JP2005066509A - Production method for catalytic reactor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a production method for a catalytic reactor by which a catalyst can be carried in a groove at a high precision and deposited there without being damaged. <P>SOLUTION: The zigzag groove 56a is formed in one face 54a of a first substrate 54. A carrier film 70 is formed in the entire surface area of a face 54a of the first substrate 54 and a protection resin film 71 is formed on the carrier film 70. If the face 54a is polished, the carrier film 70 and the protection resin film 71 remain in the inner wall face of the groove 56a, meanwhile, the carrier film 70 and the protection resin film 71 are removed from the part other than the groove 56. Next, if the remaining protection resin film 71 is removed and a catalyst dispersion or a catalyst solution is applied to the face 54a, the catalyst is deposited on the position of the naked carrier film 70 of the groove 56a prior to the exposed part of the first substrate 54 so as to form a catalyst carrier film 59 on the groove 56a. Next, a second substrate 55 is joined to the face 54a of the first substrate 54. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a method of manufacturing a catalyst reactor in which a catalyst is provided in the groove of a first substrate having a groove formed on one surface.

  In recent years, research and development have been actively conducted on fuel cells that can achieve high energy use efficiency. BACKGROUND ART A fuel cell is a promising battery that is promising and promising because it directly extracts electric energy from chemical energy by electrochemically reacting fuel and oxygen in the atmosphere. The fuel used in the fuel cell includes hydrogen, but there is a problem in handling and storage due to being a gas at room temperature. Therefore, if liquid fuels such as alcohols and gasoline are used, the system for storing the liquid fuel becomes relatively small, but the hydrogen necessary for power generation is generated by heating and reacting the liquid fuel and water vapor to a high temperature. A reformer is required. When a fuel reforming type fuel cell is used as a power source for a small electronic device, it is necessary to downsize not only the fuel cell but also the reforming apparatus.

On the other hand, application of a catalyst to such a fuel cell reforming apparatus in order to remove unnecessary by-products such as carbon monoxide generated during reforming has been studied. There is what is described in.
JP-A-10-202101

  By the way, when the catalyst is supported in the flow path formed in the reformer, there is a problem that it is difficult to efficiently support the catalyst in the flow path because the flow path is fine. As a method of supporting the catalyst in the flow path relatively easily, there is a method in which a catalyst containing metal particles or the like is sprayed into a groove that forms a flow path formed on one substrate before bonding the two substrates. In addition to the fact that it is difficult for the catalyst to be sufficiently supported in the groove, it is difficult to spray the catalyst with the position accurately aligned only in the groove. For this reason, when the catalyst is supported on the bonding surface of the substrate other than the groove, not only the substrates cannot be bonded well, but also a fluid leaks from the flow path due to a gap generated between the substrates due to the catalyst. Has caused.

  Accordingly, the present invention has been made to solve the above-described problems, and provides a method for producing a catalytic reactor that can be supported by aligning the groove accurately without damaging the catalyst. For the purpose.

In order to solve the above problems, as in the invention described in claim 1, a step of forming a carrier film on the one surface of the first substrate having a groove formed on one surface;
Next, forming a protective film on the carrier film;
Next, the step of removing the protective film and the carrier film formed on the one surface other than the groove by polishing the one surface;
Next, removing the protective film remaining in the groove;
Next, a step of supporting the catalyst on the carrier film remaining in the groove by applying a catalyst-containing liquid containing the catalyst to the one surface;
The manufacturing method of the catalytic reactor containing this is provided.

In the first aspect of the invention, when the carrier film is formed on the surface on which the groove is formed, the carrier film is also formed on the inner wall surface of the groove, and when the protective film is formed on the carrier film, the groove is also interposed through the carrier film. Thus, a protective film is formed. Next, by simply polishing the surface, the protective film and the carrier film are removed at portions other than the groove, and the carrier film and the protective film can remain on the inner wall surface of the groove. Here, since the protective film is formed in the groove, the carrier film formed in the groove is not damaged during polishing.
Then, when the catalyst-containing liquid is applied to the surface where the groove is formed after removing the protective film remaining in the groove, the catalyst is preferentially supported on the carrier film remaining in the groove rather than the portion where the carrier film is removed. .

