JP2007091499A - Reactor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a reactor in which the deformation resisting performance and fracture resisting performance of tubular materials used as gas inflow-outflow can be improved. <P>SOLUTION: The reactor is equipped with: a heat insulation package 200; a high temperature reaction part 4 stored in the heat insulation package 200 and causing the reaction of a reactant; a low temperature reaction part 6 causing the reaction of a reactant at a temperature lower than that in the high temperature reaction part 4; a connection part 8 constructed between the high temperature reaction part 4 and the low temperature reaction part 6 and feeding the reactants and products between the high temperature reaction part 4 and the low temperature reaction part 6; and a plurality of tubular materials 15, 17, 19, 21, 23 connected to the low temperature reaction part 6, further provided so as to pass through the heat insulation package 200, and performing the feed of the reactants to the high temperature reaction part 4 or the low temperature reaction part 6 or performing the exhaust of the products from the high temperature reaction part 4 or the low temperature reaction part 6. Then, the plurality of tubular materials 15, 17, 19, 21, 23 are formed of a material having superelastic effect. <P>COPYRIGHT: (C)2007,JPO&INPIT

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 a clean power source with high energy conversion efficiency. A fuel cell is a device that directly extracts electric energy from chemical energy by electrochemically reacting fuel and oxygen in the atmosphere.

The fuel used in the fuel cell includes hydrogen alone, but there is a problem in handling due to being a gas at normal temperature and pressure as it is. 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, reformed fuel cells that produce hydrogen by reforming liquid fuels that contain hydrogen atoms, such as alcohols, can easily store the fuel in a liquid state and compare the amount of hydrogen per unit volume of fuel. Many. When such a fuel cell is used, a vaporizer that vaporizes liquid fuel, a reformer that extracts hydrogen necessary for power generation by reacting the liquid fuel with high-temperature steam, and a by-product of the reforming reaction. A carbon monoxide remover or the like that removes carbon oxide may be required (see, for example, Patent Document 1).
JP 2002-356310 A

The vaporizer, the carbon monoxide remover, and the reformer operate by being heated. In a reactor equipped with at least one of these, in order to make effective use of thermal energy, the reformer and the carbon monoxide remover are insulated to keep the reactor warm so that part of the thermal energy is not released to the outside. It is preferable. In view of this, the present inventors have housed and sealed these reformers and carbon monoxide removers in a heat-insulating package having a reduced-pressure atmosphere inside. In the heat insulation package, a plurality of tubes for supplying reactants or discharging products are passed through such chemical reactors.
Since the inside of the heat insulation package becomes higher in temperature than the outside of the heat insulation package due to the heat of the chemical reactor, a difference in expansion of these pipe materials due to non-uniform heat occurs inside and outside the heat insulation package. The stress at this time is concentrated particularly in the vicinity of the joint portion of the pipe material, and the pipe material may be distorted, causing a problem that the fluid leaks due to cracking or breakage.
This invention is made | formed in view of the said situation, and it aims at providing the reaction apparatus which can improve the deformation-proof performance and fracture-proof performance of the pipe material used for gas inflow / outflow.

In order to solve the above problems, the invention of claim 1
An insulation package;
A reaction part housed in the heat insulation package and causing a reaction of a reactant;
A plurality of pipes connected to the reaction unit and provided through the heat insulation package, for supplying reactants to the reaction unit or discharging products from the reaction unit, and
At least one of the plurality of pipe materials is formed of a material having a superelastic effect.

Invention of Claim 2 is the reaction apparatus of Claim 1,
The reaction part is supported by the plurality of pipe members in a state of being separated from the heat insulating package.

Invention of Claim 3 is the reaction apparatus of Claim 1 or 2,
The reaction part is
A high-temperature reaction part that causes the reaction of the reactants;
A low-temperature reaction part that causes the reaction of the reactant at a lower temperature than the high-temperature reaction part; and
It is characterized by having.

Invention of Claim 4 is the reaction apparatus of Claim 3,
A connecting part is provided between the high-temperature reaction part and the low-temperature reaction part, and has a connecting part for sending reactants and products between the high-temperature reaction part and the low-temperature reaction part.

Invention of Claim 5 is the reaction apparatus of Claim 3 or 4,
The low-temperature reaction part is supported by the plurality of pipe members in a state of being separated from the heat insulation package.

Invention of Claim 6 is the reaction apparatus as described in any one of Claims 3-5,
The low temperature reaction part has a carbon monoxide removal part.

Invention of Claim 7 is the reaction apparatus as described in any one of Claims 3-6,
The high temperature reaction part has a hydrogen reforming part.

Invention of Claim 8 is the reaction apparatus as described in any one of Claims 1-7,
The inner surface of the plurality of pipe materials is plated.

  According to the reaction apparatus according to the present invention, stress applied to a pipe formed of a material having a superelastic effect can be relaxed, and deformation resistance and fracture resistance can be improved.

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

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

  The microreactor module 1 is a reaction apparatus 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 is a high-temperature reaction in which a relatively high-temperature hydrogen reforming reaction occurs in an appropriate reaction temperature range in a pipe group 2 in which reactants are supplied and products are discharged and a low-temperature reaction unit 6 described later. Reaction product and production between the high temperature reaction part 4 and the low temperature reaction part 6 in which the selective oxidation reaction relatively low with respect to the appropriate reaction temperature range in the high temperature reaction part 4 and the high temperature reaction part 4 occurs. And a connecting pipe 8 for sending inflow or outflow of goods.

  FIG. 4 is a schematic side view when the microreactor module 1 is divided for each function. As shown in FIG. 4, the pipe group 2 is mainly provided with a vaporizer 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. Both the first reformer 506 and the second reformer 510 are reformers that reform hydrogen to produce hydrogen. The first reformer 506 is disposed closer to the low temperature reaction unit 6, the second reformer 510 is disposed at a position farther from the low temperature reaction unit 6 than the first reformer 506, and the second combustor 508 is disposed. Is sandwiched between the first reformer 506 and the second reformer 510 and heats the first reformer 506 and the second reformer 510 so as to be in an appropriate temperature range. One reformer 506, second combustor 508, and second reformer 510 are arranged in this order.

  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. In some cases, unreacted hydrogen gas may be included in the off-gas discharged from the fuel cell after the fuel cell has generated an electrochemical reaction with the hydrogen gas supplied from the microreactor module 1, and the first combustor 504. At least one of the second combustor 508 may generate heat by burning the unreacted hydrogen gas with a gas such as air containing oxygen. Needless to say, at least one of the first combustor 504 and the second combustor 508 is configured so that liquid fuel (for example, methanol, ethanol, butane, dimethyl ether, gasoline, etc.) stored in the fuel container is supplied by another vaporizer. The vaporized fuel may be burned with a gas such as air containing oxygen.

When the second combustor 508 burns off-gas discharged from the fuel cell, first, the first reformer 506 and the second reformer 510 are heated by a heating wire 172, which will be described later, at the time of start-up. When the reactor 506 and the second reformer 510 are heated to the operating temperature, they reform the fuel vaporized by the reforming reaction into hydrogen, and the off-gas containing hydrogen from the fuel cell supplied with the hydrogen Is steadily discharged, the second combustor 508 burns hydrogen in the off-gas and heats the first reformer 506 and the second reformer 510. When the second combustor 508 becomes the main heat source, the heating wire 172 lowers the applied voltage so as to switch to the 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. In the carbon monoxide remover 512, carbon monoxide is selectively oxidized in the air-fuel mixture, whereby a chemical reaction as shown in the following formula (3) occurs, and carbon monoxide is removed.
CO + 1 / 2O ₂ → CO ₂ (3)
An air-fuel mixture mainly composed of hydrogen from which carbon monoxide has been removed is supplied to the fuel electrode of the fuel cell.

