow channel 68 of the lower frame 30 and The upper part of the exhaust gas flow path 70 is covered. 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.

  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 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 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. 5, the lid plate 36 is joined to the upper frame 34 by brazing or the like, so that the upper portion 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. An example of the catalyst for selective oxidation of carbon monoxide is 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 plate-like metal material such as stainless steel.

  As shown in FIG. 7, a plurality of partition walls are provided on the upper surface of the base plate 102 so as to protrude, thereby being divided into a supply flow path 114, a distorted 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. In the combustion mixture flow path 120 and the exhaust gas flow path 122, a bottom plate 126 is provided, 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 discharge flow path 115 of the base plate 102 are joined by the bottom plate 126. The top of is covered. 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. In addition, a bottom plate 136 is provided in the middle frame 106, and the middle frame 106 is joined to the lower frame 104 by brazing or the like, so that the bottom plate 136 is connected to the upper part of the combustion mixture flow path 120 and the exhaust gas flow path 122 of the lower frame 104. Is covered. 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.

  As shown in FIGS. 3 and 5, the combustor plate 108 is joined to the middle frame 106 by brazing or the like, so that the reforming flow path 128 of the middle frame 106 is covered by the combustor plate 108. Is done. 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, and the blow-through hole 146 is positioned on the blow-through hole 132 of the middle frame 106. 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 located 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 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 above 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. 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, 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 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 connecting pipe 8 is also 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 section 4 and the low temperature reaction section 6, and the connecting pipe 8 is joined to the high temperature reaction section 4 by brazing or the like at the center in the width direction of the high temperature reaction section 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. 7, 8, and 12, 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 the partition wall 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. Further, 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.

  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. Here, the correspondence relationship between FIGS. 13, 14, and 4 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 from the low temperature reaction section 6 through the connecting pipe 8 to the high temperature reaction section 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.

  Next, a heat insulating structure for suppressing heat loss of the microreactor module 1 will be described. FIG. 15 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. 16 is a perspective view showing the heat insulation package 200 from obliquely below. As shown in FIGS. 15 and 16, 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 connecting pipe 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. The closing plate 204 is joined to the box 202, for example, glass. It is sealed with a 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. Moreover, you may make it form the metal reflective film which consists of aluminum, gold | metal | money, silver etc. in the surface used as the inner side of the box 202 and the obstruction board 204, for example. When such a metal reflective film is formed, heat loss due to radiation from the supply / discharge section 2, the high temperature reaction section 4, the low temperature reaction section 6 and the connecting pipe 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 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 insulation 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.

  Further, as shown in FIGS. 3 and 5, a getter material 188 may be provided in the heat insulation package 200. The getter material 188 is activated by being heated and has an adsorption action. The gas remaining in the internal space of the heat insulation package 200, the gas leaked from the microreactor module 1 to the internal space of the heat insulation package 200, or from the outside The gas that has entered the heat insulating package 200 is adsorbed. This suppresses the gas from entering the internal space of the heat insulation package 200, the deterioration of the degree of vacuum, and the heat insulation effect from being lowered. 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. Examples of the material of the getter material 188 include an alloy mainly composed of zirconium, barium, or thianium. In FIG. 3, the lead wires 192 and 194 are not shown to make the drawing easier to see. 3 and 5, the getter material 188 is provided on the surface of the low-temperature reaction unit 6, but the position where the getter material 188 is provided is not particularly limited as long as the getter material 188 is provided inside the heat insulating 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 / 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. 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 of the second combustor 508, and the combustion mixture burns. This generates combustion heat. Since 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 first reformer 506 are generated by combustion heat. The two reformer 510 is 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. Since there are few parts, heat loss is small. 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. 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 8, the external flow pipe 10, the combustor plate 12, etc. is stainless steel SUS304 with a thickness of about 0.1 mm to 0.2 mm, for example. Consists of. 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. 17 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. 17, 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 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, the hydrogen rich gas is generated as described above, and the hydrogen rich gas is the fuel electrode of 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. 18 is a perspective view showing an example of an electronic device 701 that uses the power generation unit 601 as a power source. As shown in FIG. 18, 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 pipe 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.

  If the flow paths 162, 164, 166, and 168 are provided as separate connecting pipes, and are installed between the high temperature reaction part 4 and the low temperature reaction part 6 with these connection pipes separated, the low temperature reaction part 6 The stress is generated in the connecting pipe material, the low temperature reaction part 6 and the high temperature reaction part 4 due to the displacement difference between the high temperature reaction part 4 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 this embodiment, generation | occurrence | production of such a stress can be suppressed and airtightness can be kept favorable.

  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 discharge path 24 are provided in one external circulation pipe 10. Therefore, the surface area exposed to the outside can be suppressed, heat radiation 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, the heating wire 172 can be patterned relatively easily and the disconnection of the heating wire 172 can be suppressed. Can do.