As in the invention according to claim 2, a step of forming a carrier film on the one surface of the first substrate having a groove formed on one surface;
Next, a step of supporting the catalyst on the carrier film by applying a catalyst-containing liquid containing a catalyst to the one surface;
Next, a step of forming a protective film on the carrier film carrying the catalyst;
Next, the step of removing the protective film and the carrier film formed on the one surface other than the groove by polishing the one surface;
Next, removing the protective film remaining in the groove;
The manufacturing method of the catalytic reactor containing this is provided.

  In the invention according to claim 2, when the carrier film is formed on the surface on which the groove is formed, the carrier film is also formed on the inner wall surface of the groove, and the catalyst is applied to the carrier film by applying the catalyst-containing liquid to the carrier film. Supported. When a protective film is formed on the carrier film carrying the catalyst, a protective film is also formed in the groove via the carrier film. Next, by simply polishing the surface, the protective film and the carrier film are removed at portions other than the groove, and the carrier film and the protective film can be left together with the catalyst on the inner wall surface of the groove. Here, since the protective film is formed in the groove, the carrier film formed in the groove is not damaged during polishing.

  According to a third aspect of the present invention, there is provided a method for producing a catalytic reactor according to the first or second aspect, wherein the carrier film is a metal oxide film.

  According to a fourth aspect of the present invention, in the catalyst reactor manufacturing method according to any one of the first to third aspects, the second substrate is moved to the first after the step of removing the protective film. Provided is a method for producing a catalytic reactor including a step of bonding to one surface of a substrate.

  In the invention according to claim 4, when the second substrate is joined to the surface on which the groove is formed, the groove becomes an internal space, and the catalyst is supported on the wall surface of the internal space.

  A method for producing a catalytic reactor according to any one of claims 1 to 4, as in the invention according to claim 5, wherein the protective film is a resin soluble in an alkaline solution. A manufacturing method is provided.

According to the first aspect of the present invention, since the protective film is formed in the groove at the time of polishing, the carrier film formed in the groove is not damaged, and therefore the carrier of the groove is satisfactorily damaged without damaging the catalyst. It can be supported on a membrane.
In addition, since the carrier film is removed in the portion other than the groove by polishing, the catalyst is preferentially supported on the carrier film in the groove, not on the portion from which the carrier film has been removed. Can be supported.
Further, since the catalyst does not remain in the portion deviated from the groove, there is almost no catalyst at the bonding interface when the second substrate is bonded to the first substrate. Therefore, it can be avoided that the bondability at the interface between the first substrate and the second substrate becomes weak.

According to the invention described in claim 2, since the protective film is formed in the groove at the time of polishing, the carrier film formed in the groove is not damaged, and the catalyst supported on the carrier film is not damaged. .
In addition, since the carrier film is removed in the portion other than the groove by polishing, the catalyst can be supported while accurately aligning with the groove.
Further, since the catalyst does not remain in the portion deviated from the groove, there is almost no catalyst at the bonding interface when the second substrate is bonded to the first substrate. Therefore, it can be avoided that the bondability at the interface between the first substrate and the second substrate becomes weak.

  According to invention of Claim 3, there exists an effect similar to the invention of Claim 1 or 2.

  According to the fourth aspect of the present invention, since the catalyst does not remain in the portion deviated from the groove, there is almost no catalyst at the bonding interface when the second substrate is bonded to the first substrate. Therefore, it can be avoided that the bondability at the interface between the first substrate and the second substrate becomes weak.

  According to invention of Claim 5, if an alkaline solution is apply | coated to a protective film, a protective film can be removed.

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

  FIG. 1 is a perspective view showing a fuel cell type power generation system 1 incorporating a catalytic reactor manufactured by the manufacturing method of the present invention, with a part thereof broken.

  As shown in FIG. 1, a fuel cell power generation system 1 includes a fuel storage module 2 that stores fuel 9, a reforming reactor 42 that is a catalytic reactor manufactured by the manufacturing method of the present invention, and an aqueous shift reactor. And a power generation module 3 that generates power using the fuel 9 stored in the fuel storage module 2.

