JP2008063177A - Reactor, power generator, electronic equipment and method for fixing catalyst - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To restrain combustion fuel such as hydrogen from burning locally. <P>SOLUTION: A micro reactor 1 is constituted so that substrates 30, 40, 50 are laminated and joined each other. Reforming passages 34, 44 are formed respectively on the substrates 30, 40, and a reforming reaction is caused at the reforming passages 34, 44. A burning passage 54 is formed on the substrate 50, and hydrogen is catalytically burned at the burning passage 54. A catalyst 57 for combustion is fixed in the burning passage 54. The catalyst 57 for combustion is obtained by depositing a catalyst composition 57b containing platinum as an active component on a carrier body 57a. The carrier body 57b is formed into a film-like shape and the catalyst compositions 57b are dotted on the film-like carrier body at predetermined intervals. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a reaction device having a processor that generates heat and a combustor overlaid on the processor, a power generation device including the reaction device, and an electronic device including the power generation device, and a catalyst in the combustor. The present invention relates to a catalyst fixing method for fixing.

  A fuel cell takes out electric power by the electrochemical reaction of a fuel, and research and development of a fuel cell are widely performed. The fuel used in the fuel cell is hydrogen gas, and the hydrogen gas is generated by reforming raw fuel such as methanol with a reformer. Further, in order to increase the energy utilization efficiency, unreacted hydrogen gas discharged from the fuel cell is burned in a combustor, and the reformer is heated by the combustion heat.

FIG. 16 schematically shows the configuration of a conventional combustor. FIG. 16A is a partial cross-sectional view of a conventional combustor, and FIG. 16B is a plan view of a combustion path in the combustor.
As shown in FIG. 16A, a combustion path 501 is formed inside the combustor 500, and a catalyst 502 such as platinum is fixed to the combustion path 501. When hydrogen, oxygen, or the like flows through the combustion path 501, the hydrogen burns to generate combustion heat, and the reaction rate is very fast. In order to fix the catalyst 502 to the combustion path 501, a method of applying slurry to the combustion path 501 with a coating member such as a brush, a dip coating method, or a spin coating method is generally used.

A catalyst is also used in a fuel cell, and there is a method using an ink jet method as a method of applying the catalyst (Patent Document 1). If the method described in Patent Document 1 is applied to a method for applying a catalyst in a combustor, the catalyst 502 can be fixed in the combustion path 501.
JP 2005-267916 A

However, when the dip coating method or the like is used, the peripheral portion 503 of the catalyst 502 becomes thick as shown in FIG. 16 (b) due to a step on the side wall surface of the combustion path 501, and hydrogen is combusted locally in that portion. Resulting in. As a result, there is a portion that locally becomes hot. Even in the method using the ink jet method, since the catalyst droplets are further ejected between the droplets of the impacted catalyst, the thickness does not become uniform due to the bleeding of the droplets and the like. The phenomenon that becomes high temperature occurs. For this reason, the combustion path may be thermally destroyed.
Therefore, the present invention has been made to solve the above-described problems, and an object of the present invention is to suppress local combustion of combustion fuel such as hydrogen.

  In order to solve the above-mentioned problems, the invention according to claim 1 is a reactor in which a heat generating device that absorbs heat, a combustor that is superimposed on the processing device and that forms a combustion path through which combustion fuel and oxidant flow are formed. The catalyst composition as the active component is fixed to the wall surface of the combustion path at intervals.

  The invention according to claim 2 is the reactor according to claim 1, wherein the amount per unit area of the catalyst composition at a certain position of the combustion path corresponds to the endothermic amount to the processor at that position. It is characterized by.

  The invention according to claim 3 is the reactor according to claim 1, wherein the catalyst composition is dotted and scattered on the wall surface of the combustion path, and the catalyst composition at a certain position of the combustion path. The dot density corresponds to the heat absorption amount to the processor at that position.

  According to a fourth aspect of the present invention, in the reaction apparatus according to any one of the first to third aspects, a support is formed in a film shape on the wall surface of the combustion path, and the catalyst composition is applied to the support. It is supported.

  According to a fifth aspect of the present invention, there is provided the reaction apparatus according to the first aspect, wherein the carrier is spotted in the form of dots on the wall surface of the combustion path, and the catalyst composition is carried on the carrier, thereby the catalyst. The composition is dotted in the form of dots, and the dot density of the catalyst composition at a certain position in the combustion path corresponds to the amount of heat absorbed by the processor at that position.

  An invention according to claim 6 is a power generation apparatus, comprising: the reaction apparatus according to any one of claims 1 to 5; and a power generation cell that generates electric power using fuel generated by the reaction apparatus. To do.

  According to a seventh aspect of the present invention, there is provided an electronic device comprising: the power generation device according to the sixth aspect; and an electronic device main body that operates by electricity generated by the power generation device.

  The invention according to claim 8 is the catalyst fixing method, wherein a catalyst composition as an active component is provided in a reaction apparatus in which a heat generating endothermic processor is overlapped with a combustor in which a combustion path in which a combustion fuel and an oxidant flow are formed. And fixing to the wall surface of the combustion path at intervals.

  The invention according to claim 9 is the catalyst fixing method according to claim 8, wherein the amount per unit area of the catalyst composition at a certain position of the combustion path corresponds to the heat absorption amount to the processor at the position. The catalyst composition is distributed such that the catalyst composition is distributed.

  The invention according to claim 10 is the catalyst fixing method according to claim 8, wherein the catalyst composition is dotted on the wall surface of the combustion path in the form of dots, and the catalyst composition at a certain position of the combustion path is formed. The catalyst composition is distributed so that the dot density corresponds to the amount of heat absorbed by the processor at that position.

  The invention according to claim 11 is the catalyst fixing method according to any one of claims 8 to 10, wherein the catalyst composition is formed on the wall surface of the combustion path in the form of a film and then the catalyst composition is loaded on the wall. It is characterized by being carried on the body.

