JP4715586B2 - Reactor - Google Patents

Description

The present invention relates to a reaction apparatus .

  In recent years, small reactors called microreactors have been developed and put into practical use. A microreactor is a small reactor that reacts multiple types of raw materials, reagents, fuels, and other reactants while mixing them together. Chemical reaction experiments, drug development, artificial organ development, genome / DNA analysis in the micro domain It is used for tools and basic analysis tools for microfluidics. A chemical reaction using a microreactor has characteristics that are not found in a normal chemical reaction using a beaker, a flask, or the like. For example, since the entire reactor is small, there is an advantage that the heat exchange rate is extremely high and temperature control can be performed efficiently. Therefore, a reaction that requires precise temperature control or a reaction that requires rapid heating or cooling can be easily performed.

  Specifically, in the microreactor, for example, a substrate in which grooves having a predetermined pattern are bonded together to form a flow path for flowing a gaseous or liquid reactant, for example, a catalyst is provided in the flow path to flow the reactant, There are some in which a reaction vessel such as a reactor (reaction tank) for causing a reaction of the reactant by heating the reactant to an appropriate reaction temperature is formed.

By the way, in order to heat the reactant in the microreactor to a predetermined temperature, a thin film heater may be provided on the substrate on which the microreactor is formed (see, for example, Patent Document 1).
JP-T-2001-505819 (see FIG. 6)

  However, in the reaction apparatus as described above, the thin film heater for heating the reaction product in the reaction vessel is difficult to form by patterning the thin film heater in the groove formed in the substrate. It was provided outside the substrate forming the flow path. For this reason, since the thin film heater heats the reactant by heat conduction through the substrate, it is difficult to quickly raise the temperature of the reactant flowing in the flow path, and the response time such as the startup time of the reactor It was difficult to shorten.

The subject of this invention is providing the reaction apparatus which can provide a thin film heater in reaction container.

In order to solve the above problems, the invention according to claim 1 is a reaction apparatus including a reaction vessel that causes reaction of a reactant, and the reaction vessel has a heating wire pattern formed by a thin film heater on one surface. A heater plate, a lid plate disposed in parallel with the heater plate on a side of the heater plate on which the heating wire pattern is formed, and provided between the heater plate and the lid plate, and at least the heating wire On the one surface of the heater plate corresponding to the inside of the opening, the partition plate having an opening along the pattern and arranged to partition the space between the heater plate and the lid plate A pair of upper substrates having a recess that opens to communicate with both outer surfaces of the partition plate and forms a sealed space. And lower board A plurality of substrates including at least the lid plate, the partition plate, and the heater plate are provided between the upper substrate and the lower substrate via a bonding layer, and each of the plurality of substrates is A slit portion that communicates with the sealed space, and the reaction vessel and a surrounding portion that accommodates the reaction vessel are formed integrally through the sealed space and the slit portion, and the surrounding portion and the upper substrate; The lower substrate constitutes a heat-insulated container whose inside is depressurized, a plurality of the substrates are stacked, and a supply port to which the reaction product in the reaction container is supplied and a discharge port from which the product in the reaction container is discharged A connection part formed and holding the reaction container in the heat insulation container is provided at one end of the reaction container, and the connection part has the supply port and the discharge port .

  According to a second aspect of the present invention, there is provided the reaction apparatus according to the first aspect, wherein a reaction catalyst for promoting a reaction of the reactant is provided on at least the insulating film of the heater plate corresponding to the opening. It is characterized by being.

  According to a third aspect of the present invention, in the reaction apparatus according to the second aspect, the reaction vessel is a reformer that reforms the reactant, and the catalyst is a reforming catalyst that promotes a reforming reaction. It is characterized by that.

  According to a fourth aspect of the present invention, in the reactor according to the second aspect, the reaction vessel is a carbon monoxide remover that removes carbon monoxide contained in the reactant, and the catalyst is made of carbon monoxide. It is a carbon monoxide removal catalyst that promotes oxidation.

  Invention of Claim 5 is a reaction apparatus as described in any one of Claims 1-4. WHEREIN: A recessed part is provided in the other surface on the opposite side to the surface in which the said heating wire pattern of the said heater plate was formed. A bottom plate for closing the recess is provided, and a combustion catalyst for burning fuel supplied from the outside is provided on at least a surface of the recess facing the heating wire pattern.

  A sixth aspect of the present invention is the reaction apparatus according to the fifth aspect, wherein the concave portion is formed corresponding to the opening.

The invention according to claim 7 is the reaction apparatus according to any one of claims 1 to 6 , wherein the reaction apparatus is set to a first temperature and causes a reaction of the reactant. And a second reaction part set to a second temperature lower than the first temperature and causing the reaction of the reactant, at least one of the first reaction part and the second reaction part is The reaction vessel is provided.

The invention according to claim 8 is the reaction apparatus according to claim 7 , wherein the first product is generated from the first reactant supplied to the first reaction section, and the second reaction section is formed. The first product is supplied to the first product, and a second product is produced from the first product. The first reaction product is a gas mixture obtained by vaporizing water and a hydrocarbon-based liquid fuel. The first reaction unit is a reformer that causes a reforming reaction of the first reactant, and the first product contains hydrogen and carbon monoxide, and the second reaction The section is a carbon monoxide remover that removes carbon monoxide contained in the first product.

  According to the present invention, the substrate having the opening along the heating wire pattern is laminated on the substrate on which the heating wire pattern by the thin film heater is formed on one surface and the insulating film covering the heating wire pattern is formed. Then, since the reaction container is formed by laminating the substrates that close the opening, a thin film heater can be provided in the reaction container, and the response time of the reaction apparatus can be shortened.

  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.

<First Embodiment>
FIG. 1 is a block diagram of a power generator 1 in which a reactor 10 to which the present invention is applied is used. The power generation device 1 is provided in, for example, 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 these electronic device bodies.

  The power generation device 1 includes a fuel container 2, a reformed fuel vaporizer 3, a reaction device 10, and a power generation cell 5. The fuel container 2 stores fuel (for example, methanol, ethanol, dimethyl ether, butane, gasoline) and water separately or in a mixed state, and the fuel and water mixture is reformed fuel vaporizer 3 by a micro pump (not shown). Via, it is supplied to the reactor 10.

