JP4305432B2 - Reactor - Google Patents

Description

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

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

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

The system mainly uses a “reformer” that provides liquid fuel for the reforming reaction and a “carbon monoxide remover” that removes by-products (carbon monoxide) generated by the reforming reaction (for example, patents). Reference 1).
JP 2002-356310 A

In the above reaction apparatus, the proper operating temperature range of the carbon monoxide remover is lower than the operating temperature range of the reformer, and the temperature environment in which the reformer and the carbon monoxide remover operate properly is different. Therefore, when connecting the reformer and the carbon monoxide remover with a completely separate pipe from the reformer and the carbon monoxide remover, the pipe can propagate heat too much to maintain the temperature difference. The inventor of the present application has attempted to narrow the piping itself so as not to disappear. However, the thinner the pipes, the more difficult the manufacturing process becomes. In particular, in a small reactor called a microreactor, fine handling is required.
An object of the present invention is to provide a reaction apparatus having a part where a reaction occurs at a high temperature and a part where a reaction occurs at a low temperature, which can be easily manufactured.

In order to solve the above problems, the reaction apparatus according to the first aspect of the present invention provides:
A first part having a top surface and a bottom surface, each having a rectangular shape, a second part having a rectangular shape having one side opposite to one side of the first part, the first part, and the second part A third portion having a side along the width direction that is shorter than a length in the width direction along opposite sides of the first portion and the second portion. An integrated member in which the lower surfaces of the first part, the second part, and the third part are flush with each other;
A first frame disposed on an upper surface of the first portion;
A first lid disposed on the opposite side of the side in contact with the first portion of the first frame;
A second frame disposed on the upper surface of the second portion;
A second lid disposed on the opposite side of the side in contact with the second portion of the second frame;
With
At least a part of the high-temperature reaction part that causes the reaction of the reactant is laminated and joined in order of the integrated member, the first frame, and the first lid from below, and the first part, wherein the first frame, the is defined by a first lid, at least a part of the low temperature reaction unit causing a reaction of the reactants at a temperature lower than the high temperature reaction unit, the integrated member from below, the The second frame body and the second lid body are laminated and joined in this order, and are defined by the second part, the second frame body, and the second lid body, and the high temperature reaction part And a connecting portion having a flow path for sending fluid between the low-temperature reaction portion and the upper surface of the third portion, and at least a portion is defined by the third portion, and in the width direction , the length of the connecting portion, Ri length and same der of the third part, the reformer the high temperature reaction unit is for reforming fuel Has the low temperature reaction unit is characterized Rukoto which have a carbon monoxide remover for removing carbon monoxide from the reformed gas from the reformer.

In the above reactor,
It is preferable that the connecting portion is provided at a center portion in the width direction of the first portion and the second portion .

In the above reactor,
The connecting portion is
A first connecting portion formed integrally with the integrated member and having a partition wall that partitions the flow path;
A second connecting portion formed integrally with the first and second frame bodies and having a partition wall for partitioning a flow path different from the first connecting portion;
Is preferably provided.

In the above reactor,
It is preferable that a partition for forming a flow path is provided on the upper surface of the first part and the front second part .

In the above reactor,
A heating wire is arranged on the lower surfaces of the first and second parts ,
It is preferable to heat the high temperature reaction part and the low temperature reaction part .

In the above reactor ,
The connecting part preferably has a flow path for supplying fuel to the reformer and a flow path for supplying reformed gas from the reformer to the carbon monoxide remover.

  According to the present invention, the reaction apparatus can be easily manufactured.

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

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

  The microreactor module 1 is 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 for a fuel cell. The microreactor module 1 has a high temperature at which a relatively high temperature hydrogen reforming reaction occurs with respect to an appropriate reaction temperature range in a supply / discharge unit 2 in which reactants are supplied and products are discharged and a low-temperature reaction unit 6 described later. Reaction between the reaction unit 4, the low-temperature reaction unit 6 in which a selective oxidation reaction relatively low with respect to the appropriate reaction temperature range in the high-temperature reaction unit 4 occurs, and between the high-temperature reaction unit 4 and the low-temperature reaction unit 6 A first connecting part 8 and a second connecting part 9 are provided for inflow or outflow of the product.

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

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

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

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

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

  Hereinafter, specific configurations of the supply / discharge unit 2, the high temperature reaction unit 4, the low temperature reaction unit 6, the first connection unit 8, and the second connection unit 9 will be described with reference to FIGS. 3 and 5 to 14. Here, FIG. 5 is an exploded perspective view of the microreactor module 1, and FIG. 6 is a cross-sectional view taken along the plane direction of the combustor plate 12 described later from the cutting line VI-VI in FIG. 7 is a cross-sectional view taken along the plane direction of a base plate 28 and a base plate 102, which will be described later, from a cutting line VII-VII in FIG. 3, and FIG. 8 is a lower frame 30 which will be described later, from a cutting line VIII-VIII in FIG. FIG. 9 is a cross-sectional view taken along the plane direction of the lower frame 104, and FIG. 9 is an arrow view cut along the plane direction of the middle frame 32 and the middle frame 106, which will be described later, from the cutting line IX-IX in FIG. FIG. 10 is a cross-sectional view, in which an integrated member 55 having a base plate 28, a first connecting portion 8 and a base plate 102, which are integrally formed, is joined to the partition wall 29 at the bottom plate 53 of the base plate 28, 11 is a perspective view of a structure in which the bottom plate 113 of the base plate 102 is joined to the partition wall 117. FIG. 11 shows an integrated member 57 having the lower frame 30, the second connecting portion 9, and the lower frame 104 formed integrally. 12 is a perspective view of the structure joined to the partition wall 73 in the bottom plate 72, and FIG. 12 is cut along the plane direction of the bottom plate 86 of the upper frame 34 and the bottom plate 152 of the upper frame 110 from the cutting line XII-XII of FIG. 13 is a cross-sectional view taken along the arrow, and FIG. 13 is a cross-sectional view taken along the plane direction of the bottom plate 141 of the combustor plate 108 from the cutting line XIII-XIII in FIG. 3, and FIG. It is arrow sectional drawing cut | disconnected along the thickness direction of the 1st connection part 8 and the 2nd connection part 9 from -XII.