  Hereinafter, the specific structure of the pipe group 2, the high temperature reaction part 4, the low temperature reaction part 6, and the connection pipe 8 is demonstrated using FIG. 3, FIG. 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 29 (base portion 28 and base portion 102) to be described later from a cutting line VII-VII in FIG. 3, and FIG. 8 is a cutting line VIII-VIII in FIG. FIG. 9 is a cross-sectional view taken along the plane direction of the base plate 29, and FIG. 9 is a cross-sectional view taken along the plane direction of the base plate 29 from the cutting line IX-IX in FIG.

  As shown in FIGS. 3, 5, and 6, the pipe group 2 includes a liquid fuel introduction pipe 10 made of a metal material such as a superelastic material or stainless steel (SUS304) having excellent corrosion resistance, and a liquid fuel introduction pipe. Combustor plate 12 made of a metal material such as a superelastic material or stainless steel (SUS304) provided so as to surround the liquid fuel introduction pipe 10 at the upper end of 10, and a metal material such as stainless steel (SUS304), 5 pipe members 15, 17, 19, 21, 23 arranged around the liquid fuel introduction pipe 10. The combustor plate 12 is joined to the liquid fuel introduction pipe 10 and the low-temperature reaction section 6 by hard brazing, and the brazing agent includes the highest temperature among the temperatures of the fluid flowing through the liquid fuel introduction pipe 10 and the combustor plate 12. A gold wax containing silver, copper, zinc and cadmium in gold, a wax mainly composed of gold, silver, zinc and nickel, or gold, palladium, Particularly preferred are waxes based on silver. The combustor plate 12 also functions as a flange for joining the liquid fuel introduction pipe 10 to the low temperature reaction unit 6.

  The liquid fuel introduction pipe 10 is provided with a vaporization introduction path 14 that circulates outside the microreactor module 1. The vaporization introduction path 14 is filled with a liquid absorbing material 33 such as a felt material, a ceramic porous material, a fiber material, and a carbon porous material. The liquid-absorbing material 33 absorbs liquid, and the liquid-absorbing material 33 may be obtained by solidifying inorganic fibers or organic fibers with a binder, may be obtained by sintering inorganic powder, and inorganic powder may be bound with a binder. It may be hardened or a mixture of graphite and glassy carbon.

The pipes 15, 17, 19, 21, and 23 are respectively provided with an air introduction path 16, a combustion mixture introduction path 18, an exhaust gas discharge path 20, a combustion mixture introduction path 22, and a hydrogen gas discharge path 24. The pipe members 15, 17, 19, 21, and 23 are joined to the lower surface of the low temperature reaction unit 6 by their flanges, and are connected to the flow paths in the low temperature reaction unit 6.
Further, the liquid fuel introduction pipe 10 and the pipe materials 15, 17, 19, 21, and 23 have a thickness of 0.1 mm or more and 0.2 mm or less, preferably 0.1 mm, in any part. The pipe members 15, 17, 19, 21, 23 all have an inner diameter of 0.4 mm, and the inner diameter of the liquid fuel introduction pipe 10 is sufficiently longer than the inner diameters of the pipe members 15, 17, 19, 21, 23.

The pipe members 15, 17, 19, 21, 23 are made of a superelastic material. A superelastic material is a material that deforms beyond the elastic range of ordinary metal by deforming beyond the elastic range, and has the property that the deformation strain disappears and returns to its original shape when external stress is removed. Yes.
When an external stress exceeding the elastic limit is applied to a normal metal material, an atom dissociates and breaks the bond between the next atom and a bond between the next atom and a bond between the next atom and a specific crystal plane. Occurs. When plastic deformation occurs, the strain returns only to the elastic deformation even if the external stress is removed, and a permanent deformation remains due to the displacement of the atoms.
On the other hand, a superelastic material has a crystal structure called an austenite phase in the absence of external stress. However, when external stress is applied thereto, it transforms into a crystal structure called stress-induced martensite phase and deforms. The transformation from the austenite phase to the stress-induced martensite phase is carried out without breaking the bond, so when the external stress is removed, the energy-unstable martensite phase immediately returns to the original austenite phase, and the original shape Return to. Such a superelastic material has a property (superelastic effect) that even when deformation of 10 times the proportional limit is applied by external stress, the strain disappears when the external stress is removed and no permanent deformation remains.
FIG. 20 shows the characteristics of a material exhibiting superelasticity. Even if the material is deformed by receiving a stress of st1 or more, the amount of strain (deformation amount) decreases as the external stress decreases. Try to restore to the shape of. When this stress is below st2, it becomes the same as the original shape and draws a hysteresis loop. As will be described later, the maximum stress applied to the pipe materials 15, 17, 19, 21, and 23 due to thermal expansion due to the temperature difference between the low-temperature reaction section 6 and the heat insulation package 200 is about 100 MPa. The elastic material only needs to have superelasticity with a maximum value stmax of recoverable stress of 100 MPa (kgf / mm ² ) or more. That is, the pipe materials 15, 17, 19, 21, and 23 need only have a maximum stress stmax that can be restored with respect to the maximum stress applied to the pipe materials 15, 17, 19, 21, and 23.
Specifically, as a material having a superelastic effect, a superelastic alloy containing Ni and Ti (Ni-Ti alloy), in particular, an alloy containing Ni and Ti, and a superelastic alloy further containing chromium (Ni-Ti-Cr). Alloys) and nickel-titanium-copper alloys. Specifically, NT-N (manufactured by Furukawa Techno Material Co., Ltd.) can be used. This material exhibits a superelastic effect when the stress acting on the superelastic material is in the range of 300 to 900 kgf / mm ² , and can be a material that resists deformation and fracture.
Note that some superelastic alloys have chemical characteristics that absorb hydrogen and become brittle, so when such materials are used, the inner surfaces of the pipes 15, 17, 19, 21, 23 are Plating treatment with nickel or gold inert to hydrogen is preferably performed.

The combustor plate 12 is made of a metal material such as stainless steel (SUS304) or a superelastic material like the liquid fuel introduction pipe 10. A through hole 12A is formed at the center of the combustor plate 12, and the liquid fuel introduction pipe 10 is fitted into the through hole 12A, and the liquid fuel introduction pipe 10 and the combustor plate 12 are joined. A partition wall 12 </ b> B is provided on one surface of the combustor plate 12. A part of the partition wall 12B is provided over the entire outer edge of the combustor plate 12, the other part is provided in the radial direction, and the combustor plate 12 is joined to the lower surface of the low temperature reaction section 6. A combustion channel 26 is formed on the joint surface, and the liquid fuel introduction pipe 10 is surrounded by the combustion channel 26. The combustor plate 12 has a wall thickness of 0.1 mm or more and 0.2 mm or less, preferably 0.1 mm, in any part.
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 liquid fuel introduction pipe 10 is filled up to the position of the combustor plate 12.