  The reaction apparatus 10 has a high temperature reaction section 11 and a low temperature reaction section 12 and is accommodated in a heat insulating container 18 (not shown in FIG. 1). The high temperature reaction unit 11 has a reformer 13, a combustor 15 and a high temperature heater 17, and the low temperature reaction unit 12 has a CO remover 14 and a low temperature heater 16.

  The fuel and water supplied from the fuel container 2 to the reformed fuel vaporizer 3 are vaporized by the reformed fuel vaporizer 3 and supplied to the reformer 13. In the reformer 13, hydrogen gas or the like is generated from the steam and vaporized liquid 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. The reaction for generating hydrogen is an endothermic reaction, and the combustion heat of the combustor 15 is used.

CH ₃ OH + H ₂ O → 3H ₂ + CO ₂ (1)
H ₂ + CO ₂ → H ₂ O + CO (2)

  The CO remover 14 removes carbon monoxide, which is by-produced in a trace amount by a formula such as the chemical reaction formula (2), which sequentially occurs after the chemical reaction formula (1), and removes it from the mixed gas. Hereinafter, the mixed gas from which the carbon monoxide is removed is referred to as a reformed gas. The reformed gas is supplied to the fuel electrode side of the power generation cell 5.

  The reformed gas is supplied from the CO remover 14 to the fuel electrode side of the power generation cell 5. Hydrogen gas in the reformed gas is separated into hydrogen ions and electrons by a catalyst provided in the fuel electrode as shown in the electrochemical reaction formula (3). Hydrogen ions pass through the electrolyte membrane and move to the oxygen electrode side, and electrons move to the oxygen electrode through an external circuit. On the oxygen electrode side, as shown in the electrochemical reaction formula (4), a chemical reaction between hydrogen ions that have passed through the electrolyte membrane, electrons supplied from the oxygen electrode through an external circuit, and oxygen gas supplied from the outside air To produce water. Electrical energy can be extracted from the difference in electrode potential between the fuel electrode and the oxygen electrode.

H ₂ → 2H ⁺ + 2e ⁻ (3)
2H ⁺ + 2e ⁻ + 1 / 2O ₂ → H ₂ O (4)

The combustor 15 mixes the hydrogen gas (off-gas) remaining without the electrochemical reaction in the power generation cell 5 and oxygen, burns by a catalytic reaction, and heats the high-temperature reaction unit 11 to a predetermined temperature by combustion heat. .
The low-temperature heater 16 heats the low-temperature reaction part 12 to less than 200 ° C., for example, about 110 to 190 ° C. at startup.

[Specific structure of the reactor]
Next, a specific configuration of the reaction apparatus 10 will be described. FIG. 2 is a perspective view of the reaction apparatus 10 of the present embodiment, and FIG. 3 is an exploded perspective view of the reaction apparatus 10 of the present embodiment. As shown in FIGS. 2 and 3, the reaction apparatus 10 is formed by bonding six substrates 30, 40, 50, 60, 70, 80 together. Each substrate 30, 40, 50, 60, 70, 80 can be processed by photolithography, sandblasting, or the like, and each substrate 30, 40, 50, 60, 70, 80 is bonded by anodic bonding. be able to. Specifically, as will be described later, an anodic bonding film is provided on one substrate, a cathode 97 is brought into contact with the other glass substrate, and an anode 98 is brought into contact with the anodic bonding film and heated to a temperature of about 200 to 500 ° C. Then, by applying a high voltage of about 100 to 1000 V and moving the movable ions (positive ions) contained in the glass substrate to the cathode 97 side, the SiO 2 oxygen atoms on the glass substrate side are negatively charged, and the anode Bonding is performed by covalently bonding a positively charged metal on the bonding film side at the interface.
In the following description, for convenience, the substrate 30 side is described as the upper side, and the substrate 80 side is described as the lower side.

  The substrates 30, 40, 50, 60, 70, 80 are glass substrates in the present embodiment, and more specifically, glass substrates containing Na and Li that become mobile ions. As such a glass substrate, a heat-resistant glass such as a Pyrex (registered trademark) substrate can be used.

  FIG. 4 is a cross-sectional view taken along line II of the reactor 10 of the present embodiment shown in FIG. As shown in FIGS. 3 and 4, the reaction apparatus 10 includes a high temperature reaction unit 11, a low temperature reaction unit 12 (reaction vessel), and a heat insulation vessel 18. In addition, the high temperature reaction part 11 and the low temperature reaction part 12, and the low temperature reaction part 12 and the heat insulation container 18 are partially connected by the board | substrate 40,50,60,70.

A connecting portion between the high temperature reaction section 11 and the low temperature reaction section 12 serves as a flow path for supplying the reactant to the high temperature reaction section 11 and a flow path for carrying out the product. The connecting portion between the low temperature reaction section 12 and the heat insulation container 18 serves as a reactant supply flow path from the outside of the heat insulation container 18 of the high temperature reaction section 11 and the low temperature reaction section 12 and a product delivery flow path to the outside of the heat insulation container 18. . 2 to 4, the connecting portion between the low temperature reaction section 12 and the heat insulating container 18 is provided at the end of the reaction apparatus 10 in the longitudinal direction.
In addition, in the following description, the connection part side of the low temperature reaction part 12 and the heat insulation container 18 is demonstrated as a front side for convenience.

  A heat insulating chamber 19 is provided between the high temperature reaction unit 11 and the low temperature reaction unit 12 and the heat insulating container 18. A slit 19 a integrated with the heat insulation chamber 19 is provided between the high temperature reaction portion 11 and the low temperature reaction portion 12. The inside of the heat insulation chamber 19 and the slit 19a is depressurized, the heat conduction chamber 19 reduces the heat conduction from the high temperature reaction section 11 and the low temperature reaction section 12 to the heat insulation container 18, and the slit 19a reduces the heat conduction from the high temperature reaction section 11 to the low temperature reaction section. The heat conduction to 12 is reduced.