  Since the base plate 28, the first connecting portion 8 and the base plate 102 of the integrated member 55 are integrally formed by the same member, there is no seam between them, and the surrounding frame and a low partition wall at a predetermined location are short. Is provided. Since the lower frame 30, the second connecting portion 9 and the lower frame 104 of the integrated member 57 are integrally formed by the same member, there is no joint between them, and the back of the surrounding frame and a predetermined place A low partition is provided.

  As shown in FIGS. 3, 5, and 6, the supply / exhaust unit 2 has an external circulation made of a metal material such as stainless steel (SUS304) that has flexibility against thermal expansion and is excellent in thermal conductivity and corrosion resistance. A tube 10 and three combustor plates 12 stacked around the outer circulation tube 10 are provided. The combustor plate 12 is joined to the external flow pipe 10 by hard soldering. As the wax, it is preferable to apply a wax having a melting point higher than the maximum temperature of the fluid flowing through the external flow pipe 10 and the combustor plate 12 and having a melting point of 700 degrees or more. In particular, gold wax containing silver, copper, zinc and cadmium, wax containing gold, silver, zinc and nickel as main components, or wax containing gold, palladium and silver as main components are particularly preferable.

  The external circulation pipe 10 is a pipe having a plurality of channels through which each fluid in the microreactor module 1 is circulated to the outside of the microreactor module 1. In the external circulation pipe 10, the vaporization introduction path 14, the air introduction path 16, the combustion mixture introduction path 18, the exhaust gas discharge path 20, the combustion mixture introduction path 22 and the hydrogen gas discharge path 24 are parallel to each other. Is provided. The vaporization introduction path 14, the air introduction path 16, the combustion mixture introduction path 18, the exhaust gas discharge path 20, the combustion mixture introduction path 22 and the hydrogen gas discharge path 24 are partitioned by a partition wall 29 of the external circulation pipe 10. Yes. The vaporization introduction path 14, the air introduction path 16, the combustion mixture introduction path 18, the exhaust gas discharge path 20, the combustion mixture introduction path 22, and the hydrogen gas discharge path 24 are provided in one external circulation pipe 10. However, the external flow pipe 10 may be one in which these flow paths 14, 16, 18, 20, 22, 24 are provided in separate pipe materials and these pipe materials are bundled. The hydrogen gas discharge path 24 of the external flow pipe 10 is connected to a fuel electrode of a power generation module 608 described later, and the vaporization introduction path 14 of the external flow pipe 10 is connected to a fuel container 604 via a flow rate control unit 606 described later. It is connected.

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

The combustor plate 12 is also made of a metal material such as stainless steel (SUS304) having excellent corrosion resistance. 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. Further, a partition wall 31 is provided on one surface of the combustor plate 12 so as to protrude. A part of the partition wall 31 is provided over the entire outer edge of the combustor plate 12, and another part of the partition wall 31 is provided in the radial direction, and the three combustor plates 12 are brazed around the outer circulation pipe 10. When the uppermost combustor plate 12 is joined to the lower surface of the low-temperature reaction section 6, the combustion channel 26 is formed on the 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 33 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 the base plate 28 of the integrated member 55, the lower frame 30, the middle frame 32, the upper frame 34, and the lid plate 36 of the integrated member 57 in this order from the bottom. It is laminated and joined, and has a rectangular parallelepiped shape. The base plate 28, the lower frame 30, the middle frame 32, the upper frame 34, and the lid plate 36 are made of a metal material such as stainless steel (SUS304) having excellent corrosion resistance.

  The outer circulation pipe 10 and the uppermost combustion 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, the partition wall 29 is provided on the upper surface of the base plate 28 so as to protrude, so that a distorted carbon monoxide removal flow path 44 is formed, and the partition wall 29 is formed on the upper surface of the base plate 28. 29 is provided so that a partition wall 41 lower than 29 protrudes, a mixed gas flow path 38, a mixed flow path 40, a carbon monoxide removal flow path 42, a U-shaped carbon monoxide removal flow path 46, The combustion mixture channel 48 and the exhaust gas channel 50 are divided.

  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 removing channel 46 surrounds the through hole 52, and a through hole 54 is formed at the end of the carbon monoxide removing channel 46, and the carbon monoxide removing channel 46 passes through the through hole 54. To the hydrogen gas 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. An air channel 59 is provided at the end of the mixing channel 40, and the air channel 59 communicates with the through hole 60, and the mixing channel 40 communicates with the air introduction channel 16 through the through hole 60. . A bottom plate 53 is provided on the lower surface of the base plate 28 except for the through hole 52, the through hole 54, the through hole 56, the through hole 58, and the through hole 60.