  The fuel storage module 2 has a substantially cylindrical casing 4, and the casing 4 is detachably attached to the power generation module 3. A circular through hole 5 is formed at the top of the casing 4, and a first drain pipe 6 for circulating the by-product water generated by the power generation module 3 is provided on the outer peripheral side of the casing 4. Is formed. A drainage container 7 (shown in FIG. 2) for storing drainage water is disposed at the bottom of the fuel storage module 2, and the first drainage pipe 6 is connected to the drainage container 7.

  A fuel tank 8 is housed inside the housing 4, and a part of the outer peripheral surface of the fuel tank 8 is exposed to the outside of the housing 4. Liquid fuel 9 is stored inside the fuel tank 8. The fuel tank 8 is a transparent or translucent columnar member having an internal space, and is made of a material such as polyethylene, polypropylene, polycarbonate, or acrylic. Since part of the fuel tank 8 is exposed and the fuel tank 8 is transparent or translucent, the presence / absence and the remaining amount of the internal fuel 9 can be easily confirmed through the fuel tank 8.

  The fuel 9 is a liquid mixture of a liquid chemical fuel and water. As the chemical fuel, alcohols such as methanol and ethanol, and compounds containing hydrogen elements such as gasoline are applicable. In the present embodiment, a mixed liquid in which methanol and water are mixed is used as the fuel 9.

  A supply port 10 for supplying the fuel 9 to the power generation module 3 protrudes from the top of the fuel tank 8 and is inserted into the through hole 5 of the housing 4. Inside, a blocking film 11 that blocks the entire supply port 10 is disposed. Inside the fuel tank 8, a supply pipe 12 extending in the vertical direction in FIG. 1 and inserted into the supply port 10 is disposed. The supply pipe 12 extends from the bottom of the fuel tank 8 to a position immediately below the blocking film 11 in the supply port 10. The supply port 10 is blocked by the blocking film 11, thereby preventing the fuel 9 from leaking from the fuel tank 8 to the outside.

Next, the power generation module 3 will be described.
The power generation module 3 includes a substantially cylindrical housing 30, a small reformer 40 disposed inside the housing 30, and a peripheral portion of the housing 30 around the small reformer 40. A fuel cell 91 provided.

  A plurality of slits 13, 13,... For inhaling air in the atmosphere are formed outside the fuel cell 91 and in parallel with each other on the outer peripheral surface of the housing 30.

  A terminal 32 for supplying electric energy to an external device is disposed on the top of the housing 30, and by-product dioxide dioxide is provided around the terminal 32 and on the top of the housing 30. A plurality of ventilation holes 33, 33,... For exhausting carbon, water vapor, and the like are formed.

A second drain pipe 34 is disposed on the outer peripheral side of the housing 30. The second drain pipe 34 projects downward from the bottom of the housing 30 and is disposed at a position corresponding to the first drain pipe 6 of the fuel storage module 2. The second drain pipe 34 is for circulating the by-product water generated in the fuel cell 91, and the by-product water is drained to the drainage container 7 through the second drain pipe 34 and the first drain pipe 6. It has come to be.
Further, a valve 35 is disposed in the second drain pipe 34, and a water introduction pipe 36 provided in the housing 30 communicates with the second drain pipe 34 via the valve 35. The valve 35 and the water introduction pipe 36 are used to introduce by-product water produced in the fuel cell 91 into the small reformer 40 as necessary, and thereby the chemical contained in the fuel 9 in the fuel tank 8. The fuel concentration can be increased.

  A suction nipple portion 37 is disposed at the bottom portion of the housing 30 at the center thereof so as to protrude downward. The suction nipple portion 37 is formed with a flow path penetrating from the tip along the center line. The suction nipple portion 37 is disposed at a position corresponding to the through hole 5 of the fuel storage module 2 and is for sucking the fuel 9 from the fuel tank 8.