  Moreover, you may provide the infrared reflective film (not shown) which reflects the heat ray radiated | emitted from the high temperature reaction part 11 and the low temperature reaction part 12 in the wall surface of the heat insulation chamber 19 and the slit 19a. This infrared reflection film is formed by depositing, for example, gold, aluminum, silver or copper by a vapor phase method such as a sputtering method or a vacuum deposition method, and is an operating temperature of the high temperature reaction unit 11 and the low temperature reaction unit 12. The reflectance of infrared rays (wavelength: 5 to 30 μm) generated in the temperature range of several hundred degrees Celsius is almost 100%. In the case where the infrared reflecting film is formed of gold, a layer of tungsten, chromium, titanium, tantalum, molybdenum, or the like may be provided as a base in order to improve adhesion.

Further, for example, a film-like getter material 21 may be provided on a part of the wall surface of the heat insulating chamber 19 or the slit 19a. The getter material 21 is activated by heating and adsorbs surrounding gas and fine particles, and adsorbs gas existing in the heat insulating chamber 19 or the slit 19a to increase the degree of vacuum in the heat insulating chamber 19, or Can be maintained. Examples of such a getter material 21 include an alloy mainly composed of zirconium, barium, titanium, or vanadium. The getter material 21 is preferably provided on the low temperature reaction part 12 side so as not to exceed its activation temperature. In addition, an electric heater such as an electric heating material for heating and activating the getter material 21 may be provided, and an electric wire of the electric heater may be drawn out of the heat insulating container 18.
Hereinafter, each substrate 30, 40, 50, 60, 70, 80 will be described.

[First substrate]
FIG. 5 is a top view of the first substrate 30 in the present embodiment. The first substrate 30 has a rectangular plate shape, and as shown in FIG. 5, a protruding frame portion 31 is provided on the outer peripheral portion of the lower surface, and a concave portion 32 is formed inside the frame portion 31. The recess 32 forms a part of the heat insulation chamber 19. The infrared reflection film (not shown) may be provided on the inner surface of the recess 32. Moreover, you may make it provide said getter material 21 on said infrared reflective film of the area | region corresponding to the low temperature reaction part 12 among the inner surfaces of the recessed part 32, for example. In addition, triangular corners 30a, 30b, 30c, and 30d are formed at the four corners of the first substrate 30.

[Second board]
FIG. 6 is a top view of the second substrate 40 in the present embodiment. As shown in FIG. 6, the second substrate 40 includes a lid plate 42 and a rectangular frame 43 provided outside the lid plate 42. The cover plate 42 and the frame body 43 are integrally formed on the front side. An opening 42 a that forms a slit 19 a is provided in the central portion of the lid plate 42. The lid plate 42 is formed with a triangular chamfered portion 40e at the right rear corner. A gap 43 a between the lid plate 42 and the frame body 43 forms the heat insulation chamber 19. In the frame, triangular corners 40a, 40b, and 40c are formed at the left front corner, the left rear corner, and the right rear corner.

A buffer film (not shown) is formed on the upper surface of the frame 43, and an anodic bonding film 44 (see FIG. 4) is formed on the buffer film. The buffer film prevents damage to the metal for anodic bonding due to the movement of mobile ions during anodic bonding. For example, the composition ratio of La, Sr, Mn, and O is a compound containing Ta, Si, and O as component elements. May be La: Sr: Mn: O = 0.7: 0.3: 1: (3-x). Here, 0 ≦ x ≦ 0.3.
As the metal thin film used as the anodic bonding film 44, a metal thin film containing a metal that combines with oxygen constituting the glass substrate, for example, Ta, Ti, Al or the like can be used. The buffer film and anodic bonding film 44 are formed by sputtering, for example. Further, the getter material 21 may be provided on the upper surface of the second substrate 4 in a region corresponding to, for example, the carbon monoxide remover 21. The position where the getter material 21 is provided is preferably a position where the temperature of the getter material 21 does not exceed the activation temperature during operation of the reaction apparatus 10.

[Third board]
FIG. 7 is a top view of the third substrate 50 in the present embodiment, FIG. 8 is a bottom view of the third substrate 50, and FIG. 9 is a perspective view of the third substrate 50 as viewed obliquely from the lower left rear. As shown in FIGS. 7 to 9, the third substrate 50 includes a partition plate 52 and a rectangular frame 53 provided outside the partition plate 52.
The partition plate 52 and the frame 53 are integrally formed on the front side. At the joint between the partition plate 52 and the frame 53, six notches (51a, 51b, 51c, 51d, 51e, 51f from the left) are provided from the front end. As will be described later, the notches 51a, 51b, 51c, 51d, 51e, and 51f are combined with the notches 61a, 61b, 61c, 61d, 61e, and 61f provided on the fourth substrate, and the upper portion is the second substrate 40 and the lower portion. Are closed by the fifth substrate 70 in order from the left, the combustion fuel supply port 21a, the combustion air supply port 21b, the carbon monoxide removal air supply port 21c, the reforming fuel supply port 21d, and the exhaust gas discharge port 21e. Then, the reformed gas discharge port 21f is formed (see FIG. 2). In the central part of the partition plate 52, an opening 52a for forming the slit 19a is provided. A twisted through hole 52b is provided in front of the opening 52a. The through hole 52b is closed at the upper part by the second substrate 40 and at the lower part by the fourth substrate 60 to form the carbon monoxide removal channel 27 (CO remover 14).
Further, a twisted through hole 52c serving as the reformer 13 is provided behind the opening 52a. The through hole 52c is closed by the second substrate 40 at the top and the fourth substrate 60 at the bottom to form the reforming channel 24 (the reformer 13). A gap 53 a between the partition plate 52 and the frame body 53 forms the heat insulating chamber 19. The frame 53 is formed with triangular corners 50a, 50b, 50c at the left front corner, the left rear corner, and the right rear corner. A buffer film and an anodic bonding film 54 (see FIG. 4) are formed on the entire top surface of the third substrate 50 in the same manner as the second substrate 40.