  As shown in FIGS. 3 and 5, the high-temperature reaction unit 4, the low-temperature reaction unit 6, and the connection pipe 8 use the laminated insulating plate 290 and base plate 29 as a common base. Therefore, the insulating plate 290 is a lower surface common to the high temperature reaction unit 4, the low temperature reaction unit 6, and the connection pipe 8, but the lower surface of the connection pipe 8 is flush with the lower surface of the high temperature reaction unit 4, Furthermore, it is flush with the lower surface of the low temperature reaction part 6.

The base plate 29 includes a base portion 28 serving as a base of the low temperature reaction portion 6, a base portion 102 serving as a base of the high temperature reaction portion 4, and a connection base portion 7 serving as a base of the connection pipe 8. These are integrally formed. In other words, the connection base portion 7 is in a constricted state. The base plate 29 is made of a metal material such as stainless steel (SUS304). The insulating plate 290 includes a base portion 296 serving as a base body for the low temperature reaction portion 6, a base portion 294 serving as a base body for the high temperature reaction portion 4, and a connection base portion 298 serving as a base body for the connection pipe 8. The connection base portion 297 is in a constricted state. The insulating plate 290 is made of an electrical insulator such as ceramic, and is interposed so that the heating wire 170, the heating wire 172, and the heating wire 174 do not conduct to the conductive base plate 29.
The base portion 296 communicates with a through hole 296A for communicating with the liquid fuel introduction pipe 10, a through hole 296B for communicating with the air introduction path 16 of the pipe material 15, and a combustion mixture introduction path 18 of the pipe material 17. A through hole 296B for communicating with the exhaust gas discharge path 20 of the pipe material 19, a through hole 296B for communicating with the combustion mixture introduction path 22 of the pipe material 21, and a hydrogen gas discharge path 24 of the pipe material 23. A through hole 296B for communication and through holes 296C and 296C connected to through holes 53 and 55 of the base plate 29 described later are provided.

The low temperature reaction part 6 is formed by laminating the base part 296, the base part 28, the lower frame 30, the upper frame 34, and the lid plate 36 in this order from the bottom, and has a rectangular parallelepiped shape. The lower frame 30, the upper frame 34, and the lid plate 36 are all made of a metal material such as stainless steel (SUS304), and the thickness of each portion is 0.1 mm or more and 0.2 mm or less, preferably 0.1 mm. It is said that.
The high temperature reaction part 4 covered the base part 294, the base part 102 joined to the base part 294, the reformer base body 104 superimposed on the base part 102, and a part of the reformer base body 104. A first box 110, a second box 112 covering another part of the reformer base body 104, and a combustor plate 106 sandwiched between the first box 110 and the second box 112. , 108 and has a rectangular parallelepiped shape. The reformer base body 104, the first box body 110, the second box body 112, and the combustor plates 106 and 108 are all made of a metal material such as stainless steel (SUS304), and the thickness of each portion is 0. It is set to 1 mm or more and 0.2 mm or less, preferably 0.1 mm.
The connection pipe 8 includes a connection base part 298, a connection base part 7 joined to the connection base part 298, and a connection lid 280 joined to the connection base part 7. The connection lid 280 is made of a metal material such as stainless steel (SUS304), and the thickness of any portion is 0.1 mm or more and 0.2 mm or less, preferably 0.1 mm. By joining the connection base portion 7 so that the connection lid 280 is closed, the reformed fuel supply flow path 38, the mixing flow path 40, the combustion fuel supply flow path 48, and the exhaust gas flow path 50 are formed.

FIG. 10 is a perspective view of a state in which the insulating plate 290 is joined to the base plate 29. As shown in FIGS. 7 and 10, the through holes 51, 52, 53, 54, 55, 56, 58 and 60 penetrate the base portion 28 of the base plate 29. Here, the through hole 52 communicates with the through hole 296A of the base portion 296, the through holes 51, 54, 56, 58, 60 communicate with the respective through holes 296B of the base portion 296, and the through holes 53, 55 The base portion 296 communicates with each through hole 296C.
Therefore, as shown in FIGS. 2, 3, 5 to 7, and 21, the base portion 296 of the insulating plate 290 becomes the lower surface of the low temperature reaction portion 6, and the pipe materials 15, 17, 19 are formed on the lower surface of the low temperature reaction portion 6. , 21 and 23 and the liquid fuel introduction pipe 10 are joined, the vaporization introduction path 14 of the liquid fuel introduction pipe 10 communicates with the through hole 52 through the through hole 296A, and the air introduction path 16 of the pipe member 15 is the through hole 296B. The combustion mixture introduction path 18 of the pipe material 17 communicates with the through hole 58 via the through hole 296B, and the exhaust gas discharge path 20 of the pipe material 19 communicates with the through hole 56 via the through hole 296B. The combustion mixture introduction path 22 of the tube material 21 communicates with the through hole 51 via the through hole 296B, and the hydrogen gas discharge path 24 of the tube material 23 communicates with the through hole 54 via the through hole 296B. 2, 5, 6, and 21, the combustor plate 12 is joined to the lower surface of the low-temperature reaction unit 6, and one end of the combustion flow path 26 of the combustor plate 12 is a through hole 296 </ b> C. The other end of the combustion flow channel 26 communicates with the through hole 55 through the through hole 296C.

  As shown in FIGS. 7 and 10, the base plate 29 has a reformed fuel supply channel 38, a mixing channel 40, a carbon monoxide removing channel 42, and a carbon monoxide removing channel on one surface. The height of the channel 44, the combustion fuel supply channel 47, the combustion fuel supply channel 48, the communication channel 49, and the exhaust gas channel 50 is higher than these grooves so as to be formed. The stage 41 and the stage 43 are provided on the base portion 28 and the base portion 102, respectively.

  The reformed fuel supply channel 38 is formed so as to extend from the through hole 52 of the low temperature reaction part 6 through the connection base part 7 to the corner of the base part 102 of the high temperature reaction part 4. The mixing channel 40 is formed so as to extend from the through hole 60 of the low temperature reaction part 6 through the connection base part 7 to the base part 102 of the high temperature reaction part 4. The combustion fuel supply channel 48 is formed so as to reach the base portion 102 of the high temperature reaction portion 4 from the through hole 58 of the low temperature reaction portion 6 through the connection base portion 7. The exhaust gas flow channel 50 is formed so as to reach from the through hole 56 of the low temperature reaction part 6 to the through hole 55 and from the through hole 56 to the base part 102 of the high temperature reaction part 4 through the connection base part 7. Has been. Here, a connecting lid 280 is joined to the upper side of the connecting base portion 7, and the reforming fuel supply channel 38, the mixing channel 40, the combustion fuel supply channel 48 and the exhaust gas channel 50 are connected by the connecting lid 280. Is covered in the connecting base portion 7.

  The communication channel 49 is formed by a linear groove in the base portion 102. The carbon monoxide removal channel 42 is formed by a rectangular groove in the base portion 28. The carbon monoxide removal channel 46 is formed by a groove having a detour shape so as to surround the through hole 52, and the through hole 54 is open at the bottom of one end of the carbon monoxide removal channel 46. The combustion fuel supply channel 47 is formed by a groove extending from the through hole 51 to the through hole 53 in the base portion 28.