  The invention according to claim 12 is the catalyst fixing method according to claim 8, wherein the carrier is spotted in the form of dots on the wall surface of the combustion path, and the catalyst composition is applied so as to cover the carrier. The catalyst composition is scattered in a dot shape by removing the catalyst composition except for the catalyst composition supported on the carrier.

  A thirteenth aspect of the present invention is the catalyst fixing method according to the twelfth aspect of the present invention, wherein a sol-like support is spotted in the form of dots on the wall surface of the combustion path, and the catalyst composition is contained after the support is dried. The carrier is coated by applying a slurry.

  The invention according to claim 14 is the catalyst fixing method according to claim 12, in which a sol-like carrier is spotted in the form of dots on the wall surface of the combustion path, and a powdery catalyst composition is formed before the carrier is dried. The carrier is coated by applying an object.

  The invention according to claim 15 is the catalyst fixing method according to any one of claims 12 to 14, wherein the dot density of the catalyst composition at a certain position of the combustion path is supplied to the processor at the position. The catalyst composition is distributed so as to correspond to an endothermic amount.

  According to the present invention, since the catalyst composition is fixed to the wall surface of the combustion path at intervals, the catalyst composition does not agglomerate and the combustion fuel does not burn locally but locally becomes high temperature. There is nothing.

  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 block diagram showing a power generation apparatus 900 to which the present invention is applied together with an electronic apparatus main body 1000. The power generation device 900 is provided in a notebook personal computer, a mobile phone, a PDA (Personal Digital Assistant), an electronic notebook, a wristwatch, a digital still camera, a digital video camera, a game device, a game machine, and other electronic devices. Yes, it is used as a power source for operating the electronic device main body 1000.

  The power generation device 900 converts the fuel cartridge 901, the vaporizer 902, the micro reactor (reactor) 1, the fuel cell type power generation cell 903, and the electric energy generated by the power generation cell 903 into an appropriate voltage. A DC / DC converter 904, a secondary battery 905 connected to the DC / DC converter 904, and a control unit 906 for controlling them are provided. The fuel cartridge 901 stores fuel such as methanol, ethanol, butane, and dimethyl ether and water separately or in a mixed state. The fuel and water in the fuel cartridge 901 are supplied to the vaporizer 902 by a micro pump (not shown), and the fuel and water are vaporized by the vaporizer 902.

  The micro reactor 1 includes a reformer 2 that generates an endothermic reaction, a CO remover 3 that generates an exothermic reaction, and a combustor 4 that generates an exothermic reaction.

The fuel and water vaporized by the vaporizer 902 flow into the reformer 2 of the micro reactor 1. In the reformer 2, the fuel and water undergo a reforming reaction by the reforming catalyst to generate hydrogen gas and a small amount of carbon monoxide gas (when the fuel is methanol, the following chemical formula (1) ), See (2)). Hydrogen gas or the like generated by the reformer 2 is sent to the CO remover 3, and external air (oxidant) (air contains oxygen as an oxidant) is further removed by the CO remover 3. Sent to. In the CO remover 3, a selective oxidation reaction in which the carbon monoxide gas is preferentially oxidized by the selective oxidation catalyst occurs, and the carbon monoxide gas is removed (see the following chemical formula (3)). Hydrogen gas or the like that has passed through the CO remover 3 is supplied to the fuel electrode of the power generation cell 903, and air is supplied to the oxygen electrode of the power generation cell 903.
CH ₃ OH + H ₂ O → 3H ₂ + CO ₂ (1)
H ₂ + CO ₂ → H ₂ O + CO (2)
2CO + O ₂ → 2CO ₂ (3)

The power generation cell 903 includes a fuel electrode, an oxygen electrode, and an electrolyte membrane sandwiched between the fuel electrode and the oxygen electrode. The hydrogen in the gas sent to the fuel electrode and the oxygen in the air sent to the oxygen electrode undergo an electrochemical reaction through the electrolyte membrane, whereby electric power is generated in the power generation cell 903. When the electrolyte membrane is a hydrogen ion permeable electrolyte membrane (for example, a solid polymer electrolyte membrane), a reaction such as the following equation (4) occurs in the fuel electrode, and the hydrogen ions generated in the fuel electrode are A reaction such as the following formula (5) occurs at the oxygen electrode through the electrolyte membrane.
H ₂ → 2H ⁺ + 2e ⁻ (4)
2H ⁺ + 1 / 2O ₂ + 2e ⁻ → H ₂ O (5)

  Here, it is more efficient that the hydrogen gas supplied to the fuel electrode of the power generation cell 903 does not react, and the remaining hydrogen gas is supplied to the combustor 4. In addition to hydrogen gas, air (air contains oxygen as an oxidizing agent) is also supplied to the combustor 4. The hydrogen gas supplied to the combustor 4 is combustion fuel, and the hydrogen gas is oxidized by the combustion catalyst in the combustor 4 to generate combustion heat. The difference between the heat generated in the combustor 4 and the heat that maintains the carbon monoxide removal reaction at a predetermined temperature in the CO remover 3 is used for the reaction in the reformer 2, thereby the reformer 2 and the CO remover 3. Operates at a predetermined temperature. For example, the reformer 2 operates at 300 ° C., and the CO remover 3 operates at 100 ° C.

The DC / DC converter 904 has a function of supplying electric energy generated by the power generation cell 903 to an appropriate voltage after being converted into an appropriate voltage. Further, the DC / DC converter 904 charges the secondary battery 905 with the electric energy generated by the power generation cell 903, and is stored in the secondary battery 905 when the power generation cell 903, the micro reactor 1, etc. are not operating. The function of supplying the electric energy to the electronic device main body 1000 can also be fulfilled. The control unit 906 controls the DC / DC converter 904 and the like in addition to the pumps, valves and heaters (not shown) necessary for operating the vaporizer 902, the microreactor 1, and the power generation cell 903. Control is performed to stably supply electric energy.
In addition, in FIG. 1, the reaction material and product are shown about the case where methanol is used as a fuel.