As shown in FIGS. 8 and 9, the lower surface of the partition plate 52 has a groove 52f that allows the right end cutout 51f and one end of the through hole 52b to continue, and passes through the left side of the opening 52a from the other end of the through hole 52b. A groove 52g extending to one end of the hole 52c and a groove 52h extending from the other end of the through hole 52c to the right side of the opening 52a to the low temperature reaction part 12 are provided. The lower part of the groove 52f is closed by the fourth substrate 60 to become the discharge flow path 28, the lower part of the groove 52g is closed by the fourth substrate 60 to become the air mixing flow path 26, and the lower part of the groove 52h is the fourth substrate 60. The inlet channel 23b is blocked.
The air mixing channel 26 connects the reforming channel 24 and the carbon monoxide removal channel 27 and is connected to the air supply channel 25 by a through hole 62b provided in the fourth substrate 60, as will be described later. The Further, the introduction flow path 23b is connected to the reformed fuel supply flow path 23a through a through hole 62c provided in the fourth substrate 60, as will be described later.

Further, on the lower surface of the partition plate 52, concave portions 54 and 55 are formed at the right front corner portion and the rear end portion. As will be described later, the recesses 54 and 55 serve as terminal storage chambers in which the terminals 91a, 91b, 92a, and 92b of the heating wire patterns 91 and 92 provided on the fourth substrate 60 are disposed. Grooves 54a and 55a are provided between the recess 54 and the through hole 52b and between the recess 55 and the through hole 52c, respectively. In the grooves 54a and 55a, extended portions to terminals 91a, 91b, 92a and 92b of heating wire patterns 91 and 92 which will be described later are arranged.
Further, grooves 54b and 54b and grooves 55b and 55b that are parallel to the outer sides of the recesses 54 and 55, respectively, are formed on the lower surface of the partition plate 52, and grooves 54b, 54b, 55b, On the extension of 55b, parallel grooves 54c and 54c and grooves 55c and 55c are formed, respectively. In these grooves 54b, 54c, 55b, and 55c, lead wires 95a, 95b, 96a, and 96b are disposed, respectively, as will be described later. The lead wires 95a, 95b, 96a, 96b are connected to the terminals 91a, 91b, 92a, 92b of the heating wire patterns 91, 92 disposed in the terminal storage chamber, respectively.

[Fourth substrate]
FIG. 10 is a top view of the fourth substrate 60 in the present embodiment, and FIG. 11 is a bottom view of the fourth substrate 60.
As shown in FIGS. 10 to 11, the fourth substrate 60 includes a heater plate 62 and a rectangular frame 63 provided outside the heater plate 62. The heater plate 62 and the frame 63 are integrally formed on the front side. The connecting portion between the heater plate 62 and the frame 63 is provided with six notches (61a, 61b, 61c, 61d, 61e, 61f from the left) from the front end.

  At the center of the heater plate 62, an opening 62a for forming the slit 19a is provided. Further, on the front side of the opening 62a, a through hole 62b is formed at a position overlapping the groove 52g when the third substrate 50 is overlaid on the fourth substrate 60, and an end of the groove 52h opposite to the through hole 52c. A through hole 62c is provided at the overlapping position. A gap 63 a between the heater plate 62 and the frame 63 forms the heat insulation chamber 19. The frame 63 is formed with triangular corners 60b and 60c at the left rear corner and the right rear corner.

  On the upper surface of the fourth substrate 60, a heating wire pattern 91 that becomes the low temperature heater 16 and a heating wire pattern 92 that becomes the high temperature heater 17 are located at positions corresponding to the through holes 52b, 52c and the grooves 54a, 55a of the third substrate 50. The terminals 91a, 91b, 92a, 92b of the heating wire patterns 91, 92 are provided at positions corresponding to the recesses 54, 55. The heating wire patterns 91 and 92 are formed, for example, by patterning a metal thin film formed by sputtering using photolithography, etching, or the like.

  Further, on the upper surface of the fourth substrate 60, the second substrate 40 and the third substrate 50 are formed on the entire surface except positions corresponding to the through holes 52 b and 52 c, the grooves 54 a and 55 a, and the recesses 54 and 55 of the third substrate 50. Similarly to the above, a buffer film (not shown) and an anodic bonding film 64 are formed (see FIG. 12). Note that the same metal thin film as the buffer film or the anodic bonding film 64 may be used for part of the heating wire patterns 91 and 92, but the anodic bonding film 64 and the heating wire patterns 91 and 92 are not electrically connected.

  Further, on the upper surface of the fourth substrate 60, the through holes 52 b and 52 c, the grooves 54 a and 55 a, the grooves 52 g and 52 h, the grooves 54 b to 54 e, 55 b to 55 e, and the recesses 54 and 55 are formed in the third substrate 50. Then, an insulating film 94 is formed so as to cover the heating wire patterns 91 and 92 and the anode bonding film 64 and to expose the terminals 91a, 91b, 92a and 92b (see FIG. 13). Lead wires 95a, 95b, 96a, and 96b are disposed on the exposed portions of the terminals 91a, 91b, 92a, and 92b and on the insulating film 94 at positions corresponding to the grooves 54b to 54e and 55b to 55e. 91b, 92a, 92b and lead wires 95a, 95b, 96a, 96b are connected. As the lead wires 95a, 95b, 96a, 96b, for example, Kovar wires having a thermal expansion coefficient close to that of the low-melting glass sealing agent can be used. Further, an iron-nickel alloy wire or a dumet wire in which a core material of iron-nickel alloy is covered with a copper layer can also be used. The lead wires 95a, 95b, 96a, and 96b are insulated from the anodic bonding film 64 by the insulating film 94.

  Here, the anodic bonding film 64, the heating wire patterns 91 and 92 and the insulating film 94 are formed on the upper surface of the fourth substrate 60, and the procedure for connecting the lead wires 95a, 95b, 96a and 96b is shown in FIGS. It explains using. FIGS. 12 to 14 are perspective views of the fourth substrate 60 in the present embodiment as seen from the upper right front side.

  First, as shown in FIG. 12, a buffer film (not shown), an anode bonding film 64, and heating wire patterns 91 and 92 are formed on the upper surface of the fourth substrate 60. Next, as shown in FIG. 13, anodic bonding at positions where lead wires 95a, 95b, 96a, and 96b are disposed so as to cover heating wire patterns 91 and 92 except for terminals 91a, 91b, 92a, and 92b. An insulating film 94 is formed so as to cover the film 64. Thereafter, lead wires 95a, 95b, 96a, 96b are arranged and connected to the terminals 91a, 91b, 92a, 92b.