  As shown in FIG. 8, the partition wall 29 is arranged inside the lower frame 30, so that the inside of the lower frame 30 is divided into a twisted carbon monoxide removal flow path 62. Then, by providing the partition wall 73 and the bottom plate 72 provided in the lower frame 30, the spiral carbon monoxide removing flow path 64 is divided. A blow-off hole 66 is divided by a partition wall provided in the middle of the carbon monoxide removal channel 64. Further, by providing a partition wall between the lower frame 30 and the second connecting portion 9, the combustion mixture flow path 68 and the exhaust gas flow path 70 are separated. The bottom plate 72 is provided on the lower surface of 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, the bottom plate 72 causes the mixed gas flow path 38, The top of the mixing channel 40, the carbon monoxide removing channel 46, the combustion mixture channel 48, the exhaust gas channel 50 and the air channel 59 is covered.

  One end portion 64 a of the carbon monoxide removal flow path 64 communicates with the carbon monoxide removal flow path 62, and the carbon monoxide removal flow in the base plate 28 is in the middle of the carbon monoxide removal flow path 64. A blow-through hole 74 communicating with the passage 42 is formed, and a blow-through hole 76 communicating with the exhaust gas flow path 50 of the base plate 28 is formed at the other end portion 64 b of the carbon monoxide removal flow path 64.

The partition wall 29 is partitioned so that the carbon monoxide removal flow path 62 and the carbon monoxide removal flow path 44 of the base plate 28 coincide with each other in plan view, and the carbon monoxide removal flow path 62 and the carbon monoxide removal flow are separated. The path 44 is blown through. The blow-through hole 66 is located on the mixing channel 40 of the base plate 28. A blow-through hole 69 is formed in the combustion mixture flow path 68, and the combustion mixture flow path 68 communicates with the combustion mixture flow path 48 of the base plate 28 via the blow-through hole 69. An exhaust hole 71 is formed in the exhaust gas flow path 70, and the exhaust gas flow path 70 communicates with the exhaust gas flow path 50 of the base plate 28 via the blow through hole 71.
In plan view, the external circulation pipe 10 overlaps a part of the carbon monoxide removal flow path 64, and the carbon monoxide removal flow path 64 is formed so as to spiral around the external flow pipe 10.

  As shown in FIG. 9, partition walls 29 and 73 are provided inside the middle frame 32, so that the inside of the middle frame 32 has a twisted carbon monoxide removal channel 78 and a spiral carbon monoxide removal channel. It is divided into a flow path 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, the bottom plate 83 causes the combustion mixture flow path 68 and the exhaust gas flow path 70 of the lower frame 30 to be connected. The top is covered.

  The partition wall 29 is partitioned so that the carbon monoxide removal channel 78 and the carbon monoxide removal channel 62 of the lower frame 30 coincide with each other in plan view, and the carbon monoxide removal channel 78 and the carbon monoxide removal channel are separated. The flow path 62 is blown through. The carbon monoxide removal channel 80 overlaps the carbon monoxide removal channel 64 of the lower frame 30, and the carbon monoxide removal channel 80 and the carbon monoxide removal channel 64 are blown through. The blow-through hole 82 is overlapped with the blow-through hole 66 of the lower frame 30, and the blow-through hole 82 and the blow-through hole 66 are blown through.

  Here, as shown in FIG. 10, among the partition walls provided on the base plate 28, the four partition walls 29 forming the carbon monoxide removal channel 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 through the lower frame 30 to the middle frame 32, and simultaneously partitions the twisted carbon monoxide removal channels 44, 62, 78. Yes. As shown in FIG. 11, 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 and simultaneously forms spiral carbon monoxide removal channels 64 and 80. In the lower frame 30 of the integrated member 57, a hole 75 is provided at a position facing the carbon monoxide removal channel 42 of the integrated member 55, and the partition wall is positioned at a position facing the partition wall 29 formed in the integrated member 55. A hole 77 for inserting 29 is provided. Further, in the lower frame 104 of the integrated member 57, a hole 79 is provided at a position facing the reforming flow path 116 formed in the integrated member 55.

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

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

  As shown in FIG. 5, the lid plate 36 is joined onto the upper frame 34, so that the upper side of the carbon monoxide removal channel 84 is covered with the lid plate 36. Here, a carbon monoxide selective oxidation catalyst that selectively oxidizes carbon monoxide is supported on the entire wall surfaces of the carbon monoxide removal flow paths 42, 44, 46, 62, 64, 78, 80, and 84. ing. Examples of the catalyst for selective oxidation of carbon monoxide include platinum.

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

  As shown in FIG. 7, the partition wall 117 is provided on the upper surface of the bottom plate 113 of the base plate 102 so as to protrude into the supply channel 114, the twisted reforming channel 116, and the discharge channel 115. ing. The supply channel 114 is continuous with the reforming channel 116, but the discharge channel 115 is independent of the supply channel 114 and the reforming channel 116.

  As shown in FIG. 8, the partition wall 117 is disposed inside the lower frame 104, so that the reforming channel 118, the combustion mixture channel 120, the exhaust gas channel 122, It is divided into blow-through holes 124. The combustion mixture channel 120 and the exhaust gas channel 122 are provided with a bottom plate 126, and the lower frame 104 is joined to the base plate 102, so that the bottom plate 126 covers the supply channel 114 and the discharge channel 115 above the base plate 102. Is done. 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 blown through.

  As shown in FIG. 9, the partition wall is arranged inside the middle frame 106, so that the inside of the middle frame 106 is formed into a distorted reforming flow path 128, a blow hole 130, a blow hole 132, and a blow hole 134. It is divided. The middle frame 106 is provided with a bottom plate 136, and the middle frame 106 is joined to the lower frame 104, so that the bottom plate 136 covers the combustion mixture flow path 120 and the exhaust gas flow path 122 of the lower frame 104.