FIG. 2 is a cross-sectional view of the microreaction apparatus 1.
As shown in FIG. 2, the reactor main body 11 of the micro reactor 1 is accommodated in a heat insulating package 12. A plurality of tubes 14 pass through the heat insulating package 12 and are connected to the reactor main body 11. A plurality of lead wires 13 are routed through the heat insulating package 12 to the reactor main body 11. A portion where the tube 14 and the lead wire 13 penetrate the heat insulating package 12 is hermetically sealed with a low melting point glass sealant. The tube 14 is made of glass, and the tube 14 and the heat insulation package 12 are made of the same material.

  The heat insulating package 12 is obtained by bonding the glass containers 21 and 22 with a low-melting-point glass sealing agent with the openings of the two bottomed box-shaped glass containers 21 and 22 facing each other. Therefore, the heat insulation package 12 is a box having a sealed hollow inside. The sealed space of the heat insulation package 12 is evacuated and is in a vacuum state. An infrared reflection film (not shown) is formed on the inner wall surface of the heat insulation package 12. The infrared reflection film is a film in which a Cr film formed by sputtering is used as a base, and an Au film formed by sputtering is laminated on the Cr film. A getter pump (not shown) is provided in the heat insulation package 12, and the getter material of the getter pump is activated by high frequency induction heating or the like, so that the adsorbed gas generated from the wall surface during high temperature operation is adsorbed on the getter material, and the heat insulation package 12 The degree of vacuum inside is maintained. The heat insulation package 12 may not be made of glass, and may be made of metal or ceramic, for example. The infrared reflective film need not be a laminate of Cr and Au as long as the infrared reflectance is higher than that of the heat insulating package 12, and may be another metal film such as Ag or Al.

  The reactor main body 11 is formed by laminating three substrates 30, 40 and 50 and bonding them. The substrates 30, 40, and 50 are glass substrates containing an alkali metal (Na, Li, etc.). For example, the substrates 30, 40, and 50 are substrates made of Pyrex (registered trademark) glass. A metal film (not shown) is interposed between the substrate 30 and the substrate 40, and the substrate 30 and the substrate 40 are anodically bonded by the metal film. Similarly, a metal film (not shown) is interposed between the substrate 40 and the substrate 50, and the substrate 40 and the substrate 50 are anodically bonded by the metal film.

  FIG. 3 is a cross-sectional view taken along the line III-III in FIG. As shown in FIG. 3, a notch 30 a is formed at one corner of the substrate 30. A rectangular through hole 31 is formed in the substrate 30. A groove 32 is formed in the lower surface of the substrate 30, that is, on the bonding surface with the substrate 40. The groove 32 communicates with the fuel introduction path 33 extending from the right edge of the substrate 30 to the left side of the through hole 31, and the end 33 a of the fuel introduction path 33, and at the left side of the through hole 31, the reforming path 34 has a twisted shape. A CO removal air introduction path 35 into which air that is an oxidant of the carbon monoxide removal reaction is introduced from the end 34a of the reforming path 34 to the right edge of the substrate 30, and a CO removal air introduction path 35. And a twisted carbon monoxide removal path 36 that branches from the mixing portion 35 a of the air and the reformed gas reformed by the reformer 34 and reaches the right edge of the substrate 30.

  As shown in FIG. 2, a reforming catalyst 37 is fixed on the wall surface of the reforming path 34. The reforming catalyst 37 is supported by coating the wall surface of the reforming path 34 with a catalyst dispersion in which a catalyst composition (for example, Cu / ZnO-based catalyst composition) is dispersed in a solvent, or a sol-gel. For example, an oxide (for example, alumina) deposited on the wall surface of the reforming path 34 by a method or the like may be supported by coating a catalyst dispersion.

  A selective oxidation catalyst 38 is fixed on the wall surface of the carbon monoxide removal path 36. The selective oxidation catalyst 38 is supported by coating the wall surface of the carbon monoxide removal path 36 with a catalyst dispersion in which a catalyst composition (for example, platinum-based catalyst composition) is dispersed in a solvent, or a sol-gel. For example, an oxide (for example, alumina) formed on the wall surface of the carbon monoxide removal path 36 by a method or the like may be supported by coating a catalyst dispersion.

  FIG. 4 is a cross-sectional view taken along the line IV-IV in FIG. As shown in FIG. 4, a rectangular through hole 41 facing the through hole 31 is formed in the substrate 40. A groove 42 is formed in the upper surface of the substrate 40, that is, on the bonding surface with the substrate 30. The groove 42 includes a fuel introduction path 43 that faces the fuel introduction path 33, a reforming path 44 that faces the reforming path 34, a CO removal air introduction path 45 that faces the CO removal air introduction path 35, and one It consists of a carbon monoxide removal path 46 opposite to the carbon oxide removal path 36. As shown in FIG. 2, the reforming catalyst 47 is fixed on the wall surface of the reforming path 44, and the selective oxidation catalyst 48 is fixed on the wall surface of the carbon monoxide removal path 36.

  By joining the substrate 30 and the substrate 40, the fuel introduction path 33 becomes the fuel introduction path 43, the reforming path 34 becomes the reforming path 44, and the CO removal air introduction path 35 becomes the CO removal air introduction path 45. The carbon monoxide removal path 36 overlaps the carbon monoxide removal path 46. The portion of the reactor main body 11 where the reforming paths 34 and 44 are formed is the reformer 2 shown in FIG. The region where the carbon monoxide removal paths 36 and 46 are formed in the reactor main body 11 is the CO remover 3 shown in FIG.

  As shown in FIG. 2, heaters 70 and 71 using heating wires are patterned on the lower surface of the substrate 40. The heater 70 is patterned so as to fit inside the reforming paths 34 and 44 when projected from above or below, and the heater 71 is projected from above or below to see the carbon monoxide removal paths 36 and 46. Patterned to fit inside. The electrical characteristics (for example, electrical resistance) of the heaters 70 and 71 depend on the temperature, and the temperature of the heaters 70 and 71 is obtained by measuring the current and voltage of the heaters 70 and 71. It also functions as a sensor. The heaters 70 and 71 are electrically insulated from the anodic bonding metal film formed at the bonding interface between the substrate 40 and the substrate 50. The heaters 70 and 71 are connected to the lead wire 13.