As shown in FIG. 11, a groove 62d is formed on the lower surface of the fourth substrate 60 behind the opening 62a. The lower part of the groove 62d is closed by the fifth substrate 70 to form the combustion flow path 22b (combustor 15).
Further, the lower surface of the fourth substrate 60 is connected to the notch 61a and the notch 61b, and a groove 62e is formed along the gap 63a through the left side of the through hole 62b and the opening 62a to the left end of the groove 62d. A groove 62f extends from the notch 61e along the gap 62a to the right end of the groove 62d through the right side of the through hole 62c and the opening 62a. The lower part of the groove 62e is closed by the fifth substrate 70 and becomes the combustion fuel mixing flow path 22a, and the lower part of the groove 62f is closed by the fifth board 70 and becomes the exhaust gas flow path 22c.
Further, a groove 62g extends from the notch 61c to the through hole 62b along the right side of the groove 62e, and a groove 62h extends from the notch 61d to the through hole 62c along the left side of the groove 62f. The lower part of the groove 62g is closed by the fifth substrate 70 and becomes the air supply flow path 25, and the lower part of the groove 62h is closed by the fifth substrate 70 and becomes the reformed fuel supply flow path 23a. The air supply channel 25 is connected to the air mixing channel 26 through the through hole 62b. The reformed fuel supply channel 23a is connected to the introduction channel 23b through the through hole 62c.

[Fifth substrate]
FIG. 15 is a top view of the fifth substrate 70 in the present embodiment. As shown in FIG. 15, the fifth substrate 70 includes a bottom plate 72 and a rectangular frame 73 provided outside the bottom plate 72. The bottom plate 72 and the frame body 73 are integrally formed on the front side. At the center of the bottom plate 72, an opening 72a for forming the slit 19a is provided. Further, the gap 73 a between the bottom plate 72 and the frame body 73 forms the heat insulation chamber 19. The frame body 73 is formed with a triangular chamfer 70b at the left rear corner. Similar to the second substrate 40, the third substrate 50, and the fourth substrate 60, the upper surface of the fifth substrate 70 corresponds to the through holes 62b and 62c and the grooves 62d, 62e, 62f, 62g, and 62h of the fourth substrate 60. A buffer film (not shown) and an anodic bonding film 74 (see FIG. 4) are formed on the entire surface except for the positions where they are formed.

[Sixth substrate]
FIG. 16 is a top view of the sixth substrate 80 in the present embodiment. The sixth substrate 80 has a rectangular plate shape, and as shown in FIG. 16, a protruding frame portion 81 is provided on the outer peripheral portion of the upper surface, and a concave portion 82 is formed inside the frame portion 81. The recess 82 forms a part of the heat insulation chamber 19. A buffer film (not shown) and an anodic bonding film 84 (see FIG. 4) are formed on the upper surface of the frame portion 81 in the same manner as the second substrate 40, the third substrate 50, the fourth substrate 60, and the fifth substrate 70. The In addition, the infrared reflection film (not shown) may be provided on the inner surface of the recess 82.

[Board bonding procedure]
Next, a procedure for joining the substrates 30 to 80 will be described. FIG. 17 is a perspective view showing a joining procedure between the third substrate 50 and the fourth substrate 60 in the present embodiment, and FIG. 18 is a perspective view showing a joining procedure between the second substrate 40 and the third substrate 50. FIG. 19 is a perspective view showing a procedure for joining the fourth substrate 60 and the fifth substrate 70, and FIG. 20 is a perspective view showing a procedure for joining the fifth substrate 70 and the sixth substrate 80. FIG. 21 is a perspective view showing a joining procedure between the first substrate 30 and the second substrate 40.
(1) Bonding of Third Substrate and Fourth Substrate First, as shown in FIG. 17, the lead wires 95a, 95b, 96a are formed on the fourth substrate 60 to which the lead wires 95a, 95b, 96a, 96b are connected. , 96b are overlaid on the third substrate 50 so that they are arranged at the positions of the grooves 54b, 54b, 55b, 55b, respectively. Then, the cathode 97 is brought into contact with the upper surface of the third substrate 50, the anode 98 is disposed on the corner drop portion 50 a so as not to contact the third substrate 50, and the anode 98 is brought into contact with the upper surface of the left front corner portion of the fourth substrate 60. Let Next, in the state heated to a predetermined temperature, a high voltage is applied between both electrodes, and both substrates 50 and 60 are anodic bonded. The bonding atmosphere is preferably bonded in an inert gas atmosphere or in vacuum in order to prevent the metal film surface formed on the third substrate 50 from being oxidized during bonding.
Thereafter, the gaps between the lead wires 95a, 95b, 96a, 96b and the grooves 54b, 54b, 55b, 55b are sealed with a low melting point glass sealant.

  Next, alumina sol as an adhesion layer of the catalyst is applied to the inner wall surfaces of the portions to be the combustion flow path 22b, the reforming flow path 24, and the carbon monoxide removal flow path 27 of both the substrates 50 and 60, and then the combustion is performed. A catalyst 65, a reforming catalyst 56, and a carbon monoxide selective oxidation catalyst 57 are formed by a wash coat method or the like (see FIG. 4).

(2) Bonding of Second Substrate and Third Substrate Next, as shown in FIG. 18, the second substrate 40 is disposed on the joined body of the third substrate 50 and the fourth substrate 60, and the second substrate 40. The anode 97 is brought into contact with the upper surface of the first substrate, the anode 98 is disposed on the corner drop portion 40f so as not to contact the second substrate 40, and the anode 98 is brought into contact with the upper surface of the left front corner portion of the third substrate 50. Then, a high voltage is applied between both electrodes, and the second substrate 40 and the third substrate 50 are anodically bonded. The bonding atmosphere is preferably bonded in an inert gas atmosphere or in vacuum in order to prevent the metal film surface formed on the second substrate 40 from being oxidized during bonding.