  In the fuel storage module 2 and the power generation module 3 as described above, when the fuel storage module 2 containing the fuel tank 8 is attached to the power generation module 3, the power generation module 3 is connected to the outer peripheral side of the connecting portion between the modules 2 and 3. Two drain pipes 34 are connected to the first drain pipe 6 of the fuel storage module 2. As a result, the second drain pipe 34 communicates with the first drain pipe 6, and the by-product water generated by the power generation module 3 is circulated from the second drain pipe 34 to the first drain pipe 6 to be a drain container. 7 is ready to be discharged.

  On the other hand, in the central portion of the connection location between the modules 2 and 3, the suction nipple portion 37 of the power generation module 3 is inserted into the through hole 5 of the fuel storage module 2 and the supply port 10 of the fuel tank 8. Break through 11. As a result, the suction nipple portion 37 communicates with the supply pipe 12 of the fuel tank 8, and the fuel 9 stored in the fuel tank 8 can be supplied from the supply pipe 12 to the suction nipple portion 37.

  Next, the small reformer 40 built in the power generation module 3 will be described with reference to FIGS. Here, FIG. 2 is a block diagram showing the configuration of the fuel cell power generation system 1, and FIG. 3 is a cross-sectional view showing the small reformer 40 in a broken view.

  As shown in FIGS. 2 and 3, the small reformer 40 includes an evaporator 41 for evaporating the fuel 9 supplied from the fuel tank, and hydrogen gas and carbon dioxide gas from the fuel 9 vaporized by the evaporator 41. A reforming reactor 42 for generating gas, an aqueous shift reactor 43 for generating carbon dioxide and hydrogen gas from carbon monoxide gas and water contained in the gas mixture supplied from the reforming reactor 42, A selective oxidation reactor 44 for oxidizing the carbon monoxide gas contained in the air-fuel mixture supplied from the aqueous shift reactor 43 to remove the carbon monoxide gas. The evaporator 41, the reforming reactor 42, the aqueous shift reactor 43, and the selective oxidation reactor 44 are stacked in this order.

  The evaporator 41, the reforming reactor 42, the aqueous shift reactor 43, and the selective oxidation reactor 44 all have a reaction vessel body 50 that forms an internal space for the reaction, and the reaction vessel body 50 and its internal space are heated. For this purpose, a heater 51 provided on the outer wall of the reaction vessel main body 50 and a heat insulating package 52 containing the reaction vessel main body 50 and the heater 51 are provided.

  All the heat insulation packages 52 of the evaporator 41, the reforming reactor 42, the aqueous shift reactor 43, and the selective oxidation reactor 44 are formed of a heat insulating material having a relatively low thermal conductivity such as glass. On the inner wall of the heat insulation package 52, a radiation reflection film (not shown) made of Au, Ag, Al or the like is formed. The radiation reflecting film reflects the electromagnetic wave including infrared rays with high reflectivity, and heat is transmitted to the heat insulating package 52 by the electromagnetic wave emitted from the internal reaction vessel body 50 being reflected by the radiation reflecting film. Is suppressed. Thereby, it is possible to prevent radiant heat due to electromagnetic waves from radiating outside the heat insulating package 52.

  Further, in any of the evaporator 41, the reforming reactor 42, the aqueous shift reactor 43, and the selective oxidation reactor 44, the internal space in the heat insulation package 52 is provided in a vacuum, or the interior in the heat insulation package 52 The space is filled with methane or ethane polyhalogenated derivative gas (Freon (trade name) gas) or carbon dioxide containing fluorine. Examples of the methane or ethane polyhalogenated derivative gas containing fluorine include trichlorofluoromethane and dichlorodifluoromethane.

  In each of the evaporator 41, the reforming reactor 42, the aqueous shift reactor 43, and the selective oxidation reactor 44, supports 53, 53,... Are disposed at the respective corners of the inner wall of the heat insulation package 52. ing. The reaction vessel main body 50 is disposed inside the heat insulation package 52 so as to be separated from the inner wall of the heat insulation package 52 while being supported by each support 53.