  FIG. 5 is a cross-sectional view taken along the line VV in FIG. As shown in FIG. 5, a notch 50 a is formed at one corner of the substrate 50. A rectangular through hole 51 facing the through hole 41 is formed in the substrate 50. Further, a recess 56 is formed on the upper surface of the substrate 50 on the right side of the through hole 51. A groove 52 is formed in the upper surface of the substrate 50, that is, on the bonding surface with the substrate 40. The groove 52 is a fuel introduction path 53 that extends from the right edge of the substrate 50 to the left side of the through-hole 31 and an introduction path of air that becomes an oxidant for the combustion reaction that merges from the right edge of the substrate 50 to the fuel introduction path 53. A combustion path 54 that communicates with the air introduction path 53b and the end 53a of the fuel introduction path 53 and is formed in a distorted shape on the left side of the through hole 51, and a discharge that extends from the end 54a of the combustion path 54 to the right edge of the substrate 50. Road 55.

  The groove 52 is blocked by the substrate 40 by bonding the upper surface of the substrate 50 to the lower surface of the substrate 40. As shown in FIG. 2, the heater 70 is accommodated in the combustion path 54 of the groove 52, and the heater 71 is accommodated in the recess 56. When the reactor main body 11 is projected from above or viewed from below, the combustion path 54 overlaps the reforming paths 34 and 44. A combustion catalyst 57 is fixed on the wall surface of the combustion path 54. The combustion catalyst 57 will be described in detail later. A portion of the reactor main body 11 where the combustion path 54 is formed is the combustor 4 shown in FIG. In such a reactor main body 11, the reformer 2 is superposed on the combustor 4.

  Openings 63 to 68 are formed in the right side surface of the joined body of these substrates 30, 40, and 50, and the tube 14 is fitted into each of the openings 63 to 68, and the periphery of the tube 14 is sealed with a low melting point glass at the fitting portion. Hermetically sealed with an adhesive. The opening 63 serves as an inlet for combustion fuel gas to the fuel introduction path 53, the opening 64 serves as an air inlet to the air introduction path 53b, the opening 65 serves as an air inlet to the CO removal air introduction path 35, and the opening 66 The reformed gas used for power generation from the carbon monoxide removal path 36 becomes an outlet of the reformed gas, the opening 67 becomes an inlet of the fuel gas to the fuel introduction path 33, and the opening 68 becomes an outlet of the exhaust gas from the discharge path 55. In FIG. 1, the mixture of fuel and water (fuel gas) sent from the carburetor 902 flows into the opening 67 and is a mixture (combustion fuel gas) of hydrogen or the like that remains without being used for power generation. The air-fuel mixture sent from the anode flows into the opening 63. Further, air sent from the outside flows into the opening 64 and the opening 65. Exhaust gas (water etc.) of the combustor 4 is discharged from the opening 68 to the outside. The air-fuel mixture (hydrogen or the like) obtained through the CO remover 3 is sent from the opening 66 to the fuel electrode of the power generation cell 903 as a reformed gas used for power generation.

  The combustion catalyst 57 will be described. The combustion catalyst 57 is formed by supporting a catalyst composition containing a noble metal (for example, platinum) as an active component on a support (for example, alumina). Specifically, the combustion catalyst 57 is provided as shown in FIGS. FIG. 6 is a plan view of a part of the combustion path 54, and FIG. 6 is a cross-sectional view of a surface along the width direction of the combustion path 54. Although FIG. 6 shows that the combustion catalysts 57 are arranged at equal intervals, the dot density may be arranged so as to change at the flow path position as will be described later.

  As shown in FIGS. 6 and 7, the wall surface of the combustion path 54 of the substrate 50 serving as the base material is covered with a film-like carrier 57a. The carrier 57a is made of alumina. The carrier 57a is formed by a sol-gel method. Specifically, an alumina sol is applied to the wall surface of the combustion path 54 and dried to form a gel.

  The dot-shaped catalyst composition 57b is supported on the film-shaped support 57a. In plan view, the catalyst composition 57b is scattered on the support 57a with a space therebetween, and a part of the support 57a serving as a base is exposed between the catalyst compositions 57b. The catalyst composition 57b includes a support such as alumina in addition to a noble metal such as platinum. The catalyst composition 57b may be supported in the form of dots by a droplet discharge method (inkjet method) in which the catalyst-containing slurry is discharged in droplets many times, or a method in which the catalyst-containing slurry is spotted many times with a spotter. May be supported in a dot shape. Although the catalyst composition 57b is provided in a dot shape, the catalyst composition 57b may be patterned in a mesh shape to expose a part of the support 57a serving as a base.

  Although the carrier 57a is formed on the entire bottom surface of the combustion path 54, the carrier 57a may be patterned into a predetermined shape instead of a film. For example, as shown in FIG. 8, patterning may be performed so that a part of the substrate 50 serving as a base is exposed between the carriers 57c. As shown in FIG. 8, in a plan view, dot-shaped carriers 57c are scattered at the bottom of the combustion path 54 with a space therebetween, and a part of the bottom of the combustion path 54 as a base is between the carriers 57c. It is exposed at. The catalyst compositions 57d are supported on the respective supports 57c, and dot-like catalyst compositions 57d are scattered at intervals in a plan view, and a part of the bottom of the combustion path 54 is between the catalyst compositions 57d. Exposed. The catalyst composition 57b and the catalyst composition 57d are the same component, and the support 57a and the support 57c are the same component. Although the support 57c is provided in a dot shape, the support 57c is patterned in a mesh shape, and further, the catalyst composition is supported on the mesh support so that the catalyst composition is provided in a mesh shape and serves as a base. A part of the bottom of the combustion path 54 may be exposed.

  Here, as described later, the relationship between the position of the distance x along the combustion path 54 from the start point 53a of the combustion path 54 and the dot density i of the catalyst composition 57b or the catalyst composition 57d at that position is expressed by the formula ( It is desirable to be represented by 6).