  The reforming channel 128 overlaps the reforming channel 118 of the lower frame 104, and the reforming channel 128 and the reforming channel 118 are blown through. The blow-through hole 130 is overlapped with the blow-through hole 124 of the lower frame 104, and the blow-through hole 130 and the blow-through hole 124 are blown through. The blow-through hole 132 is located on the end of the combustion mixture flow path 120, and the blow-through hole 134 is located on the end of the exhaust gas flow path 122.

  Here, as shown in FIG. 10, among the partition walls provided in 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 through the lower frame 104 to the middle frame 106, and is a twisted reforming flow path 116, 118, 128 that communicates with each other in the vertical direction. Are formed at the same time.

  As shown in FIGS. 3 and 5, the combustor plate 108 is joined onto the middle frame 106, whereby the reforming flow path 128 of the middle frame 106 is covered with the combustor plate 108. As shown in FIG. 13, the partition 109 is provided on the upper surface of the bottom plate 141 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. Yes.

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

  A blow-through hole 148 is formed at the end of the combustion chamber 140, the blow-through hole 148 is positioned on the blow-through hole 134 of the middle frame 106, and the combustion chamber 140 passes through the blow-through hole 148 and the blow-through hole 134 in the direction of the arrow. It leads to the exhaust gas flow path 122 so that the fluid advances.

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

  As shown in FIG. 12, the partition wall 111 is provided on the inner side of the upper frame 110, so that a distorted reforming flow channel 150 is formed on the inner side of the upper frame 110. Further, a bottom plate 152 is provided on the upper frame 110, and the upper frame 110 is joined onto the combustor plate 108, whereby the combustion chamber 138 and the combustion chamber 140 above the combustor plate 108 are covered.

  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. 5, the lid plate 112 is joined to the upper frame 110, so that the upper part 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. Here, a combustion catalyst is supported in advance at predetermined portions of the base plate 102, the lower frame 104, the middle frame 106, the combustor plate 108, the upper frame 110, and the lid plate 112, which are the wall surfaces, before being joined to each other. . Examples of the reforming catalyst used for reforming methanol include a Cu / ZnO-based catalyst and a Pt / ZnO-based catalyst.

  The first connecting portion 8 is constructed between the high temperature reaction portion 4 and the low temperature reaction portion 6, and each width of the high temperature reaction portion 4 and the low temperature reaction portion 6 as shown in FIGS. 5, 7, and 10. It is integrally formed with base plates 28 and 102 as a base at the center in the direction. The lower surface of the first connecting portion 8 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 9 is also constructed between the high temperature reaction portion 4 and the low temperature reaction portion 6, and each width of the high temperature reaction portion 4 and the low temperature reaction portion 6 is shown in FIGS. 5, 8, and 11. It is integrally formed with the lower frames 30 and 104 as frame bodies at the center in the direction.

  As shown in FIGS. 7 and 14, the first connecting portion 8 is provided with a connecting channel 162 and a connecting channel 164 so as to be parallel to each other. The connection channel 162 and the connection channel 164 are partitioned by a partition wall of the first connection part 8, and the upper side is partitioned by the bottom surface of the second connection part 9. As shown in FIGS. 8 and 14, the second connecting portion 9 is provided in the interior thereof so that the connecting channel 166 and the connecting channel 168 are parallel to each other, like the first connecting portion 8. The connection channel 166 and the connection channel 168 are partitioned by a partition wall of the second connection part 9, and the upper side is partitioned by a lid 167.

  As shown in FIGS. 3 and 4, the width of the connection portion 165 having the first connection portion 8, the second connection portion 9, and the lid 167 is narrower than the width of the high temperature reaction portion 4 and the low temperature reaction portion 6. The height of the connecting portion 165 is also lower than the height of the high temperature reaction portion 4 and the low temperature reaction portion 6. As described above, the first connecting portion 8 and the second connecting portion 9 of the connecting portion 165 are both short in width and low in height. However, the first connecting portion 8 is formed integrally with the base plates 28 and 102, and the lower frame 30. , 104 are formed so as to be integrated with the base plates 28, 102 and the lower frames 30, 104, so that a relatively small member such as the first connecting portion 8 and the second connecting portion 9 is relatively large. The integrated member 55 and the integrated member 57 may be joined to other members. Therefore, it is easier to manufacture than a combination of finely disassembled members.

  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 partition between the connection flow paths 162 and 164 in one first connection portion 8 is integrated as a single piece, the first connection portion 8 is formed integrally with the base plate 28 and the base plate 102 without any joint. As long as the connection flow paths 162 and 164 are separated from each other, the connection flow paths 162 and 164 may be individual partition walls. Similarly, the partition wall between the connection flow paths 166 and 168 in one second connection portion 9 is integrated as one piece, but the second connection portion 9 is formed integrally with the base plate 28 and the base plate 102 without a joint. As long as the connection channels 166 and 168 are separated from each other, the connection channels 166 and 168 may be individual partition walls.

  As described above, the flow path is partitioned by the partition walls (including the bottom plate, the top plate, the side plate, and the outer plate) inside the supply / discharge unit 2, the high temperature reaction unit 4, the low temperature reaction unit 6, and the connection unit 165. In any part, the thickness of the partition wall is 0.1 mm or more and 0.2 mm or less, preferably 0.1 mm.