The carbon monoxide removal channel 44 is formed in a serpentine shape in the base portion 28. Here, the four partition walls 45 forming the carbon monoxide removal flow path 44 are provided to stand on the base surface 39 that is one step lower than the stage 41 of the base portion 28. The partition wall 45 is joined to the base surface 39 of the base portion 28 by brazing.
FIG. 11 is a perspective view of a state in which the reformer base body 104, the lower frame 30, and the connecting lid 280 are joined to the base plate 29. As shown in FIG. 11 and the like, the lower portion is placed on the base portion 28 of the base plate 29. Although the frame 30 is joined, the partition wall 45 extends to the height of the upper end of the lower frame 30 inside the lower frame 30, and the meandering carbon monoxide removal channel 44 is blown up to the lower frame 30. Has been.

  As shown in FIGS. 8, 11, and 21, the partition wall 31 is provided on the inner side of the lower frame 30, so that the inner side of the lower frame 30 has a spiral carbon monoxide removal flow path 64, a blow-through hole 66, and a single one. It is divided into a carbon oxide removal channel 44. In the carbon monoxide removal channel 64, a bottom plate 72 is provided. When the lower frame 30 is joined to the base portion 28, that is, when the bottom plate 72 is joined to the stage 41, the carbon monoxide removal channel 46. The combustion fuel supply channel 47 is covered, and a part of each of the reformed fuel supply channel 38, the mixing channel 40, the combustion fuel supply channel 48, and the exhaust gas channel 50 is covered.

Also, one end of the carbon monoxide removal flow path 64 communicates with the carbon monoxide removal flow path 44, and the carbon monoxide removal flow in the base portion 28 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 end of the carbon monoxide removal flow path 46 of the base portion 28 is formed at the other end of the carbon monoxide removal flow path 64. Yes. The blow-through hole 66 is located on the mixing channel 40 of the base portion 28.
In plan view, the liquid fuel introduction pipe 10 overlaps a part of the carbon monoxide removal flow path 64, and the carbon monoxide removal flow path 64 swirls around the liquid fuel introduction pipe 10.

  FIG. 12 is a perspective view of the lower frame 30 with the upper frame 34 joined thereto. As shown in FIGS. 9 and 12, the upper frame 34 is provided with a bottom plate 86 on the lower surface, and a partition wall 35 is provided on the upper surface of the bottom plate 35 and inside the upper frame 34, thereby meandering inside the upper frame 34. A carbon monoxide removal channel 84 is formed. Further, when the upper frame 34 is joined to the lower frame 30, the carbon monoxide removal flow path 64 and the carbon monoxide removal flow path 44 are partitioned by the bottom plate 86. 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 66 of the lower frame 30, and the carbon monoxide removal flow path 84 communicates with the mixing flow path 40 via the blow-through hole 88 and the blow-through hole 66. The blow-through hole 90 is positioned on the end of the carbon monoxide removal flow path 44, and the carbon monoxide removal flow path 84 communicates with the carbon monoxide removal flow path 44 through the blow-through hole 90.

  As shown in FIGS. 1, 3, 5, etc., the cover plate 36 is joined to the upper frame 34, so that the carbon monoxide removal flow path 84 is covered with the cover plate 36. Here, carbon monoxide that selectively oxidizes carbon monoxide is formed on the entire wall surfaces of the carbon monoxide removal channels 42, 44, 46, 64, and 84 including the upper surface of the base surface 39 and the upper and lower surfaces of the bottom plate 86. A selective oxidation catalyst is supported. An example of the catalyst for selective oxidation of carbon monoxide is platinum.

  As shown in FIG. 5 and FIG. 11, the reformer base body 104 has four partition walls 119, 121, 123, and 125 erected on one surface of the bottom plate 117. By joining the other surface of the bottom plate 117 to the base portion 102, the reformed fuel supply flow path 38, the mixing flow path 40, the combustion fuel supply flow path 48, the communication flow path 49, and the exhaust gas in the base portion 102 are joined by the bottom plate 117. The flow path 50 is covered.

  Blow-through holes 114 are formed in the vicinity of the corners of the bottom plate 117, and the blow-through holes 114 are located on the end portions of the reformed fuel supply flow path 38. A blow-through hole 115 is formed in the vicinity of another corner of the bottom plate 117, and the blow-through hole 115 is located on the end of the mixing flow path 40. In the bottom plate 117 between the partition wall 121 and the partition wall 123, a blow-through hole 154 is formed near the partition wall 121, a blow-through hole 155 is formed near the partition wall 123, and the blow-through hole 154 is located on one end portion of the communication channel 49. The blow-through hole 155 is located on the other end of the communication flow path 49, and the blow-through hole 154 and the blow-through hole 155 communicate with each other via the communication flow path 49. Blow-through holes 132 and 134 are formed between the partition wall 121 and the partition wall 123, and the blow-through hole 132 is located on the end of the combustion fuel supply channel 48 and communicates with the combustion fuel supply channel 48. Is located above the end of the exhaust gas flow channel 50 and communicates with the exhaust gas flow channel 50.

  The first box body 110 has a rectangular parallelepiped shape with an open bottom surface. The partition walls 119 and 121 are inserted into the opening of the first box body 110 so that the partition walls 119 and 121 are accommodated in the first box body 110. The opening of one box 110 is closed by a bottom plate 117, and the first box 110 is joined to the bottom plate 117. The partition walls 119 and 121 are joined to the upper surface of the first box body 110, and a meandering reforming flow path 116 is formed inside the first box body 110 by the partition walls 119 and 121. Here, the blow-through hole 114 is at one end of the reforming flow path 116, and the blow-through hole 154 is at the other end of the reforming flow path 116. A reforming catalyst that reforms the fuel to generate hydrogen is supported on the entire wall surface, bottom surface, and ceiling surface of the reforming channel 116. Examples of the reforming catalyst used for reforming methanol include a Cu / ZnO-based catalyst and a Pt / ZnO-based catalyst.

  Thus, the first box 110 covers the partition walls 119, 121 from above and is joined to the bottom plate 117, and the reformer catalyst is provided in the internal space of the first box 110, whereby the first reformer 506 is It is formed.

  The second box body 112 has a rectangular parallelepiped shape with an open bottom surface. The partition walls 123 and 125 are inserted into the opening of the second box body 112 so that the partition walls 123 and 125 are accommodated in the second box body 112. The opening of the second box 112 is closed by the bottom plate 117, and the second box 112 is joined to the bottom plate 117. The partition walls 123 and 125 are joined to the upper surface of the second box body 112, and a meandering reforming flow path 150 is formed inside the second box body 112 by the partition walls 123 and 125. Here, the blow-through hole 155 is at one end of the reforming flow path 150, and the blow-through hole 115 is at the other end of the reforming flow path 150. A reforming catalyst that reforms the fuel to generate hydrogen is supported on the entire wall surface, bottom surface, and ceiling surface of the reforming channel 150. Examples of the reforming catalyst include a Cu / ZnO-based catalyst and a Pt / ZnO-based catalyst.

  In this way, the second box 112 covers the partition walls 123 and 125 from above and is joined to the bottom plate 117, and the reforming catalyst is provided in the internal space of the second box 112, whereby the second reformer 510 is It is formed.