  In equation (6), the dot density i is a function of the distance x from the starting point 53a of the combustion path 54 along the combustion path 54. Formula (6) represents that the catalyst composition 57b and the catalyst composition 57d having the dot density i are supported (distributed) at a position x from the starting point 53a.

Here, in the formula (6), W, X, α _x , R ₁ , Y, R ₂ , D _W , h, κ ₀ , R, T, Ea, C _O2 , u, C _{0 (H2)} are as follows: Represents this.
W: The amount of heat necessary to maintain a predetermined temperature during non-reaction,
Value determined by the configuration and structure of the microreactor 1 X: molar amount of reactants input in the reforming reaction, specification value α _x : reaction rate of the reforming reaction in a minute region at a distance x And
Specification value determined by reaction conditions and configuration R ₁ : endothermic amount per unit mole of reforming reaction, derived from stoichiometric formula Y: molar amount of reactant in catalytic combustion reaction, specification value R ₂ : calorific value per unit mole of catalytic combustion reaction, derived from stoichiometric formula D _W : weight per dot h: depth of combustion path 54 κ ₀ : frequency factor R: gas constant T : Temperature Ea: Activation energy C _O2 : Oxygen concentration u: Average flow velocity C _{0 (H2)} : Initial hydrogen concentration

Equation (6) will be described below. Here, for simplification, the influence of the heat balance for maintaining the carbon monoxide removal reaction at a predetermined temperature in the CO remover 3 is not considered.
The amount of heat required to operate the reformer 2 at a predetermined reaction temperature at the position of the distance x is the sum of maintaining the reformer 2 at the reaction temperature and the endothermic amount due to the reforming reaction. It is represented by Formula (7). When this is represented in a graph, it is represented as a curve A in FIG. 9, for example.

On the other hand, the amount of heat generated by the catalytic combustion of the combustion catalyst 57 at the position of the distance x is expressed by Expression (8). In Equation (8), β _x is the reaction rate of the catalytic combustion reaction in the minute region at the position of the distance x, and is a specification value determined by the reaction conditions and configuration.

  If the equations (7) and (8) are equal at the position of the distance x, the heat absorption and heat generation can be balanced, and the reformer 2 can be operated at a predetermined reaction temperature by catalytic combustion.

Here, when the reaction rate in the micro region space is γ _z and the dot density in the micro region is i, the reaction rate equation of the following equation (9) is established. In the formula (9), the order of the RT and C _O2 is referred to as reaction order, the experimental value is a value that is determined by the hydrogen combustion reaction using Pt / Al ₂ O _3.

Moreover, Formula (10) is materialized from material balance.

式（１２）から、式（８）の熱量が式（７）の熱量に等しくなるようにする条件より、ドット密度ｉは式（６）のように求まる。 From Expressions (9) and (10) to Expression (11), that is, the dot density i is as shown in (12).

From the equation (12), the dot density i can be obtained as in equation (6) from the condition that the amount of heat in equation (8) is equal to the amount of heat in equation (7).

A dot density distribution corresponding to FIG. 9 is schematically shown in FIG.
As shown in FIG. 10, the distribution is such that the dot density continuously changes from dense to sparse from the upstream side to the downstream side of the combustion path 54. Therefore, the distance P1 between the catalyst compositions 57b (or catalyst composition 57d, which is the same in FIG. 10 below) located upstream of the combustion path 54 (near the starting point 53a of the combustion path 54) and adjacent to each other is the same. The distance P2 between the catalyst compositions 57b located in the midstream portion and adjacent to each other is shorter than the distance P2 between the catalyst compositions 57b in the midstream portion, and is located in the downstream portion (near the end point end portion 54a of the combustion path 54). And shorter than the distance P3 between the catalyst compositions 57b adjacent to each other.

As described above, at a certain position in the combustion path 54, the amounts of the catalyst composition 57b and the catalyst composition 57d per unit area correspond to the heat absorption amount to the reformer 2 at that position. Specifically, when the dot density is used as the amount per unit area, the dot density of the catalyst composition 57b or the catalyst composition 57d per unit area at a certain position in the combustion path 54 is based on the equation (6). Further, it is desirable to arrange them corresponding to the amount of heat absorbed by the reformer 2 at that position (reaction rate α _x of the reforming reaction).

Next, a method for manufacturing the microreaction apparatus 1 will be described.
First, a metal film for anodic bonding is formed on both surfaces of the substrate 40 by sputtering, and the heaters 70 and 71 are formed on the lower surface of the substrate 40 by photolithography, etching, etc., and the heaters 70 and 71 and the metal film are formed. Insulate. Next, the through holes 31 and the grooves 32 are processed in the substrate 30 by a photolithography method and a sand blast method. The through-hole 31 is formed by sandblasting from both sides. Similarly to the substrate 30, the through holes 41 and 51 and the grooves 42 and 52 are formed on the substrates 40 and 50. Then, the substrates 30, 40, 50 are cut out by dicing.

  Next, a dry film photoresist is affixed to the substrate 30, and the same shape as the grooves 32 is processed into a dry film photoresist by photolithography. Next, the reforming catalyst 37 is fixed on the wall surface of the reforming path 34, and the selective oxidation catalyst 38 is fixed on the wall surface of the carbon monoxide removal path 36. Specifically, the wall surface of the reforming path 34 is coated with a catalyst dispersion in which a catalyst composition (for example, a Cu / ZnO-based catalyst composition) is dispersed in a solvent. As another method, an adhesion improving layer of oxide (for example, alumina) is formed on the wall surface of the reforming path 34 by a sol-gel method or the like, and the catalyst dispersion is coated on the adhesion improving layer. As a fixing method of the selective oxidation catalyst 38, a catalyst dispersion liquid in which a catalyst composition (for example, a platinum-based catalyst composition) is dispersed in a solvent is coated on the wall surface of the carbon monoxide removal path 36. As another method, an adhesion improving layer of oxide (for example, alumina) is formed on the wall surface of the carbon monoxide removal path 36 by a sol-gel method or the like, and the catalyst dispersion is coated on the adhesion improving layer.