  The reaction vessel body 50 of each of the evaporator 41, the reforming reactor 42, the aqueous shift reactor 43, and the selective oxidation reactor 44 has two substrates 54 and 55 formed of a material such as silicon crystal, aluminum, or glass. Are superposed on each other and joined together. 4 shows a perspective view of the reaction vessel main body 50. As shown in this figure, the joint portion between the first substrate 54 and the second substrate 55 has a twisted shape along the joint surface. The micro flow path 56 is formed. As shown in FIG. 3, the cross-sectional shape perpendicular to the longitudinal direction of the microchannel 56 has an arch shape. The first substrate 54 and the second substrate 55 must be sufficiently bonded at the bonding portion so that the fluid flowing in the microchannel 56 does not leak. For this purpose, the first substrate 54 and the second substrate 55 are bonded by anodic bonding. In order to seal well, it is preferable that one is a silicon substrate and the other is a glass substrate.

  5A is a plan view showing one surface 54a of the first substrate 54 before bonding, and FIG. 5B is a plan view showing the other surface 54b of the first substrate 54. As shown in FIG. On one surface 54a of the first substrate 54, a crease-like groove 56a is formed. Specifically, the grooves 56a are alternately arranged such that the vertical straight portions 56b that are long in the vertical direction and the horizontal straight portions 56c that are long in the horizontal direction go from one end of the groove 56a to the other end. It is formed to be continuous. The microchannel 56 is formed by bonding the first substrate 54 and the second substrate 55 with the surface 54a of the first substrate 54 on the groove 56a side facing the second substrate 55, and the second substrate 55 is joined. The groove 56 a covered with 55 becomes the microchannel 56. The groove 56a as the microchannel 56 is formed by appropriately applying a photolithography method, an etching method, or the like to one surface 54a of the first substrate 54.

  On the other surface 54 b of the first substrate 54, that is, on the outer wall of the reaction vessel main body 50, a twisted heater 51 is formed. The heater 51 is formed by forming an electric resistance heating element and a semiconductor heating element in a thin film shape, and generates heat by electric energy when a current flows or a voltage is applied. Lead wires (not shown) are respectively connected to both ends of the twisted heater 51, and both lead wires extend through the heat insulating package 52 to the outside and are connected to the heater 51 through the lead wires. Electric energy is supplied. The portion where the lead wire penetrates is sealed, so that gas does not leak between the internal space of the heat insulation package 52 and the outside.

  As shown in FIGS. 3 and 4, an inflow pipe 57 is connected to one end of the micro flow path 56, and an outflow pipe 58 is connected to the other end of the micro flow path 56. Yes. The inflow pipe 57 extends through the second substrate 55 and the heat insulation package 52 from the reaction vessel main body 50 to the outside of the heat insulation package 52. The outflow pipe 58 also passes through the first substrate 54 and the heat insulation package 52 and extends from the reaction vessel main body 50 to the outside of the heat insulation package 52.

  The inflow pipe 57 of the evaporator 41 communicates with the suction nipple portion 37 shown in FIG. 1, and the fuel 9 stored in the fuel tank 8 is supplied to the micro flow path 56 through the suction nipple portion 37 and the inflow pipe 57. It has come to be. A pump (not shown) is provided between the inflow pipe 57 of the evaporator 41 and the suction nipple portion 37, and the flow rate of the fuel 9 flowing into the inflow pipe 57 of the evaporator 41 can be adjusted by this pump. It is like that.

  The outflow pipe 58 of the evaporator 41 communicates with the inflow pipe 57 of the reforming reactor 42, and the outflow pipe 58 of the reforming reactor 42 communicates with the inflow pipe 57 of the aqueous shift reactor 43. 43 is connected to an inflow pipe 57 of the selective oxidation reactor 44. The outflow pipe 58 of the selective oxidation reactor 44 leads to a fuel electrode of a fuel cell 91 described later.

  An air inflow pipe 60 communicates with the micro flow path 56 of the selective oxidation reactor 44, and the air inflow pipe 60 extends through the heat insulating package 52 to the outside. The air inflow pipe 60 leads to the slit 13 through a valve or a pump, and the outside air is supplied to the micro flow path 56 of the selective oxidation reactor 44 through the slit 13 and the air inflow pipe 60. Yes.