  FIG. 13 is a perspective view of the combustor plates 106 and 108. As shown in FIG. 13, a partition wall 139 is provided on one surface of the combustor plate 106 so as to protrude along the edges excluding the lower edge, and another partition wall 141 extends vertically in the center. Projected. Then, the combustor plate 108 is joined to the partition walls 139 and 141 of the combustor plate 106 to form a combustor box with the combustion chambers 138 and 140 opened at the lower side thereof. However, since the partition wall 141 does not reach the upper edge of the combustor plate 106, the combustion chamber 138 on the right side and the combustion chamber 140 on the left side of the partition wall 141 communicate with each other. Further, as shown in FIGS. 5 and 13, the combustor plates 106 and 108 are joined to the bottom plate 117 of the reformer base body 104 between the first box body 110 and the second box body 112, thereby The lower openings of the chambers 138 and 140 are closed by the bottom plate 117. Here, as shown in FIGS. 8 and 9, the blow-through hole 132 is in the combustion chamber 138, and the blow-through hole 134 is in the combustion chamber 140. A combustion catalyst for burning the combustion mixture is carried on the wall surfaces of the combustion chamber 138 and the combustion chamber 140. An example of the combustion catalyst is platinum.

  Thus, the combustor plates 106 and 108 are joined to the bottom plate so as to close the lower openings of the combustion chambers 138 and 140 formed between the combustor plates 106 and 108, and the combustion catalyst is added to the combustion chambers 138 and 140. Is provided, the second combustor 508 is formed.

  The combustor plate 106 is in close contact with the first box 110, and the combustor plate 108 is in close contact with the second box 112. Therefore, the first reformer 506 and the second reformer 510 are stacked along a direction parallel to the bottom plate 117 of the reformer base body 104 with the second combustor 508 interposed therebetween. The second combustor 508 serves as a heating unit so as to heat the first reformer 506 and the second reformer 510 evenly.

As shown in FIG. 1 and the like, the outer shape of the connecting pipe 8 is a prism, the width of the connecting pipe 8 is narrower than the width of the high temperature reaction part 4 and the low temperature reaction part 6, and the height of the connection pipe 8 is also high temperature reaction. It is lower than any of the height of the 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. The connecting pipe 8 is connected to the high temperature reaction section 4 at the center in the width direction of the high temperature reaction section 4 and at a low temperature. The reaction part 6 is connected to the low temperature reaction part 6 in the center in the width direction.
As described above, the connecting pipe 8 is provided with the reformed fuel supply channel 38, the mixing channel 40, the combustion fuel supply channel 48, and the exhaust gas channel 50.

  The paths of the flow paths provided inside the pipe group 2, the high temperature reaction unit 4, the low temperature reaction unit 6 and the connecting pipe 8 are as shown in FIGS. Here, the correspondence relationship between FIGS. 14, 15, and 4 will be described. The vaporization introduction path 14 corresponds to the flow path of the vaporizer 502, and the reforming flow path 116 serves as the flow path of the first reformer 506. The reforming channel 150 corresponds to the second reformer 510, and the carbon monoxide removing unit 512 extends from the start end of the carbon monoxide removing channel 84 to the end of the carbon monoxide removing channel 46. 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 insulating plate 290, is patterned in such a manner that the heating wire 170 meanders and passes from the low temperature reaction unit 6 through the connecting pipe 8 to the high temperature reaction unit. 4 are patterned in such a manner that the heating wire 172 meanders on their lower surfaces. A heating wire 174 is patterned from the lower surface of the low temperature reaction section 6 through the surface of the combustor plate 12 to the side surface of the liquid fuel introduction pipe 10. The heating wire 170 is a heater for heating the low temperature reaction part 6 to a predetermined appropriate temperature range, the heating wire 172 is a heater for heating the high temperature reaction part 4 to a predetermined appropriate temperature range, and the heating wire 172 is This is a heater for heating the vaporizer 502 to a predetermined appropriate temperature range. Here, an insulating film such as silicon nitride or silicon oxide is formed on the side surface of the liquid fuel introduction pipe 10 and the surface of the combustor plate 12, and a heating wire 174 is formed on the surface of the insulating film. By patterning the heating wires 170, 172, and 174 on the insulating film or insulating plate 290, the voltage to be applied is not applied to the base plate 29 made of a metal material, the liquid fuel introduction pipe 10, the combustor plate 12, etc. The heat generation efficiency of the heating wires 170, 172, and 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 or insulating plate 290 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. For the diffusion prevention layer, it is preferable to use a substance (for example, W) having a relatively high melting point and low reactivity so that the material of the heat generation layer does not diffuse into the diffusion prevention layer or the adhesion layer. The adhesion layer is used when the diffusion preventing layer does not have excellent adhesion to the insulating film or the insulating plate 290, and adheres to both the diffusion preventing layer and the insulating film or the insulating plate 290. It is made of an excellent material (for example, Ta, Mo, Ti, Cr). The heating wire 170 heats the low-temperature reaction unit 6 at startup, the heating wire 172 heats the high-temperature reaction unit 4 and the connecting pipe 8 at startup, and the heating wire 174 is connected to the vaporizer 502 and the first combustion of the pipe group 2. The vessel 504 is heated. Thereafter, off-gas containing hydrogen remaining without being used in the electrochemical reaction is exhausted from the fuel cell that generates power using the hydrogen gas discharged from the microreactor module 1. When this off gas is introduced into the second combustor 508 and combusted, the heating wire 172 heats the high temperature reaction section 4 and the connecting pipe 8 as an auxiliary to the second combustor 508. Similarly, when off-gas containing hydrogen from the fuel cell is burned in the first combustor 504, the heating wire 170 and the heating wire 174 heat the low-temperature reaction unit 6 and the pipe group 2 as assistance of the first combustor 504. .

  Further, since the electric resistances of the heating wires 170, 172, and 174 change according to changes in temperature, they also function as temperature sensors that can read the temperature from a resistance value with respect to a predetermined applied voltage or current. 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 low temperature reaction portion 6, and these end portions are arranged so as to surround the combustor plate 12. Lead wires 176 and 178 are connected to both ends of the heating wire 170, lead wires 180 and 182 are connected to both ends of the heating wire 172, and lead wires 184 and 186 are connected to both ends of the heating wire 174, respectively. Is connected. In FIG. 3, the heating wires 170, 172, 174 and the lead wires 176, 178, 180, 182, 184, 186 are omitted for easy understanding of the drawing.