  As with the substrate 30, the reforming catalyst 47 is fixed on the wall surface of the reforming path 44 and the selective oxidation catalyst 48 is fixed on the wall surface of the carbon monoxide removal path 46.

  After fixing the catalyst, the substrates 30 and 40 are dried on a hot plate at 110 ° C. for 1 hour to evaporate water. Thereafter, when the substrates 30 and 40 are cooled to room temperature, the dry film photoresist is peeled off by a peeling method.

A method for fixing the combustion catalyst 57 to the wall surface of the combustion path 54 of the substrate 50 will be described.
First, JRC-ALO-6 (manufactured by JGC) is pulverized and subjected to a firing treatment at 500 ° C. for 1 hour under an air flow to prepare alumina as a carrier. Prepared by putting pure water and alumina in hexachloroplatinic acid (IV) hexahydrate aqueous solution, evaporating water to support platinum on alumina, and then reducing with hydrogen, platinum loading is 0.1wt% A Pt / Al ₂ O ₃ catalyst composition is obtained. A slurry is obtained by mixing the Pt / Al ₂ O ₃ catalyst composition thus prepared (weight ratio 1), pure water (weight ratio 10 to 30) and hydroxyethyl cellulose (weight ratio 0.1).

The process diagram shown in FIG. 11 shows the process of fixing the combustion catalyst 57 of the form shown in FIG.
As shown in FIG. 11A, an alumina sol is applied to the wall surface of the combustion path 54 of the substrate 50, and an alumina carrier 57a is formed by a sol-gel method. Next, the substrate 50 is fixed on a positioning device (for example, an XY stage) 91 as shown in FIG. A driving jig having a spotter 92 that can reciprocate in a direction orthogonal to the surface of the substrate 50 is arranged, and the driving jig is controlled by a control device. As shown in FIG. 11 (b), a slurry droplet 58 containing a Pt / Al ₂ O ₃ catalyst composition is attached to the tip of the spotter 92, and as shown in FIG. 11 (c), the tip of the spotter 92. Is brought into contact with the wall surface of the combustion path 54 to adhere the slurry droplet 58 to the carrier 57a. While the substrate 50 is moved by the positioning device 91, the spotter 92 is repeatedly moved up and down to attach a large number of droplets 58 to the carrier 57a (see FIGS. 11D and 11E). At this time, the droplets 58 are distributed so that a portion of the carrier 57a serving as a base is exposed with a space between the droplets 58. Further, the droplets 58 of the slurry are distributed so that the dot density of the droplets 58 at the position x from the start point 53a is determined by the endothermic amount (reaction rate α _x of the reforming reaction) at that position as shown in the equation (6). It is desirable to make it. When a large number of droplets 58 are spotted, the substrate 50 is placed on a hot plate at 100 ° C. for 1 hour, and when the moisture of the droplets 58 is evaporated and dried, the droplets 58 become the catalyst composition 57b (FIG. 7). reference). According to such a method, since the droplets 58 are spotted in a separated state, even if the droplets 58 bleed, they do not aggregate, and the catalyst composition 57b can also be scattered in a separated state.

The process chart shown in FIG. 13 shows the process of fixing the combustion catalyst 57 of the form shown in FIG. Hereinafter, a method of fixing the combustion catalyst 57 will be described with reference to FIG.
The substrate 50 is fixed on the positioning device 91. Next, while moving the substrate 50 by the positioning device 91, alumina sol is attached to the tip of the spotter 92, and the spotter 92 is repeatedly moved up and down to attach a large number of droplets 59 of alumina sol to the wall surface of the combustion path 54. (FIG. 13A). At this time, the droplets 59 are distributed so that a part of the substrate 50 serving as a base is exposed at intervals of the droplets 59. Further, the alumina sol droplets 59 are distributed so that the dot density of the droplets 59 at a position x from the starting point 53a is determined by the endothermic amount (reaction rate α _x of the reforming reaction) at that position as shown in the equation (6). It is desirable to make it. When a large number of droplets 59 are spotted, the substrate 50 is placed on a hot plate at 100 ° C. for 1 hour, and when the moisture of the droplets 59 is evaporated and dried, the droplets 59 become the support 57c (FIG. 13 ( b)). Next, the slurry 60 containing the Pt / Al ₂ O ₃ catalyst composition is applied to the entire combustion path 54, and the support body 57c is covered with the slurry 60 (FIG. 13C). Then, when the applied slurry 60 is blown off by a blower or the like, the slurry 60 fixed on the carrier 57c remains, and the other part is removed (FIG. 13D). Subsequently, when the substrate 50 is placed on a hot plate at 100 ° C. for 1 hour and the moisture of the slurry 60 is evaporated and dried, the slurry 60 becomes the catalyst composition 57d.
According to the method shown in FIG. 13, the catalyst composition 57d can be scattered in a separated state without agglomeration. In addition, since the slurry 60 is applied in a state that is not in the form of droplets, it is not necessary to specially prepare the physical properties (viscosity, etc.) of the slurry 60, and the possibility of reaction inhibition due to additives for physical property preparation is eliminated. Can do.