  In any of the reaction vessel main bodies 50 of the reforming reactor 42, the aqueous shift reactor 43, and the selective oxidation reactor 44, a catalyst supporting film 59 of metal, metal oxide or the like is provided on the inner wall surface of the microchannel 56. . The catalyst supporting film 59 is obtained by dispersing a catalyst on a carrier and supporting the catalyst on the carrier. As the carrier, a porous substance such as a metal oxide can be used. As the catalyst, one or more metal species, one or more metal oxides, or a combination of these metal species and metal oxides can be used. In particular, the catalyst contained in the catalyst supporting film 59 is a heterogeneous catalyst.

  Further, between the reforming reactor 42, the aqueous shift reactor 43, and the selective oxidation reactor 44, the catalyst supporting film 59 may be formed of the same material or may be formed of different materials. In any of the reforming reactor 42, the aqueous shift reactor 43, and the selective oxidation reactor 44, the catalyst supporting film 59 of one reactor may be formed of one kind of material, or a plurality of kinds of materials. It may be formed and differ depending on the location in the microchannel 56.

In particular, the catalyst supporting film 59 of the reforming reactor 42 supports a catalyst that promotes the generation of carbon dioxide and water by reacting methanol and water as in chemical reaction formula (1).
CH ₃ OH + H ₂ O → 3H ₂ + CO ₂ (1)

On the other hand, the catalyst supporting film 59 of the aqueous shift reactor 43 supports a catalyst that promotes the generation of carbon dioxide and hydrogen by reacting carbon monoxide and water as in chemical reaction formula (2). .
CO + H ₂ O → CO ₂ + H ₂ (2)

Further, carbon monoxide in the air-fuel mixture is selected for the catalyst supporting film 59 of the selective oxidation reactor 44 as shown in the chemical reaction formula (3), and carbon monoxide and oxygen are reacted to generate carbon dioxide. A catalyst for promoting this is supported.
2CO + O ₂ → 2CO ₂ (3)

  In this embodiment, the catalyst support film is not provided on the inner wall surface of the micro flow path 56 of the evaporator 41. However, the catalyst support film that promotes the reaction of the chemical reaction formula (1) is a micro flow of the evaporator 41. It may be provided on the inner wall surface of the path 56.

  Next, the fuel cell 91 will be described. The fuel cell 91 includes a fuel electrode (cathode) carrying catalyst fine particles, an air electrode (anode) carrying catalyst fine particles, and a film-like ion conductive membrane sandwiched between the fuel electrode and the air electrode. Are provided.

In the fuel cell 91, as shown in the electrochemical reaction formula (4), when hydrogen gas is supplied to the fuel electrode, hydrogen ions from which electrons are separated are generated by the catalyst of the fuel electrode, and the hydrogen ions are ion-conducting membrane. It is conducted to the air electrode through, and electrons are taken out from the fuel electrode.
3H ₂ → 6H ⁺ + 6e ⁻ (4)
On the other hand, as shown in the electrochemical reaction equation (5), when oxygen gas is supplied to the air electrode, hydrogen ions that have passed through the ion conductive film, oxygen gas, and electrons react to generate water as a by-product. It is generated as a product.
6H ⁺ + 3 / 2O ₂ + 6e ⁻ → 3H ₂ O (5)
Electrical energy is generated by the electrochemical reaction as described above occurring in the fuel cell 91.

  Next, a method for producing the evaporator 41, the reforming reactor 42, the aqueous shift reactor 43, and the selective oxidation reactor 44 will be described with reference to FIGS. The catalytic reactor production method of the present invention is applied to the shift reactor 43 and the selective oxidation reactor 44.

  First, for each of the evaporator 41, the reforming reactor 42, the aqueous shift reactor 43, and the selective oxidation reactor 44, square or rectangular substrates 54 and 55 that are flat on both sides are prepared.