(3) Joining of Fourth Substrate and Fifth Substrate Next, as shown in FIG. 19, a joined body of the second substrate 40, the third substrate 50, and the fourth substrate 60 is disposed on the fifth substrate 70. The cathode 97 is disposed at the corners 40a and 50a so as not to contact the second substrate 40 and the third substrate 50, and is brought into contact with the upper surface of the left front corner of the third substrate 50. 50. An anode 98 is disposed on the corners 40c, 50c, 60c so as not to contact the fourth substrate 60, and the anode 98 is brought into contact with the upper surface of the right rear corner of the fifth substrate 70. And in the state heated to predetermined temperature, a high voltage is applied between both electrodes, and the 4th board | substrate 60 and the 5th board | substrate 70 are anodically bonded. The bonding atmosphere is preferably bonded in an inert gas atmosphere or in vacuum in order to prevent the metal film surface formed on the second substrate 40 from being oxidized during bonding.

(4) Joining of the fifth substrate and the sixth substrate Next, as shown in FIG. 20, the second substrate 40, the third substrate 50, the fourth substrate 60, and the fifth substrate 70 are placed on the sixth substrate 80. The joined body is disposed, and the cathode 97 is disposed on the corner drop portions 40c, 50c, 60c so as not to contact the second substrate 40, the third substrate 50, and the fourth substrate 60, and on the upper surface of the left front corner portion of the third substrate 50. An anode 98 is disposed on the corners 40b, 50b, 60b, 70b so as not to contact the second substrate 40, the third substrate 50, and the fourth substrate 60, and the upper surface of the left rear corner of the sixth substrate 80. Anode 98 is brought into contact with And in the state heated to predetermined temperature, a high voltage is applied between both electrodes, and the 5th board | substrate 70 and the 6th board | substrate 80 are anodically bonded. The bonding atmosphere is preferably bonded in an inert gas atmosphere or in vacuum in order to prevent the metal film surface formed on the second substrate 40 from being oxidized during bonding.

(5) Bonding of First Substrate and Second Substrate Next, as shown in FIG. 21, a joined body of a second substrate 40, a third substrate 50, a fourth substrate 60, a fifth substrate 70, and a sixth substrate 80. The first substrate 30 is disposed on the upper surface, the cathode 97 is brought into contact with the upper surface of the first substrate 30, and the anode 98 is disposed at the corner drop portion 30 d so as not to contact the first substrate 30. The anode 98 is brought into contact with the upper surface of the corner. And in the state heated to predetermined temperature, a high voltage is applied between both electrodes, and the 1st board | substrate 30 and the 2nd board | substrate 40 are anodically bonded. The bonding atmosphere is preferably bonded in an inert gas atmosphere or in a vacuum.
By the above, the reaction apparatus 10 which joined the 1st board | substrate 30, the 2nd board | substrate 40, the 3rd board | substrate 50, the 4th board | substrate 60, the 5th board | substrate 70, and the 6th board | substrate 80 can be formed. Here, when the first substrate 30 to the sixth substrate 80 are bonded by anodic bonding in a vacuum, the inside of the heat insulating chamber 19 and the slit 19a is vacuum-pressured simultaneously with the bonding of the first substrate 30 to the sixth substrate 80. It can be. Therefore, it is possible to save the labor of separately joining the first substrate 30 to the sixth substrate 80 and exhausting the heat insulation chamber 19 and the slit 19a, thereby reducing the manufacturing process of the reaction apparatus 10 and facilitating the manufacturing. Can be

<Modification 1>
FIGS. 22 and 23 show a modified flow channel structure as a modification of the first embodiment. FIG. 22 is a bottom view of the third substrate 50, and FIG. 23 is a bottom view of the fourth substrate 60. In the following modification, the same reference numerals are assigned to the same components as those in the first embodiment, and the description thereof is omitted.
In the first modification, as shown in FIG. 22, the fold-like through-hole 52 b of the first embodiment is divided in the third substrate 50 at 52 d and 52 e in the middle.

  Then, as shown in FIG. 23, through holes 62i and 62j are respectively provided at positions corresponding to the above-mentioned dividing locations 52d and 52e of the third substrate 50 on the lower surface of the fourth substrate 60, and the through holes 62i and 62j are provided. A kink-shaped groove 62k that connects the two is provided. The lower part of the groove 62k is closed by the fifth substrate 70, and becomes a carbon monoxide removal channel 27b (a part of the CO remover 14) communicating with the carbon monoxide removal channel 27 through the through holes 62i and 62j. The mixed gas from the air mixing passage 26 passes through the carbon monoxide removal passages 27a, 27b, and 27c in this order, and the reformed gas is discharged from the reformed gas discharge port 21f through the discharge passage 28. Thereby, the length of the flow path in the CO remover 14 can be increased without changing the external dimensions of the reaction apparatus 10.

<Modification 2>
In the first embodiment, the shape of the slit 19a is a rectangular parallelepiped shape, but the shape is not limited to this shape as long as the length of the connecting portion between the high temperature reaction portion 11 and the low temperature reaction portion 12 can be maintained sufficiently. For example, as shown in FIG. 24, the slit 19b (FIG. 24 (a)) in which the rear part of the low-temperature reaction part 12 is convex, and the slit 19c (FIG. b)), the rear part of the low temperature reaction part 12 and the front part of the high temperature reaction part 11 may be formed as a slit 19d (FIG. 24C). By doing so, the reforming flow path 24 and the carbon monoxide removal flow path 27 can be extended, and the space can be used effectively, so the reactor 10 can be downsized.

<Second Embodiment>
Next, a second embodiment of the present invention will be described. FIG. 25 is an exploded perspective view of the reactor 100 according to the second embodiment as viewed from the lower left front obliquely. Unlike the first embodiment, the reactor 100 is formed separately from the above-described heat insulating container 18, and is formed by sequentially stacking a lid plate 142, a partition plate 152, a heater plate 162, and a bottom plate 172. In addition, about the groove | channel etc. which form a flow path, since it is the same as that of the cover plate 42, the partition plate 52, the heater plate 62, and the bottom plate 72 of 1st Embodiment, the same code | symbol is attached | subjected and description is omitted.