Hereinafter, another method for fixing the combustion catalyst 57 having the configuration shown in FIG. 8 will be described with reference to FIG.
In this method, instead of using a slurry containing Pt / Al ₂ O ₃ catalyst composition, used in the Pt / Al ₂ O ₃ catalyst composition into powder. First, the substrate 50 is fixed on the positioning device 91. Next, while moving the substrate 50 by the positioning device 91, alumina sol is attached to the tip of the spotter 92, and the spotter 92 is repeatedly moved up and down to attach a large number of droplets 59 of alumina sol to the wall surface of the combustion path 54. (FIG. 14A). At this time, it is desirable to distribute the droplets 59 so that a part of the substrate 50 serving as a base is exposed with an interval between the droplets 59. Further, the alumina sol droplets 59 are distributed so that the dot density of the droplets 59 at a position x from the starting point 53a is determined by the endothermic amount (reaction rate α _x of the reforming reaction) at that position as shown in the equation (6). It is desirable to make it. When a large number of droplets 59 are spotted, a powdery Pt / Al ₂ O ₃ catalyst composition 61 is applied to the entire combustion path 54, and the droplets 59 are covered with the catalyst composition 61 (FIG. 14B). ). When the Pt / Al ₂ O ₃ catalyst composition 61 blown off by a blower or the like, Pt / Al ₂ O ₃ catalyst composition 61 adhering to the droplets 59 remain, the other portions are removed (FIG. 14 ( c)). The catalyst composition 61 blown off can be recovered and reused. Subsequently, when the substrate 50 is placed on a hot plate at 100 ° C. for 1 hour and the moisture mixed in the Pt / Al ₂ O ₃ catalyst composition 61 and the moisture of the droplet 59 are evaporated and dried, the droplet 59 is carried. The Pt / Al ₂ O ₃ catalyst composition 61 that becomes the body 57c and adheres to the droplet 59 becomes the catalyst composition 57d.
According to the method shown in FIG. 14, the catalyst composition 57d can be scattered in a separated state without agglomeration. Furthermore, since the powdered catalyst composition 61 is applied, it is not necessary to add anything to the catalyst composition 61, there is no possibility of reaction inhibition, and the catalyst composition 61 can be recovered. Therefore, the cost is low.

  In the above description, the dot-like droplets 58 and the droplets 59 are distributed by being spotted by the spotter 92. However, the droplets 58 and the droplets 59 are ejected many times from the droplet ejection head (inkjet head). By doing so, the dot-like droplets 58 and the droplets 59 may be distributed.

  After the catalyst is fixed, the substrate 30 and the substrate 40 are overlapped, and a voltage is applied using the metal film of the substrate 40 as an anode and the substrate 30 side as a cathode, thereby performing anodic bonding of the substrate 30 and the substrate 40. Subsequently, the lead wire 13 is resistance-welded to the thin film heater pads at both ends of the heaters 70 and 71. Subsequently, the substrate 40 and the substrate 50 are overlapped, and a voltage is applied using the metal film of the substrate 40 as an anode and the substrate 50 side as a cathode, thereby performing anodic bonding of the substrate 40 and the substrate 50. In the anodic bonding, the contact terminal is brought into contact with the metal film from the notches 30a and 50a, and a voltage is applied to the metal film.

  Subsequently, the tube 14 is inserted into the openings 63 to 68, and the gaps between the openings 63 to 68 are hermetically sealed with a low-melting glass sealant. The joined body of the substrates 30, 40, 50 and the getter pump (not shown) are accommodated in the glass containers 21, 22, the tube 14 and the lead wire 13 are fitted into the grooves of the glass containers 21, 22, and the glass containers 21, 22 are aligned. Then, the glass containers 21 and 22 are bonded with low melting point glass. Thereby, the heat insulation package 12 is assembled. A gap between the tube 14 or the lead wire 13 and the heat insulating package 12 is sealed with a low melting point glass. Further, the heat insulation package 12 has a hole (not shown) for attaching a vacuum drawing tube, the vacuum drawing tube is inserted into the hole, and the vacuum drawing tube is also sealed to the heat insulation package 12 using low melting point glass. To do. Finally, a vacuum pump is attached to the vacuum pulling tube, and the vacuum pulling tube is sealed while evacuating the air in the heat insulating package 12 with the vacuum pump.

Next, the operation of the microreaction apparatus 1 will be described.
During startup, the heaters 70 and 71 generate heat due to voltage, and during normal operation, hydrogen remaining from the fuel electrode of the power generation cell 903 without being used for power generation is supplied to the opening 63. Further, external air is supplied to the opening 64, and hydrogen and air are mixed in the fuel introduction path 53. When an air-fuel mixture such as hydrogen and air flows into the combustion path 54 and the air-fuel mixture flows through the combustion path 54, the hydrogen burns to generate combustion heat. The combustion heat is absorbed by the reformer 2. Water or the like generated by the combustion is discharged outside through the opening 68 through the discharge path 55. On the other hand, a mixture of fuel and water is supplied from the vaporizer 902 to the opening 67, and a reforming reaction occurs when the fuel and water flow through the reforming paths 34 and 44. The reforming reaction is an endothermic reaction, and the combustion heat in the combustor 4 is used. In addition, external air is supplied to the opening 65 and mixed with the generated hydrogen, carbon monoxide, or the like, and the mixed gas flows through the carbon monoxide removal paths 36 and 46. In the carbon monoxide removal paths 36 and 46, carbon monoxide is oxidized and removed. The generated hydrogen or the like is supplied from the opening 67 to the fuel electrode of the power generation cell 903.

  According to this embodiment, since the catalyst compositions 57b and 57d are spotted at intervals, the catalyst compositions 57b and 57d do not aggregate, hydrogen does not burn locally, and locally high temperature. Never become. Therefore, thermal destruction of the combustor 4 etc. due to high temperature can be suppressed.

  In the above embodiment, the reformer 2 is taken as an example of a processor that generates heat, but another reactor that generates an endothermic reaction may be provided instead of the reformer 2. Further, a vaporizer that generates heat by vaporizing the liquid may be provided instead of the reformer 2.

  In the method shown in FIG. 11, the catalyst is fixed on the combustion path wall surface of the glass substrate at intervals, and the amount of hydrogen necessary for heat generation of 1.3 W is mixed with air and supplied to the combustion path 54 of the combustor 4. did. Heat generation by the heaters 70 and 71 and combustion heat in the combustion path 54 were used in combination, and the reformer 2 was controlled at 300 ° C. and the CO remover 3 was controlled at 100 ° C., and the operation was performed for 1 hour. As a result, when the microreactor 1 was disassembled, the destruction of the microreactor 1 due to combustion could not be confirmed. Moreover, the result of the combustion energy with respect to the supply amount of an oxidizing agent (oxygen in the air) is shown in FIG. In FIG. 15, the vertical axis represents combustion efficiency or combustion energy, and has a relationship of “combustion efficiency = (combustion energy contributing to the reformer 2) ÷ (hydrogen energy contributing to reaction)”. Further, the horizontal axis represents “2 × (molar flow rate of oxygen) ÷ (molar flow rate of supplied hydrogen)”. As apparent from FIG. 15, when the amount of oxygen contained in the air is supplied more than the stoichiometry of the amount of hydrogen, combustion energy of about 1.05 W could be stably secured. At this time, when the gas exhausted after combustion was measured with a micro gas chromatography CP2002 (manufactured by Varian, column Molsieve 5A, carrier gas Ar), hydrogen was not detected, and it was confirmed that all the hydrogen was combusted. .