As shown in FIGS. 16 and 17, the microreactor module 1 includes a heat insulation package 200, 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 case 202 whose bottom surface is open, and a base plate 204 which closes the bottom surface opening of the case 202, and the base plate 204 is joined to the case 202. Both the case 202 and the base plate 204 are made of a metal such as stainless steel (SUS304) having a thickness of about 0.1 mm to 0.2 mm. The heat insulation package 200 suppresses propagation of heat radiation from the pipe group 2, the high temperature reaction unit 4, the low temperature reaction unit 6, and the connecting pipe 8 to the outside of the heat insulation package 200. The internal space between the heat insulation package 200 and the microreactor module 1 is evacuated so that the internal pressure becomes 1 Pa or less. The pipe material 23 of the hydrogen gas discharge path 24 of the pipe group 2 is exposed from the heat insulation package 200 and connected to a fuel electrode of a power generation module 608 described later, and the liquid fuel introduction pipe 10 is fueled via a flow rate control unit 606. The container 604 is connected.
A part of the wiring group 197 having the lead wires 176, 178, 180, 182, 184, 186, 192, 194 is exposed from the heat insulating package 200. In the liquid fuel introduction pipe 10 and the lead wires 176, 178, 180, 182, 184, 186, 192, and 194, outside air enters the heat insulation package 200 from the portions exposed from the heat insulation package 200, and the internal pressure increases. The liquid fuel introduction pipe 10 and the lead wires 176, 178, 180, 182, 184, 186, 192, and 194 are joined to the base plate 204 of the heat insulation package 200 with metal wax, glass material, or insulating sealing material so that no gap is generated. Has been. Since the heat insulating package 200 is metallic, it exhibits conductivity. However, since the lead wires 176, 178, 180, 182, 184, 186, 192, 194 are covered with a high melting point insulator, the lead wires 176, 178, 180, 182, 184, 186, 192, and 194 do not conduct with the heat insulation package 200, respectively. Since the internal pressure of the internal space of the heat insulating package 200 can be kept low, the medium that propagates the heat generated by the microreactor module 1 becomes dilute, and heat convection in the internal space is suppressed, so that the heat retention effect of the microreactor module 1 is increased.
And in the space sealed with the heat insulation package 200, the connecting pipe 8 of a predetermined distance is interposed between the high temperature reaction part 4 and the low temperature reaction part 6 of the microreactor module 1, but the volume of the connecting pipe 8 is Since the volume of the high temperature reaction part 4 and the low temperature reaction part 6 is extremely small, the propagation of heat from the high temperature reaction part 4 to the low temperature reaction part 6 by the connecting pipe 8 is suppressed, and the high temperature reaction part 4 and the low temperature reaction part 6 In the meantime, the thermal gradient required for the reaction can be maintained, the temperature in the high temperature reaction unit 4 can be easily equalized, and the temperature in the low temperature reaction unit 6 can be easily equalized.

  As shown in FIGS. 3 and 5, the surface of the low-temperature reaction unit 6 includes a fluid that can leak from the microreactor module 1 over time, a fluid that is generated from the microreactor module 1 over time, and a box 202 and a base plate 204. By adsorbing factors that increase the pressure in the interior space of the heat insulation package 200 such as a part of the remaining outside air that cannot be sufficiently evacuated at the time of joining, and the outside air that enters the heat insulation package 200 over time, A getter material 188 to be removed from the internal space is provided, and a heater such as an electric heating material is provided in the getter material 188, and a wiring 190 is connected to the heater. Both ends of the wiring 190 are positioned on the lower surface of the base plate 28 around the combustor plate 12, and lead wires 192 and 194 are connected to both ends of the wiring 190, respectively. The getter material 188 is activated by being heated and has an adsorption action. Examples of the material of the getter material 188 include an alloy mainly composed of zirconium, barium, titanium, or vanadium. 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 metal, glass material or insulating sealing material. The wiring group 197 is desirably spaced apart so that the intervals between the lead wires are uniform, and is preferably disposed around the liquid fuel introduction pipe 10.

  In this way, the plurality of through holes 206 penetrate the base plate 204, and the pipe members 15, 17, 19, 21, 23, the liquid fuel introduction pipe 10 and the lead wires 176, 178, 180, 182, 184, 186, 192, 194 Are sealed with metal or glass while being inserted into the respective through holes 206. Although the internal space of the heat insulation package 200 is sealed, since the internal space is depressurized, the heat insulation effect is high. Therefore, heat loss can be suppressed.

  The pipe members 15, 17, 19, 21, 23 and the liquid fuel introduction pipe 10 are in a state of projecting both inside and outside the heat insulating package 200. Therefore, inside the heat insulation package 200, the pipe materials 15, 17, 19, 21, 23 and the liquid fuel introduction pipe 10 are in a state of standing with respect to the base plate 204 as support columns, and the high temperature reaction unit 4, the low temperature reaction unit 6 and the connection The pipe 8 is supported by the pipe materials 15, 17, 19, 21 and 23 and the liquid fuel introduction pipe 10, and the high temperature reaction unit 4, the low temperature reaction unit 6 and the connection pipe 8 are separated from the inner surface of the heat insulation package 200.

The liquid fuel introduction pipe 10 is preferably connected to the lower surface of the low temperature reaction section 6 at the center of gravity of the high temperature reaction section 4, the low temperature reaction section 6 and the connection pipe 8 as viewed in plan.
If the liquid fuel introduction pipe 10, the pipe group 2, and the wiring group 197 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. Although the pipe group 2 and the wiring group 197 are heated to a high temperature, the amount of heat transferred from the liquid fuel introduction pipe 10, the pipe group 2, and the wiring group 197 to the heat insulation package 200 is increased, but the liquid fuel introduction pipe 10, Since the pipe group 2 and the wiring group 197 are provided in the low temperature reaction part 6, the amount of heat transferred from the liquid fuel introduction pipe 10, the pipe group 2 and the wiring group 197 to the heat insulation package 200 and escaped is small, and the liquid fuel introduction pipe 10 The amount of heat dissipated from the exposed portion of the heat insulation package 200 in the pipe group 2 and the wiring group 197 can be reduced.

  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.

  Here, the upper ends of the pipe members 15, 17, 19, 21, and 23 are formed in a flange shape, and the flange portion is fixed to the base plate 296 that contacts the lower surface of the low-temperature reaction unit 6. The base plate 296 is heated to 120 ° C. to 200 ° C., more preferably 140 ° C. to 180 ° C. similarly to the low temperature reaction section 6, the heat insulation package 200 is heated to about 80 ° C., and the base plate 29 and the heat insulation package 200 are several tens of degrees C. Temperature difference occurs. Therefore, the pipe members 15, 17, 19, 21, and 23 provided around the liquid fuel introduction pipe 10 in a regular pentagon shape are portions between the connection portion with the base plate 29 and the contact portion with the base plate 204. That is, stress (for example, about 100 MPa) due to thermal expansion is applied to the portion accommodated in the heat insulating package 200. And although this pipe produces a deformation in the pipes 15, 17, 19, 21, 23, as described above, the pipes 15, 17, 19, 21, 23 are made of a material having a superelastic effect. Even if it is deformed, it returns to its original shape and does not bend. Since the liquid fuel introduction pipe 10 has a pipe diameter longer than that of the pipe materials 15, 17, 19, 21, and 23, the liquid fuel introduction pipe 10 is more resistant to stress than the pipe materials 15, 17, 19, 21, and 23. Similarly to the pipe materials 15, 17, 19, 21, and 23, they may be formed of a superelastic material so that fluid does not leak due to the distortion of the above. Similarly, the wiring group 197 may have a wiring axis made of a super elastic material.

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. As a result, factors that increase the pressure of gas or the like in the heat insulation package 200 are adsorbed by the getter material 188, the degree of decompression 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 portion of the liquid fuel introduction pipe 10 is heated. Since the liquid fuel introduction pipe 10, the high temperature reaction section 4, the low temperature reaction section 6 and the connection pipe 8 are made of a metal material, heat conduction is easy between them. In addition, the current and voltage of the heating wires 170, 172, and 174 are measured by the control device, whereby the temperatures of the liquid fuel introduction pipe 10, the high temperature reaction unit 4 and the low temperature reaction unit 6 are measured, and the measured temperature is transferred to the control device. The voltage of the heating wires 170, 172, 174 is controlled by the control device, and the temperature of the liquid fuel introduction pipe 10, the high temperature reaction unit 4 and the low temperature reaction unit 6 is thereby controlled.