[Cover plate]
FIG. 26 is a top view of the lid plate 142 in the present embodiment. At the rear end of the lid plate 142, triangular corners 40e and 40f are formed at the left and right corners, and a notch 40g is formed at the center.

(Partition plate)
FIG. 27 is a top view of the partition plate 152 in this embodiment, and FIG. 28 is a bottom view of the partition plate 152. At the rear end of the partition plate 152, triangular corners 50e and 50f are formed at the left and right corners.
A buffer film and an anodic bonding film (not shown) are formed on the upper surface of the partition plate 152 in the same manner as the partition plate 52 of the first embodiment.

[Heater plate]
FIG. 29 is a top view of the heater plate 162 in the present embodiment, and FIG. 30 is a bottom view of the heater plate 162. At the rear end portion of the heater plate 162, a triangular drop portion 60f is formed at the right corner.
A buffer film (not shown), an anodic bonding film 64, and heating wire patterns 91 and 92 are formed on the upper surface of the heater plate 162 in the same manner as the heater plate 62 of the first embodiment.

〔Bottom plate〕
FIG. 31 is a top view of the bottom plate 172 in the present embodiment. A buffer film and an anodic bonding film (not shown) are formed on the upper surface of the bottom plate 172 in the same manner as the bottom plate 72 of the first embodiment.

[Board bonding procedure]
Next, the joining procedure of the cover plate 142, the partition plate 152, the heater plate 162, and the bottom plate 172 will be described. Note that the bonding atmosphere for anodic bonding is preferably bonding in an inert gas atmosphere or in a vacuum.

(1) Joining of partition plate and heater plate First, on the heater plate 162 to which the lead wires 95a, 95b, 96a, 96b are connected, the lead wires 95a, 95b, 96a, 96b are grooves 54b, 54b, 55b, respectively. , 55b are overlapped so that they are arranged at positions 55b. Then, the cathode 97 is brought into contact with the upper surface of the partition plate 152, the anode 98 is disposed in the corner drop portion 50 e so as not to contact the partition plate 152, and the anode 98 is brought into contact with the upper surface of the left rear corner portion of the heater plate 162. Next, in the state heated to a predetermined temperature, a high voltage is applied between both electrodes, and the partition plate 152 and the heater plate 162 are anodically bonded. Thereafter, the gaps between the lead wires 95a, 95b, 96a, 96b and the grooves 54b, 54b, 55b, 55b are sealed with a low melting point glass sealant.

  Next, alumina sol as an adhesion layer of the catalyst is applied to the inner wall surfaces of the portions to be the combustion flow path 22b, the reforming flow path 24, and the carbon monoxide removal flow path 27 of both the substrates 50 and 60, and then the combustion is performed. A catalyst, a reforming catalyst, and a carbon monoxide selective oxidation catalyst are formed by a wash coat method or the like.

(2) Joining of lid plate and partition plate Next, the lid plate 142 is disposed on the joined body of the partition plate 152 and the heater plate 162, the cathode 97 is brought into contact with the upper surface of the lid plate 142, and the lid plate 142. The anode 98 is disposed in the notch 40g so as not to contact with the upper surface, and the anode 98 is brought into contact with the upper surface at the center of the rear end of the partition plate 152. And in the state heated to predetermined temperature, a high voltage is applied between both electrodes, and the lid plate 142 and the partition plate 152 are anodically bonded.

(3) Joining of heater plate and bottom plate Next, a joined body of a lid plate 142, a partition plate 152, and a heater plate 162 is disposed on the bottom plate 172, and a corner portion is formed so as not to contact the lid plate 142 and the partition plate 152. The cathode 97 is disposed at 40e and 50e and is brought into contact with the upper surface of the left front corner portion of the partition plate 152, and the anode 98 is disposed on the corner drop portions 40f, 50f and 60f so as not to contact the lid plate 142, the partition plate 152 and the heater plate 162. And the anode 98 is brought into contact with the upper surface of the left rear corner of the bottom plate 172. And in the state heated to predetermined temperature, a high voltage is applied between both electrodes, and the heater plate 162 and the baseplate 172 are anodically bonded.

<Modification 3>
FIG. 32 is an exploded perspective view of the reaction device 200 according to the modification of the second embodiment as viewed from the lower left front obliquely. The reactor 200 is formed by laminating a lid plate 242, a partition plate 252, a heater plate 262, and a bottom plate 272 in order.

  FIG. 33 is a perspective view showing the reaction device 200 in a state of being housed in the heat insulating container 18 according to this modification. In Modification 3, an input / output part 210 connected to the heat insulating container 18 is formed at the front end of the reaction container 200. The outer peripheral portion at the front end of the inlet / outlet portion 210 is sealed to the heat insulating container 18 with a low melting point glass sealing agent or the like. A gap between the reaction container 200 and the heat insulating container 18 becomes a heat insulating chamber 19.

34 is a top view of the cover plate 242 in this modification, FIG. 35 is a top view of the partition plate 252, FIG. 36 is a bottom view of the partition plate 252, FIG. 37 is a top view of the heater plate 262, and FIG. FIG. 39 is a top view of the bottom plate 272. FIG. Connection portions 244, 254, 264, and 274 are provided at the front end portions of the lid plate 242, the partition plate 252, the heater plate 262, and the bottom plate 272, respectively. The connecting portions 244, 254, 264, and 274 are stacked to form the input / output portion 210.
In addition, since it is the same as that of the reaction container 100 of 2nd Embodiment other than that, the same code | symbol is attached | subjected about the thing similar to 2nd Embodiment, and description is omitted.
Thus, by providing the inlet / outlet part 210 at the front end of the reaction container 200, the heat insulating container 18 may be integrated with the low melting point glass sealing agent or the like.