  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 165 are as shown in FIGS. Here, the correspondence relationship between FIGS. 15, 16, and 4 will be described. The vaporization introduction path 14 corresponds to the vaporizer 502, and the reforming flow paths 116, 118, and 128 correspond to the first reformer 506. The reforming flow path 150 corresponds to the second reformer 510, and the carbon monoxide removal flow path 84 from the start end to the end of the carbon monoxide removal flow path 46 corresponds to the carbon monoxide removal apparatus 512. The combustion flow path 26 corresponds to the first combustor 504, and the combustion chambers 138 and 140 correspond to the second combustor 508.

  As shown in FIGS. 2 and 5, the lower surface of the integrated member 55, that is, the lower surface of the base plate 28 that is the lower surface of the low temperature reaction portion 6, the lower surface of the base plate 102 that is the lower surface of the high temperature reaction portion 4, and the first connecting portion 8. An insulating film (not shown) such as silicon nitride, silicon oxide or the like is formed on the entire lower surface. On the lower surface of the insulating film on the low temperature reaction part 6 side, the heating wire 170 is patterned so as to meander so as to overlap with at least a part of the flow path of the carbon monoxide remover 512 in plan view. The heating wire 172 overlaps at least a part of the flow paths of the first reformer 506 and the second reformer 510 in a plan view on the lower surface from the first connecting portion 8 to the high temperature reaction portion 4. Thus, the pattern is formed in a meandering state. 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.

  By forming the insulating film, the voltage to be applied is not applied to the first connecting portion 8 made of the metal material, the base plate 28, the base plate 102, the external flow pipe 10, the combustor plate 12, and the like, and the heating wire 170 , 172, 174 can be improved.

  The heating wires 170, 172, and 174 are formed by laminating an adhesion layer, a diffusion prevention layer, and a heat generation layer in this order from the insulating film side. The heat generating layer is a material having the lowest resistivity among the three layers (for example, Au). When a voltage is applied to the heating wires 170, 172, and 174, a current flows intensively and heat is generated. The diffusion prevention layer is a material in which the material of the heat generation layer is not easily diffused into the diffusion prevention layer even when the heating wires 170, 172, and 174 generate heat, and the material of the diffusion prevention layer is difficult to thermally diffuse into the heat generation layer. It is preferable to use a substance (for example, W) having a high target melting point and low reactivity. The adhesion layer is made of a material (for example, Ta, Mo, Ti, Cr) having excellent adhesion to the diffusion prevention layer and 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 first connection unit 8 at startup, and the heating wire 174 is connected to the vaporizer 502 of the supply / exhaust unit 2 and The first 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 unit 4 and the first connecting unit 8 as an auxiliary to the second combustor 508. Similarly, when the first combustor 504 is burned with off-gas containing hydrogen from the fuel cell, the heating wire 170 heats the low-temperature reaction unit 6 as an auxiliary to the first combustor 504.

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

  In addition, the part which consists of nonmetallic materials, such as a ceramic, is formed in the lower surface of the 1st connection part 8, the baseplate 28, the baseplate 102, the side surface of the external distribution pipe 10, and the surface of the combustor plate 12, and the nonmetallic material The insulating film may be formed on the part. In this case, the mechanical strength of the 1st connection part 8, the low temperature reaction part 6, the high temperature reaction part 4, the external flow pipe 10, and the combustor plate 12 increases, and it can prevent that these members are damaged.

  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 not shown for easy viewing of the drawing.

  As shown in FIGS. 17 and 18, the reaction apparatus 1000 according to the present invention includes a heat insulating package 200 in addition to the microreactor module 1, and includes a high temperature reaction unit 4, a low temperature reaction unit 6, a first connection unit 8, and a first connection unit 8. The two connecting portions 9 are accommodated in the heat insulating package 200. The heat insulating package 200 includes a rectangular box 202 having an open bottom surface and a base plate 204 that closes the bottom opening of the box 202. The base plate 204 is joined to the box 202 with a glass material or an insulating sealing material. ing. Both the box 202 and the base plate 204 are made of a heat insulating material such as glass or ceramic, and a metal reflective film such as aluminum or gold is formed on the inner surface. When such a metal reflective film is formed, the heat-insulating package 200 reflects the radiant heat from the supply / discharge section 2, the high temperature reaction section 4, the low temperature reaction section 6, the first connection section 8 and the second connection section 9. Suppresses propagation outside of.

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

  In the space sealed with the heat insulating package 200, the connecting portion 165 that separates the high temperature reaction portion 4 and the low temperature reaction portion 6 from each other by a predetermined distance between the high temperature reaction portion 4 and the low temperature reaction portion 6 of the microreactor module 1 is provided. However, since the volume of the connecting part 165 is extremely small with respect to the volume of the high temperature reaction part 4 and the low temperature reaction part 6, the propagation of heat from the high temperature reaction part 4 to the low temperature reaction part 6 by the connection part 165 Therefore, the thermal gradient necessary for the reaction can be maintained between the high temperature reaction unit 4 and the low temperature reaction unit 6, the temperature in the high temperature reaction unit 4 can be easily equalized, and the temperature in the low temperature reaction unit 6 can be equalized easily. can do.