  In addition, for a micro reactor using a dip coat method in which a combustion catalyst is fixed in the same amount as above instead of the combustion catalyst 57, the amount of hydrogen required for heat generation of 1.3 W is mixed with air and burned. It was supplied to the combustion path 54 of the vessel 4. The heat generated by the heaters 70 and 71 and the combustion heat in the combustion path 54 were used in combination, the reformer 2 was controlled at 300 ° C., the CO remover 3 was controlled at 100 ° C., and the operation was performed for 1 hour (comparative example). It was found that when the microreactor was disassembled, cracks in the combustion path 54 of the glass substrate occurred when the thermal insulation effect of the vacuum insulation, which seems to be destroyed by the combustor 4, was lost during the operation or during the temperature decrease after the operation was completed. .

It is a block diagram of the electric power generating apparatus provided with the micro reaction apparatus to which this invention is applied, and an electronic device provided with the same. It is sectional drawing of a micro reactor. It is arrow sectional drawing of the surface along the cutting line III-III of FIG. FIG. 4 is a cross-sectional view taken along the line IV-IV in FIG. FIG. 5 is a cross-sectional view taken along an arrow line VV in FIG. 2. It is a top view of the combustion path formed in the micro reactor. It is arrow sectional drawing of the surface along the cutting line VII-VII of FIG. It is sectional drawing in a different form from FIG. It is the graph which showed the relationship between the distance x and required combustion calorie | heat amount while showing the heat absorption amount in the distance x. It is a figure which shows typically the dot density distribution corresponding to FIG. It is process drawing which showed the fixing method of the combustion catalyst of the form shown in FIG. It is drawing which showed the apparatus used for the fixing method of a combustion catalyst. It is process drawing which showed the fixing method of the combustion catalyst of the form shown in FIG. It is process drawing which showed the fixing method of another combustion catalyst of the form shown in FIG. It is the graph which showed the result of the combustion energy with respect to the supply amount of an oxidizing agent, and combustion efficiency. (A) is a fragmentary sectional view of the conventional combustor, (b) is a top view of the combustion path in the combustor.

Explanation of symbols

1 Micro reactor (reactor)
2 Reformer (Processor)
54 Combustion path 57 Combustion catalyst 57a, 57c Carrier 57b, 57d Catalyst composition 900 Power generation device 1000 Electronic device main body

Claims (15)

An endothermic processor,
A combustor that is superimposed on the processor and forms a combustion path through which combustion fuel and oxidant flow;
A reaction apparatus characterized in that a catalyst composition as an active component is fixed on a wall surface of the combustion path at intervals.   The reaction apparatus according to claim 1, wherein an amount per unit area of the catalyst composition at a certain position in the combustion path corresponds to an endothermic amount to the processor at the position. The catalyst composition is dotted and scattered on the wall surface of the combustion path,
The reaction apparatus according to claim 1, wherein a dot density of the catalyst composition at a certain position in the combustion path corresponds to an endothermic amount to the processor at the position.   The reaction apparatus according to any one of claims 1 to 3, wherein a support is formed into a film on the wall surface of the combustion path, and the catalyst composition is supported on the support. A carrier is spotted in the form of dots on the wall surface of the combustion path, and the catalyst composition is dotted in the form of dots by being carried on the carrier,
The reaction apparatus according to claim 1, wherein a dot density of the catalyst composition at a certain position in the combustion path corresponds to an endothermic amount to the processor at the position.   A power generation apparatus comprising: the reaction apparatus according to any one of claims 1 to 5; and a power generation cell that generates electric power using fuel generated by the reaction apparatus. A power generator according to claim 6;
And an electronic device body that operates by electricity generated by the power generation device.   In a reaction apparatus in which a combustor that forms a combustion path in which combustion fuel and an oxidant flow are superimposed on a processor that generates heat, a catalyst composition as an active component is fixed on the wall surface of the combustion path at intervals. And a catalyst fixing method.   9. The catalyst composition according to claim 8, wherein the catalyst composition is distributed so that an amount per unit area of the catalyst composition at a certain position of the combustion path corresponds to an endothermic amount to the processor at the position. Catalyst fixing method. The catalyst composition is dotted on the wall surface of the combustion path in the form of dots,
9. The catalyst according to claim 8, wherein the catalyst composition is distributed so that a dot density of the catalyst composition at a certain position of the combustion path corresponds to an endothermic amount to the processor at the position. Fixing method.   The catalyst fixing method according to any one of claims 8 to 10, wherein the catalyst composition is supported on the support after the support is formed into a film on the wall surface of the combustion path.   After the support is spotted on the wall surface of the combustion path in the form of dots and the catalyst composition is applied so as to cover the support, the catalyst composition is removed except for the catalyst composition supported on the support. The catalyst fixing method according to claim 8, wherein the catalyst composition is dotted in the form of dots by removing the catalyst composition.   13. A sol-like carrier is spotted in the form of dots on the wall surface of the combustion path, and a slurry containing a catalyst composition is applied after the carrier is dried to coat the carrier. The catalyst fixing method described in 1.   13. A sol-like carrier is spotted in the form of dots on the wall surface of the combustion path, and a powdered catalyst composition is applied before the carrier is dried to coat the carrier. The catalyst fixing method described in 1.   15. The catalyst composition according to claim 12, wherein the catalyst composition is distributed so that a dot density of the catalyst composition at a certain position of the combustion path corresponds to an endothermic amount to the processor at the position. The catalyst fixing method according to claim 1.

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