It is a block diagram of the electric power generating apparatus with which the reaction apparatus in this invention is used. It is a perspective view of the reaction device of a 1st embodiment. It is a disassembled perspective view of the reaction apparatus of 1st Embodiment. It is arrow sectional drawing along the II line of the reactor of 1st Embodiment. It is a top view of the 1st substrate in a 1st embodiment. It is a top view of the 2nd board | substrate in 1st Embodiment. It is a top view of the 3rd board in a 1st embodiment. It is a bottom view of the 3rd board in a 1st embodiment. It is the perspective view which looked at the 3rd board | substrate in 1st Embodiment from diagonally left lower back. It is a top view of the 4th substrate in a 1st embodiment. It is a bottom view of the 4th substrate in a 1st embodiment. It is the perspective view which looked at the 4th board | substrate in 1st Embodiment from diagonally upper right front. It is the perspective view which looked at the 4th board | substrate in 1st Embodiment from diagonally upper right front. It is the perspective view which looked at the 4th board | substrate in 1st Embodiment from diagonally upper right front. It is a top view of the 5th board in a 1st embodiment. It is a top view of the 6th substrate in a 1st embodiment. It is a perspective view which shows the joining procedure of the 3rd board | substrate and 4th board | substrate in 1st Embodiment. It is a perspective view which shows the joining procedure of the 2nd board | substrate and 3rd board | substrate in 1st Embodiment. It is a perspective view which shows the joining procedure of the 4th board | substrate and 5th board | substrate in 1st Embodiment. It is a perspective view which shows the joining procedure of the 5th board | substrate and 6th board | substrate in 1st Embodiment. It is a perspective view which shows the joining procedure of the 1st board | substrate and 2nd board | substrate in 1st Embodiment. It is a bottom view of the 3rd substrate in the modification of a 1st embodiment. It is a bottom view of the 4th substrate in the modification of a 1st embodiment. It is a top view which shows the other shape of the slit in 1st Embodiment. It is the disassembled perspective view which looked at the reactor of 2nd Embodiment from the left front diagonally downward. It is a top view of the cover board in 2nd Embodiment. It is a top view of the partition plate in 2nd Embodiment. It is a bottom view of the partition plate in 2nd Embodiment. It is a top view of the heater plate in 2nd Embodiment. It is a bottom view of the heater plate in 2nd Embodiment. It is a top view of the baseplate in 2nd Embodiment. It is the disassembled perspective view which looked at the reaction apparatus in the modification of 2nd Embodiment from the left front diagonally downward. It is a perspective view which shows the state accommodated in the heat insulation container of the reaction apparatus in the modification of 2nd Embodiment. It is a top view of the cover board in the modification of 2nd Embodiment. It is a top view of the partition plate in the modification of 2nd Embodiment. It is a bottom view of the partition plate in the modification of 2nd Embodiment. It is a top view of the heater plate in the modification of 2nd Embodiment. It is a bottom view of a heater plate in a modification of the second embodiment. It is a top view of the baseplate in the modification of 2nd Embodiment.

Explanation of symbols

11 High temperature reaction part (reaction vessel)
12 Low temperature reaction part (reaction vessel)
100, 200 Reaction vessel 42, 142, 242 Lid plate 52, 152, 252 Partition plate 56 Reforming catalyst (reaction catalyst)
57 Carbon monoxide selective oxidation catalyst (reaction catalyst)
62, 162, 262 Heater plate 72, 172, 272 Bottom plate 91, 92 Heating wire pattern 94 Insulating film

Claims (8)

In a reactor equipped with a reaction vessel that causes reaction of reactants,
The reaction vessel is
A heater plate having a heating wire pattern formed by a thin film heater on one surface;
On the side of the heater plate where the heating wire pattern is formed, a lid plate arranged in parallel with the heater plate,
A partition plate provided between the heater plate and the lid plate, having at least an opening along the heating wire pattern, and arranged to partition the space between the heater plate and the lid plate When,
On the one surface of the heater plate corresponding to the opening, an insulating film formed so as to cover the heating wire pattern;
Equipped with,
The opening is open to communicate with both outer surfaces of the partition plate;
A plurality of substrates including at least the lid plate, the partition plate, and the heater plate having a bonding layer between the upper substrate and the lower substrate. Each of the plurality of substrates has a slit portion that communicates with the sealed space, and accommodates the reaction vessel and the reaction vessel inside the sealed space and the slit portion. The surrounding portion is integrally formed, and the surrounding portion and the upper substrate and the lower substrate form a heat insulating container whose inside is decompressed,
Laminating the plurality of substrates, a supply port for supplying the reactant in the reaction vessel and a discharge port for discharging the product in the reaction vessel are formed,
Having a connection part for holding the reaction container in the heat insulating container at one end of the reaction container,
The said connection part has the said supply port and the said discharge port, The reaction apparatus characterized by the above-mentioned .   The reaction apparatus according to claim 1, wherein a reaction catalyst that promotes the reaction of the reactant is provided on at least the insulating film of the heater plate corresponding to the opening.   The reaction apparatus according to claim 2, wherein the reaction vessel is a reformer that reforms the reactant, and the catalyst is a reforming catalyst that promotes a reforming reaction. 3. The reaction vessel is a carbon monoxide remover that removes carbon monoxide contained in the reactant, and the catalyst is a carbon monoxide removal catalyst that promotes the oxidation of carbon monoxide. A reactor according to 1.   A recess is formed on the other surface of the heater plate opposite to the surface on which the heating wire pattern is formed, and a bottom plate for closing the recess is provided, and at least the heating wire pattern in the recess is opposed to the heating plate. The reaction apparatus according to any one of claims 1 to 4, wherein a combustion catalyst for combusting fuel supplied from the outside is provided on the surface to be operated.   The reaction apparatus according to claim 5, wherein the recess is formed corresponding to the opening. The reactor is
A first reaction section set at a first temperature and causing the reaction of the reactants;
A second reaction part set to a second temperature lower than the first temperature and causing the reaction of the reactant,
The reaction apparatus according to any one of claims 1 to 6 , wherein at least one of the first reaction unit and the second reaction unit includes the reaction vessel. A first product is generated from the first reactant supplied to the first reaction section,
The first product is supplied to the second reaction section, and a second product is produced from the first product;
The first reactant is an air-fuel mixture in which water and hydrocarbon liquid fuel are vaporized, and the first reaction section is a reformer that causes a reforming reaction of the first reactant. The first product includes hydrogen and carbon monoxide;
The reaction apparatus according to claim 7 , wherein the second reaction section is a carbon monoxide remover that removes carbon monoxide contained in the first product.

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