  In a state where the liquid fuel introduction pipe 10, the high temperature reaction section 4 and the low temperature reaction section 6 are heated by the heating wires 170, 172, 174, the liquid mixture of liquid fuel and water is continuously supplied to the vaporization introduction path 14 by a pump or the like. When intermittently 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. Then, the mixed liquid is heated and vaporized in the liquid absorbing material 33, and the mixture of fuel and water evaporates from the liquid absorbing material 33. The porous liquid absorbing material 33 is vaporized from a large number of fine liquid surfaces partitioned by fine holes. For this reason, since each hole has only a small amount of liquid mixture, even if an excessive amount of heat is applied, it can be vaporized quantitatively and stably without bumping.

  The air-fuel mixture evaporated from the liquid absorbing material 33 flows into the first reformer 506 (reforming channel 116) through the through hole 52, the reformed fuel supply channel 38, and the blow-through hole 114. Thereafter, the air-fuel mixture flows into the second reformer 510 (reforming channel 150) through the blow-through hole 154, the communication flow path 49, and the blow-through hole 155. When the air-fuel mixture flows through the reforming channels 116 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, the above chemical reaction). (See equations (1) and (2).)

  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 flows into the mixing channel 40 through the blow-through hole 115. . On the other hand, air is supplied to the air introduction path 16 by a pump or the like and flows into the mixing flow path 40 through the through hole 60, and the air-fuel mixture such as hydrogen gas and air are mixed.

  Then, an air-fuel mixture containing air, hydrogen gas, carbon monoxide gas, carbon dioxide gas and the like passes from the mixing flow path 40 through the blow-through holes 66 and 88 to remove the carbon monoxide remover 512 (from the carbon monoxide removal flow path 84. Into the carbon monoxide removal channel 46). The air-fuel mixture is removed from the carbon monoxide removal flow path 84 via the carbon monoxide removal flow path 44 and the carbon monoxide removal flow path 64 (including the carbon monoxide removal flow path 42). When flowing into the use channel 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 increases in the downstream (mainly from the carbon monoxide removal flow path 64 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 64 to the carbon monoxide removal channel 46. Since the liquid fuel introduction pipe 10 is located under this portion, the heat by the oxidation reaction of the carbon monoxide gas is efficiently used for the heat of vaporization of water and fuel.

  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 an electrochemical reaction of hydrogen gas, and off-gas containing unreacted hydrogen gas and the like is discharged from the fuel cell.

  The above operation is an initial operation, but the liquid mixture is continuously supplied to the vaporization introduction path 14 after that. Then, oxygen (may be 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 through the through hole 51, the combustion fuel supply channel 47, and the through hole 53, and the combustion mixture flows into the catalyst in the combustion channel 26. Burn. As a result, combustion heat is generated. However, since the combustion channel 26 circulates around the liquid fuel introduction pipe 10 below the low temperature reaction section 6, the liquid fuel introduction pipe 10, that is, the vaporizer 502 is heated by the combustion heat. At the same time, the low temperature reaction part 6 is heated. 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 through the through hole 58, the combustion fuel supply channel 48, and the blow-through hole 132, and the combustion mixture becomes the combustion chambers 138 and 140. The catalyst is combusted. As a result, combustion heat is generated. However, since the first reformer 506 and the second reformer 510 are arranged on both sides of the combustion chambers 138 and 140, the first reformer 506 and the second reformer are generated by the combustion heat. The vessel 510 is heated. Therefore, the power consumption of the heating wire 172 can be reduced and the energy utilization efficiency is increased. Here, since the high temperature reaction unit 4 must be kept at a higher temperature than the low temperature reaction unit 6, the amount of off-gas hydrogen supply per unit time in the second combustor 508 is set to be equal to the unit time in the first combustor 504. Or the supply amount of oxygen (air) as a refrigerant in the first combustor 504 per unit time is supplied to the second combustor 508 to supply oxygen (air) per unit time. You may make it more than quantity.
Alternatively, the liquid fuel stored in the fuel container 604 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 path 14 and the combustion mixture is supplied to the combustion mixture introduction paths 18 and 22, the controller controls the variable resistance values of the heating wires 170, 172 and 174. While controlling 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 high temperature reaction unit 4, the low temperature reaction unit 6 and the pipe group 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. to Temperature control is performed so that it may become 180 degreeC. More specifically, the line L1 located in the vicinity of the base part 296 of the low temperature reaction part 6 in FIG. 21 is 150 ° C., the line L2 located at the upper end of the liquid absorbent 33 is 120 ° C., and the line on the outer surface position of the base plate 204. It is preferable that the temperature distribution is such that L3 is 80 ° C. and the line L4 located below the liquid absorbing material 33 is 65 ° C.
That is, while keeping the inside of the heat insulation package 200 at a high temperature, the liquid fuel introduction pipe 10, the pipe group 2, and the wiring group 197 exposed from the heat insulation package 200 are reacted at a high temperature in order to suppress the amount of heat radiated to the outside of the heat insulation package 200. It is provided not on the part 4 side but on the low temperature reaction part 6 side. Further, the combustion heat of the first combustor 504 propagates to the liquid fuel introduction pipe 10, and the temperature gradually increases as the liquid absorbing material 33 in the vaporization introduction path 14 moves from the bottom to the top. The first combustor 504 is disposed only around the upper part of the liquid absorbing material 33 so that it can be vaporized.

  As shown in FIG. 18, the microreactor module 1 as described above can be used by being assembled in the power generation unit 601. The power generation unit 601 includes a frame 602, a fuel container 604 that can be attached to and detached from the frame 602, a flow rate control unit 606 having a flow path, a pump, a flow rate sensor, a valve, and the like, and a state in which the heat generation unit 601 is accommodated in the heat insulation package 200. A microreactor module 1, a power generation cell 608 having a fuel cell, a humidifier, a recovery device, and the like, an air pump 610, and a power supply unit 612 having a secondary battery, a DC-DC converter, an external interface, and the like are provided. 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 gas is generated as described above, and the hydrogen gas is supplied to the fuel cell of the power generation cell 608. The generated electricity is stored in the secondary battery of the power supply unit 612.

  FIG. 19 is a perspective view of an electronic device 701 using the power generation unit 601 as a power source. As shown in FIG. 19, the electronic device 701 is a portable electronic device, and in particular 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 hinged, and are formed so that the upper casing 708 can be folded with the liquid crystal display 706 facing the keyboard 702 with the upper casing 708 overlapped with the lower casing 704. . 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, since the plurality of pipe members 15, 17, 19, 21, 23 are formed of a material having a superelastic effect, the temperature between the low temperature reaction part 6 and the heat insulation package 200 is determined. Due to the thermal expansion due to the difference, stress is applied to the relatively thin pipe materials 15, 17, 19, 21, and 23, and between the connection portion of the low temperature reaction portion 6 with the base plate 296 and the contact portion of the heat insulation package 200 with the base plate 204. Although deformation occurs, the original shape is restored by removing the stress by itself. Therefore, the deformation resistance performance and the fracture resistance performance of the pipe materials 15, 17, 19, 21, 23 can be improved.
Further, among the pipe materials 15, 17, 19, 21, 23, the inner surface of the pipe containing hydrogen in the flowing fluid is plated, so that it is possible to suppress embrittlement by absorbing hydrogen. it can.