  In addition, since the vaporization introduction path 14 of the external circulation pipe 10 is filled with a liquid absorbing material and the vaporization introduction path 14 is used as the vaporizer 502, the microreactor module 1 can be reduced in size and simplified, A temperature state necessary for vaporization (for example, a state where the upper portion of the vaporization introduction path 14 is 120 ° C.) can be obtained.

  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 in the vaporization introduction path 14 further reaches the height of the combustor plate 12. Since it is filled, the combustion heat in the first combustor 504 can be efficiently used for vaporization of the mixed liquid.

  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. Evenly conducted to the reformer 510, no temperature difference is generated between the first reformer 506 and the second reformer 510, and temperature unevenness can be reduced.

  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 relatively thin, so that these heat capacities can be reduced, In the initial stage, the supply / discharge section 2, the high temperature reaction section 4, the low temperature reaction section 6 and the connecting pipe 8 can be immediately warmed from room temperature to high temperature. Furthermore, the power supplied to the heating wires 170, 172, and 174 can also be lowered.

  The present invention is not limited to the above-described embodiment, and various improvements and design changes may be made without departing from the spirit of the present invention.

  For example, although the combustor (second combustor 508) is used as the heating unit in the above embodiment, the present invention is not limited to this, and the heating unit is interposed between the first reformer 506 and the second reformer 510. Alternatively, a heating wire covered with an insulating film may be provided, and power may be supplied to the heating wire to generate heat. Alternatively, both the combustor and the heating wire may be provided between the first reformer 506 and the second reformer 510.

It is the perspective view which showed the microreactor module in embodiment of the reaction apparatus concerning this invention from diagonally upward. It is the perspective view which showed the micro reactor module in this embodiment from diagonally lower. It is a side view of the micro reactor module in this embodiment. It is a schematic side view at the time of dividing the micro reactor module in this embodiment for every function. It is a disassembled perspective view of the micro reactor module in this embodiment. 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 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 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

4 High temperature reaction part 6 Low temperature reaction part 8 Connecting pipe 200 Heat insulation package 506 First reformer 508 Second combustor (heating part)
510 Second reformer

Claims (13)

At least with the bottom plate,
A first reaction section provided on the bottom plate, set to a first temperature and causing a reaction of a reactant;
A second reaction part set to a second temperature lower than the first temperature and causing a reaction of the reactant;
The reaction product that is installed between the first reaction unit and the second reaction unit and that is generated by the reaction between the first reaction unit and the second reaction unit is sent between the first reaction unit and the second reaction unit. A connecting pipe;
With
The first reaction section is provided on the bottom plate in a stacked manner, and communicates with each other between the first reactor and the second reactor, and between the first reactor and the second reactor. And a heating unit that heats the first reactor and the second reactor and sets the first reactor to the first temperature.   The reaction apparatus according to claim 1, wherein the heating unit sets the second reaction unit to the second temperature via the connecting pipe.   The reaction apparatus is further provided in the second reaction unit, and supplies a reactant to at least the first reaction unit and discharges a reaction product from the second reaction unit. The reaction apparatus according to claim 1, further comprising a supply / discharge portion having a flow path. 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. To produce a reaction product of
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. The reaction product contains carbon monoxide,
2. The reaction apparatus according to claim 1, wherein the second reaction unit is a carbon monoxide remover that removes carbon monoxide contained in the first reaction product by selective oxidation. 3.   2. The reaction apparatus according to claim 1, wherein the first reaction unit and the second reaction unit are provided with a partition wall in a box to form a flow path through which a reaction product flows.   The reactor according to claim 5, wherein the box and the partition are formed by joining plate-like metal materials.   The reaction apparatus according to claim 1, wherein the connection pipe is formed by joining plate-like metal materials and is joined to the first reaction unit and the second reaction unit.   The reaction apparatus further includes a heat insulating container that covers the entire bottom plate, the first reaction unit, the second reaction unit, and the connecting pipe, and that has an internal space at a vacuum pressure. The reaction apparatus according to claim 1.   The reaction apparatus according to claim 8, wherein the heat insulating container is a box formed by joining plate-like metal materials.   The reaction apparatus according to claim 1, wherein the heating unit includes a combustor that burns gaseous fuel.   The reactor according to claim 10, wherein the combustor includes a combustion catalyst that promotes a combustion reaction of the gaseous fuel. The combustor has a combustion flow path for circulating the gaseous fuel,
The reaction apparatus according to claim 11, wherein the combustion catalyst is applied to a bottom surface and a side surface of the combustion channel.   The reaction apparatus according to claim 1, wherein the heating unit is a heating wire that generates heat when supplied with electric power.

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