  As shown in FIGS. 3 and 5, a fluid that can leak from the microreactor module 1 over time, a fluid generated from the microreactor module 1 over time, and sufficient evacuation can be performed when the box body 202 and the base plate 204 are joined. A getter material 188 that is removed from the internal space of the heat insulation package 200 by adsorbing a factor that increases the pressure in the internal space of the heat insulation package 200 such as a part of the remaining outside air and the outside air that enters the heat insulation package 200 over time. 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. Examples of the material of the getter material 188 include an alloy mainly composed of zirconium, barium, or titanium. In FIG. 3, the lead wires 192 and 194 are not shown to make the drawing easier to see.

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

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

  The external circulation pipe 10 is in a state of protruding both inside and outside the heat insulating package 200. Therefore, inside the heat insulation package 200, the external flow pipe 10 is in a state of standing with respect to the base plate 204 as a support, and the high temperature reaction section 4, the low temperature reaction section 6, and the connection section 165 are supported by the external flow pipe 10, The high temperature reaction part 4, the low temperature reaction part 6, and the connection part 165 are separated from the inner surface of the heat insulation package 200.

  In addition, it is desirable that the external circulation pipe 10 is connected to the lower surface of the low temperature reaction unit 6 at the center of gravity of the high temperature reaction unit 4, the low temperature reaction unit 6, and the connection unit 165 in plan view.

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

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

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

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

  Further, when a voltage is applied between the lead wires 176 and 178, the heating wire 170 generates heat and the low temperature reaction part 6 is heated. When a voltage is applied between the lead wires 180 and 182, the heating wire 172 generates heat and the high temperature reaction unit 4 is heated. When a voltage is applied between the lead wires 184 and 186, the heating wire 174 generates heat, and the upper part of the external circulation pipe 10 is heated mainly in the supply / discharge section 2. Since the supply / exhaust part 2, the high temperature reaction part 4, the low temperature reaction part 6, and the connection part 165 are made of a metal material, it is easy to conduct heat among them.

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

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

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

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

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

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

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

  The above operation is an initial operation, and the mixed liquid continues to be supplied to the vaporization introduction path 14 during power generation. Then, air is mixed with the off-gas discharged from the fuel cell, and the mixture (hereinafter referred to as “combustion mixture”) is supplied to the combustion mixture introduction path 22 and the combustion mixture introduction path 18.

  The combustion mixture supplied to the combustion mixture introduction path 22 flows into the combustion channel 26 of the first combustor 504, and the combustion mixture burns. As a result, the first combustor 504 circulating around the external flow pipe 10 below the low temperature reaction section 6 heats the external flow pipe 10 to a desired temperature and heats the low temperature reaction section 6 to a desired temperature. Therefore, the power consumption of the heating wires 170 and 174 can be reduced, and the energy utilization efficiency is increased.

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

  Alternatively, the liquid fuel stored in the fuel container may be vaporized and the vaporized liquid fuel and 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 controller controls the temperature by the resistance of the heating wires 170, 172 and 174. The voltage applied to the heating wires 170, 172, and 174 is controlled while the pump is controlled. When the pump is controlled by the control device, the flow rate of the combustion mixture supplied to the combustion mixture introduction passages 18 and 22 is controlled, whereby the amount of combustion heat of the combustors 504 and 508 is controlled. As described above, the control device controls the heating wires 170, 172, 174 and the pump, thereby controlling the temperatures of the high temperature reaction unit 4, the low temperature reaction unit 6 and the supply / discharge unit 2, respectively.

  Here, the high temperature reaction part 4 is 250 ° C. to 400 ° C., preferably 300 ° C. to 380 ° C., and the low temperature reaction part 6 is lower than the high temperature reaction part 4, specifically 120 ° C. to 200 ° C., more preferably 140 ° C. Temperature control is performed so as to be ˜180 ° C. More specifically, as shown in FIG. 19, the line L1 located near the bottom plate 53 of the low temperature reaction part 6 is 150 ° C., the line L2 located at the upper end of the liquid absorbing material 33 is 120 ° C., and the outer surface of the base plate 204 is The temperature distribution is preferably such that the position line L3 is 80 ° C. and the line L4 located below the liquid absorbent 33 is 65 ° C.

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

  Further, the fuel sucked into the liquid absorbing material 33 in the vaporization introduction path 14 and the air introduced from the air introduction path 16 are first combusted before reaching the high temperature reaction section 4 and the low temperature reaction section 6, respectively. Not only the combustion heat of the vessel 504 but also the heat of the gas discharged from the exhaust gas discharge path 20 and the hydrogen gas discharge path 24 in advance.

  Similarly, the air-fuel mixtures introduced from the combustion mixture introduction path 18 and the combustion mixture introduction path 22 are preliminarily exhaust gas discharge path 20 and hydrogen gas before reaching the second combustor 508 and the first combustor 504. The gas is heated by the heat of the gas discharged from the discharge path 24.

  Accordingly, while heating the fluid in the vaporization introduction path 14, the air introduction path 16, the combustion mixture introduction path 18, and the combustion mixture introduction path 22 with the heat of the fluid in the exhaust gas discharge path 20 and the hydrogen gas discharge path 24, The fluid in the exhaust gas discharge path 20 and the hydrogen gas discharge path 24 is cooled by the fluid in the vaporization introduction path 14, the air introduction path 16, the combustion mixture introduction path 18, and the combustion mixture introduction path 22. Heat exchange can be performed.

  For this reason, it is not necessary to separately use cooling means for cooling the fluid in the exhaust gas discharge path 20 and the hydrogen gas discharge path 24, or the cooling means can be reduced in size.