  The reformer 506, the combustor 508, and the reformer 510 are stacked in a direction parallel to the bottom plate 117 of the reformer base body 104, and the box bodies 110 and 112 and the combustor plates 106 and 108 are joined to the bottom plate 117. Therefore, it is not necessary to join the box bodies 110, 112 or the box bodies 110, 112 and the combustor plates 106, 108, and the joining surface can be reduced. Therefore, it is possible to provide a reaction apparatus in which internal reactants and products do not leak.

  Further, the reformer base body 104 is joined on the base portion 102 of the base plate 29, and the carbon monoxide remover 512 is provided on another base portion 28 of the base plate 29. 506, second reformer 510, second combustor 508, and carbon monoxide remover 512 are shared as a base plate 29. Therefore, the number of parts of the microreactor module 1 is reduced by the amount related to the sharing, and the joining process between the reformers 507 and 510 and the carbon monoxide remover 512 is not required, so that the manufacturing process of the microreactor module 1 is simplified. Can be achieved.

  Further, the reformers 506, 510 are provided by covering the box bodies 110, 112 on the partition walls 119, 121, 123, 125 standing on the bottom plate 117 of the reformer base body 104, so that the reformers 506. When the flow path is formed inside 510, it is not necessary to provide a partition wall in the boxes 110 and 112. Therefore, the joining surfaces of the reformers 506 and 510 are reduced, and when joining the bottom plate 117 and the boxes 110 and 112, a joining process for joining the partition walls becomes unnecessary. 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 pipe 8. 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 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 difference between the appropriate temperature of the high-temperature reaction unit 4 and the appropriate temperature of the low-temperature reaction unit 6 can be maintained, heat loss of the high-temperature reaction unit 4 can be suppressed, and the temperature of the low-temperature reaction unit 6 rises to a set temperature or higher. It can also 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, an appropriate temperature difference can be generated between the high temperature reaction unit 4 and the low temperature reaction unit 6.

  Further, since the flow paths 38, 40, 48, 50 passing between the low temperature reaction part 6 and the high temperature reaction part 4 are combined into one connecting pipe 8, the stress generated in the connecting pipe 8 or 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.

  The pipes 15, 17, 19, 21, 23, the liquid fuel introduction pipe 10, and the lead wires 176, 178, 180, 182, 184, 186, 192, 194 extend to the outside of the heat insulation package 200. It is connected to the low temperature reaction part 6. Therefore, direct heat transfer from the high temperature reaction unit 4 to the outside of the heat insulation package 200 can be suppressed, and heat loss of the high temperature reaction unit 4 can be suppressed. Therefore, even when the high temperature reaction unit 4 and the low temperature reaction unit 6 are accommodated in one heat insulating package 200, a temperature difference can be generated between the high temperature reaction unit 4 and the low temperature reaction unit 6.

  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 liquid fuel introduction pipe 10 is filled with the liquid absorbing material 33 and the vaporization introduction path 14 is used as the vaporizer 502, the microreactor module 1 can be reduced in size and simplified while mixing. A temperature state necessary for vaporization of the liquid (a state where the upper portion of the vaporization introduction path 14 is 120 ° C.) can be obtained.

  Further, the combustor plate 12 is provided around the liquid fuel introduction pipe 10 at the upper end portion of the liquid fuel introduction pipe 10, and the liquid absorbing material 33 in the vaporization introduction path 14 is 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 pipe group 2, the high temperature reaction part 4, the low temperature reaction part 6 and the connecting pipe 8, the partition walls partitioning the flow path are made thin, so that these heat capacities can be reduced, and in the initial stage of operation The pipe group 2, the high temperature reaction part 4, the low temperature reaction part 6 and the connecting pipe 8 can be immediately warmed from room temperature to high temperature. Furthermore, the power consumption of the heating wires 170, 172, and 174 can be reduced.

  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.

In the said embodiment, the number of pipe materials is not limited to the above-mentioned number, It can change suitably. Furthermore, even if all the pipe materials 15, 17, 19, 21, and 23 are not formed of a material having superelasticity, at least one of them may be formed of a material having superelasticity. Especially when the flow rate of the fluid flowing through each pipe material is different, the pipe material with a high flow rate has a long diameter and is resistant to stress, and the pipe material with a low flow rate has a short diameter and insufficient resistance to stress. In this case, only a tube having a short diameter may be formed of a superelastic material, or only a tube having a wall thickness thinner than that of a tube having a large thickness may be formed of a superelastic material.
Moreover, in the said embodiment, although the 2nd combustor 508 was provided by joining the combustor plate 106,108 to the baseplate 117, the box body which the downward opening was provided previously, and the box body is used as the 1st reformer. The lower opening of the box may be closed by the bottom plate 117 by joining to the bottom plate 117 between 506 and the second reformer 510. In this case, the inside of the box serves as a combustion chamber. However, the combustion chamber may be divided into two or more by a partition, and a through hole may be formed in the partition.

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. 6 is a perspective view of a state in which a base plate 29 is joined to an insulating plate 290. FIG. 3 is a perspective view of a state in which a reformer base body 104 and a lower frame 30 are joined to a base plate 29. FIG. 3 is a perspective view of a state in which a box body 110 and the like are joined to the reformer base body 104 and an upper frame 34 is joined to the lower frame 30. FIG. 3 is an exploded perspective view of a second combustor 508. FIG. It is drawing which showed the path | route after supplying liquid fuel and water until the hydrogen 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. 3 is a perspective view of a power generation unit 601. FIG. 2 is a perspective view of an electronic device 701. FIG. It is the figure which showed the characteristic of the material which has a superelastic effect. It is arrow sectional drawing of the surface along the cutting line XXI-XXI of FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Microreactor module 4 High temperature reaction part 6 Low temperature reaction part 8 Connection pipe 15,19,21,23 Pipe material 200 Thermal insulation package

Claims (8)

An insulation package;
A reaction part housed in the heat insulation package and causing a reaction of a reactant;
A plurality of pipes connected to the reaction unit and provided through the heat insulation package, for supplying reactants to the reaction unit or discharging products from the reaction unit, and
At least one of the plurality of pipe members is formed of a material having a superelastic effect.   The reaction apparatus according to claim 1, wherein the reaction unit is supported by the plurality of pipe members in a state of being separated from the heat insulation package. The reaction part is
A high-temperature reaction part that causes the reaction of the reactants;
A low-temperature reaction part that causes the reaction of the reactant at a lower temperature than the high-temperature reaction part; and
The reaction apparatus according to claim 1, wherein: A connecting part that is installed between the high-temperature reaction part and the low-temperature reaction part, and sends reactants and products between the high-temperature reaction part and the low-temperature reaction part;
The reaction apparatus according to claim 3, wherein   The reaction apparatus according to claim 3 or 4, wherein the low-temperature reaction part is supported by the plurality of pipe members in a state of being separated from the heat insulation package.   The reaction apparatus according to any one of claims 3 to 5, wherein the low-temperature reaction unit includes a carbon monoxide removal unit.   The reaction apparatus according to any one of claims 3 to 6, wherein the high-temperature reaction section includes a hydrogen reforming section. The reaction apparatus according to any one of claims 1 to 7, wherein an inner surface of the plurality of pipe materials is plated.

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