  As shown in FIG. 20, the reaction apparatus 1000 as described above can be used by being assembled in a power generation unit 601. The power generation unit 601 includes a frame 602, a fuel container 604 that can be attached to and detached from the frame 602, a flow rate control unit 606 having a flow path, a pump, a flow rate sensor, a valve, and the like, and a state in which the heat generation unit 601 is accommodated in the heat insulation package 200. A power generation module 608 having a microreactor module 1 (reaction apparatus 1000), a fuel cell, a humidifier for humidifying the fuel cell, a recovery unit for recovering by-products generated in the fuel cell, and the like, and the microreactor module 1 and the power generation module 608 A power source having an air pump 610 for supplying air (oxygen) to the battery, an external interface for electrically connecting a secondary battery, a DC-DC converter, and an external device that the power generation unit 601 drives with the output of the power generation unit 601 A unit 612. By supplying the mixture of water and liquid fuel in the fuel container 604 to the microreactor module 1 by the flow rate control unit 606, hydrogen rich gas is generated as described above, and the hydrogen rich gas is the fuel of the power generation module 608 that is a fuel cell. The electricity generated and supplied to the electrodes is stored in the secondary battery of the power supply unit 612.

  FIG. 21 is a perspective view of an electronic device 701 using the power generation unit 601 as a power source. As shown in FIG. 21, the electronic device 701 is a portable electronic device, particularly a notebook personal computer. The electronic device 701 includes a lower housing 704 that includes an arithmetic processing circuit composed of a CPU, a RAM, a ROM, and other electronic components and includes a keyboard 702, and an upper housing 708 that includes a liquid crystal display 706. Prepare. The lower casing 704 and the upper casing 708 are connected by a hinge portion 712, and the upper casing 708 is overlapped with the lower casing 704 and can be folded with the liquid crystal display 706 facing the keyboard 702. Has been. A mounting portion 710 for mounting the power generation unit 601 is recessed from the right side surface to the bottom surface of the lower housing 704, and when the power generation unit 601 is mounted on the mounting portion 710, the electronic device 701 operates by electricity of the power generation unit 601. .

  As described above, according to the present embodiment, as shown in FIG. 10, since the base plates 28 and 102 and the first connecting portion 8 are integrated, the base plates 28 and 102 are shared as one member. The total number of members of the high temperature reaction unit 4, the low temperature reaction unit 6, and the first connection unit 8 is reduced by the amount related to the sharing. Therefore, the total number of members of the high temperature reaction unit 4, the low temperature reaction unit 6, and the first connection unit 8 is reduced. Further, the base plate 28, 102 of the high temperature reaction unit 4 and the low temperature reaction unit 6 and the first connection unit 8 are reduced. A joining process is also unnecessary, and the manufacturing process can be simplified.

  Although it is the same as the above, as shown in FIG. 11, since the lower frames 30, 104 and the second connecting portion 9 are also integrated, the lower frames 30, 104 and the second connecting portion 9 are shared, The total number of members of the high-temperature reaction unit 4, the low-temperature reaction unit 6, and the second connection unit 9 is reduced. A process is also unnecessary, and the manufacturing process can be simplified.

  Further, in the low temperature reaction section 6, the partition wall 29 extends from the base plate 28 through the lower frame 30 to the middle frame 32, the partition wall 73 extends from the lower frame 30 to the middle frame 32, and in the high temperature reaction section 4, the partition wall 117 is the base plate. Since it extends from 102 to the middle frame 106 via the lower frame 104, it is not necessary to separately provide a partition that forms a flow path for the lower frames 30 and 104 and the middle frames 32 and 106. Therefore, the number of members of the high temperature reaction section 4 and the low temperature reaction section 6 is reduced. Furthermore, when the base plates 28 and 102 and the lower frames 30 and 104 are joined, the lower frames 30 and 104 and the middle frames 32 and 106 are joined. In this case, the process of joining the partition walls becomes unnecessary, and the manufacturing process can be simplified.

  Further, the internal space of the heat insulation package 200 is a heat insulation space, the high temperature reaction part 4 is separated from the low temperature reaction part 6, and the distance from the high temperature reaction part 4 to the low temperature reaction part 6 is the length of the connecting part 165. ing. 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 165, and heat transfer to the low temperature reaction section 6 that does not require high temperature is limited. Particularly, since the height and width of the connecting portion 165 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 165 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.

Moreover, since the connection flow paths 162, 164, 166, and 168 are put together in one place of the connection portion 165, the stress generated in the connection portion 165 can be reduced. That is, since there is a temperature difference between the high temperature reaction part 4 and the low temperature reaction part 6, the high temperature reaction part 4 expands more than the low temperature reaction part 6, but the high temperature reaction part 4 is connected to the connection part 165. Since the portion other than the portion is a free end, the stress generated in the connecting portion 165 or the like can be suppressed. In particular, the connecting part 165 is smaller in height and width than the high-temperature reaction part 4 and the low-temperature reaction part 6, and the connecting part 165 is a high-temperature reaction part 4 and a low-temperature reaction at the center in the width direction of the high-temperature reaction part 4 and low-temperature reaction part 6. Since it connects with the part 6, the stress which arises in the connection part 165 can be suppressed rather than being located in the edge part of the width direction.
Since the single external circulation pipe 10 is connected between the low temperature reaction part 6 and the heat insulation package 200, the stress generated in the external circulation pipe 10 and the like can be reduced.

  In addition, since the temperature difference between the high temperature and the low temperature of the high temperature reaction part 4 is larger than the temperature difference between the high temperature and the low temperature of the low temperature reaction part 6, when an external circulation pipe is arranged on the high temperature reaction part 4 side, Since the thermal expansion and contraction of the pipe material is larger than the thermal expansion and contraction of the pipe material when the external circulation pipe material is arranged on the low temperature reaction part 6 side, the airtightness in the heat insulating package 200 is easily impaired. In the present embodiment, occurrence of such stress can be suppressed.

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

  Since the lower surface of the first connecting portion 8, the lower surface of the high temperature reaction portion 4, and the lower surface of the low temperature reaction portion 6 are flush and there is no step, the heating wire 172 can be patterned relatively easily. Disconnection can be suppressed.

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

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

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

  In any part of the supply / discharge section 2, the high temperature reaction section 4, the low temperature reaction section 6, and the connection section 165, since the partition walls partitioning the flow path are thinned, these heat capacities can be reduced, and the initial stage of operation The heating / discharging part 2, the high temperature reaction part 4, the low temperature reaction part 6, and the connecting part 165 can be immediately heated from room temperature to high temperature. Furthermore, the power consumption of the heating wires 170, 172, and 174 can be reduced.

  Since the connecting part 165 is formed integrally with a part of the members constituting the high temperature reaction part 4 and the low temperature reaction part 6, it is connected seamlessly between the high temperature reaction part 4 and the low temperature reaction part 6. In some places, it is less likely to be disengaged from the high temperature reaction part 4 or the low temperature reaction part 6 when stress is applied, compared to the case where the high temperature reaction part 4 or the low temperature reaction part 6 is completely joined separately.

It is a perspective view of the micro reactor module 1 shown diagonally from the top. It is a perspective view of the micro reactor module 1 shown from diagonally below. 1 is a side view of a microreactor module 1. FIG. It is a schematic side view at the time of dividing the micro reactor module 1 for every function. 1 is an exploded perspective view of a microreactor module 1. FIG. 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 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 arrow sectional drawing of the surface along the cutting line XII-XII of FIG. It is arrow sectional drawing of the surface along the cutting line XIII-XIII of FIG. It is arrow sectional drawing of the surface along the cutting line XIV-XIV of FIG. It is drawing which showed the path | route from liquid fuel and water being supplied until the hydrogen rich gas which is a product is discharged | emitted. It is drawing which showed the path | route until a water etc. which are a product are discharged | emitted after a combustion air-fuel mixture is supplied. 2 is an exploded perspective view of a heat insulation package 200 of the microreactor module 1. FIG. It is a perspective view of the heat insulation package 200 shown from diagonally below. It is arrow sectional drawing of the surface along the cutting line XIX-XIX of FIG. 3 is a perspective view of a power generation unit 601. FIG. 2 is a perspective view of an electronic device 701. FIG.

Explanation of symbols

1000 reactor 4 high temperature reaction section 6 low temperature reaction section 8 first connection section 9 second connection section 28 base plate (base)
29 Bulkhead 30 Lower frame (frame)
102 Base plate (base)
104 Lower frame (frame)
117 Partition 170, 172, 174 Heating wire 165 Connection portion 506 First reformer (reformer)
510 Second reformer (reformer)
512 carbon monoxide remover

Claims (6)

A first part having a top surface and a bottom surface, each having a rectangular shape, a second part having a rectangular shape having one side opposite to one side of the first part, the first part, and the second part A third portion having a side along the width direction that is shorter than a length in the width direction along opposite sides of the first portion and the second portion. An integrated member in which the lower surfaces of the first part, the second part, and the third part are flush with each other;
A first frame disposed on an upper surface of the first portion;
A first lid disposed on the opposite side of the side in contact with the first portion of the first frame;
A second frame disposed on the upper surface of the second portion;
A second lid disposed on the opposite side of the side in contact with the second portion of the second frame;
With
At least a part of the high-temperature reaction part that causes the reaction of the reactant is laminated and joined in order of the integrated member, the first frame, and the first lid from below, and the first part, wherein the first frame, the is defined by a first lid, at least a part of the low temperature reaction unit causing a reaction of the reactants at a temperature lower than the high temperature reaction unit, the integrated member from below, the The second frame body and the second lid body are laminated and joined in this order, and are defined by the second part, the second frame body, and the second lid body, and the high temperature reaction part And a connecting portion having a flow path for sending fluid between the low-temperature reaction portion and the upper surface of the third portion, and at least a portion is defined by the third portion, and in the width direction , the length of the connecting portion, Ri length and same der of the third part, the reformer the high temperature reaction unit is for reforming fuel Has, reactor wherein the low temperature reaction unit, characterized in Rukoto which have a carbon monoxide remover for removing carbon monoxide from the reformed gas from the reformer. The reactor according to claim 1,
The reactor is characterized in that the connecting portion is provided at the center in the width direction of the first portion and the second portion. The reactor according to claim 1 or 2,
The connecting portion is
A first connecting portion formed integrally with the integrated member and having a partition wall that partitions the flow path;
A second connecting portion formed integrally with the first and second frame bodies and having a partition wall partitioning a flow path different from the first connecting portion;
A reaction apparatus comprising: In the reaction apparatus according to any one of claims 1 to 3,
A reactor for forming a flow path is provided on the upper surfaces of the first part and the front second part. In the reaction apparatus according to any one of claims 1 to 4,
A heating wire is arranged on the lower surfaces of the first and second parts,
A reaction apparatus for heating the high temperature reaction section and the low temperature reaction section. The reactor according to claim 1 ,
The connecting device has a flow path for supplying fuel to the reformer and a flow path for supplying reformed gas from the reformer to the carbon monoxide remover.

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