  A mask (resist) is applied to one surface 54a of the first substrate 54 by a photolithography method, but the shape of the portion not covered by the mask, that is, the portion exposed on the one surface 54a of the first substrate 54 is twisted. It is made into a shape. Then, by etching the one surface 54a of the first substrate 54, the exposed part of the one surface 54a of the first substrate 54 is removed. By the shape processing by such photolithography method / etching method, a groove 56a having a fold shape and a cross-sectional arch shape is formed on one surface 54a of the first substrate 54. Thereafter, the mask is removed (shown in FIG. 6A or FIG. 7A). The groove 56a may be formed by grinding, blasting, other mechanical methods, or chemical methods, without depending on the photolithography method or the etching method. Alternatively, the first substrate 54 having the grooves 56a may be formed in advance by an injection molding method, a mold molding method, or other molding methods.

  Next, each of the reforming reactor 42, the aqueous shift reactor 43 and the selective oxidation reactor 44 is formed on the inner wall surface of the groove 56a in one of the following two methods (method 1 and method 2). A catalyst support film 59 is formed.

[Method 1]
First, as shown in FIG. 6B, the carrier film 70 is formed on the entire surface 54a (including the inner wall surface of the groove 56a) on which the groove 56a of the first substrate 54 is formed. Here, when the carrier film 70 is formed from a metal oxide such as alumina, asbestos, or diatomaceous earth, the formed carrier film 70 is porous and its surface area is much larger than the apparent area. Examples of the film formation method of the carrier film 70 include a sol-gel method, a vapor phase growth method (CVD method, PVD method, sputtering method, etc.), and other coating methods. Further, a metal film is formed on one surface 54a of the first substrate 54 by a vapor deposition method or the like, and the metal film is oxidized by a thermal oxidation method, an anodic oxidation method or the like, thereby forming a carrier film 70. Also good. Among these film forming methods, the sol-gel method and the vapor phase growth method-anodizing method are suitable for increasing the surface area of the carrier film 70.

  Hereinafter, a method for forming the carrier film 70 by the sol-gel method will be specifically described. First, aluminum isopropoxide is dissolved in water to prepare an aqueous solution of aluminum isopropoxide having a concentration of 0.1 to 2 mol / l. Next, when the prepared aqueous solution is heated, hydrolysis occurs in the aqueous solution, which decomposes into aluminum hydroxide fine particles and isopropyl alcohol to obtain a sol. Here, the particle size of aluminum hydroxide can be prepared according to the heating temperature and the holding time of the heating temperature, but when the solution is held at 80 ° C. for 24 hours, the particle size of aluminum hydroxide of about 10 nm is obtained. be able to. Then, after the generated isopropyl alcohol is sufficiently volatilized, a stabilizer is added to the sol in order to stop the growth of aluminum hydroxide particles. The stabilizer to be used may be an acid or an alkali, but by adding 0.1 mol of nitric acid to 1 mol of aluminum hydroxide, the growth of aluminum hydroxide particles is stopped. The sol thus prepared is cooled to room temperature, and the first substrate 54 on which the grooves 56a are formed is immersed in the sol (dip coating method). Then, after the first substrate 54 is lifted from the sol, the first substrate 54 is fired at 360 ° C. in an atmosphere (air) in which oxygen is present, so that the boehmite film that is a precursor of γ-alumina is a carrier film. 70 is obtained.

  Next, the protective resin film 71 is formed on the entire surface of the carrier film 70 by a screen printing method, a roll coating method, a spin coating method, a dip coating method, a droplet discharge method (dispenser method, ink jet method), or other coating methods. A film is formed (FIG. 6C). The protective resin film 71 is preferably a resin that is soluble in an alkaline solution so that the catalyst is not damaged, and is preferably removable by oxygen plasma. For example, the PMER (alkali developing negative or positive type Tokyo Ohka Kogyo Co., Ltd.) series is used. is there. The thickness of the protective resin film 71 is preferably at least twice the film thickness of the carrier film 70, more desirably thick enough to fill the groove 56 a with the protective resin film 71, and further covering the carrier film 70. It is most desirable to increase the thickness of the protective resin film 71 deposited without a gap until the surface becomes flat. Here, when the resin to be applied is a thermosetting resin, the protective resin film 71 is formed by heating and curing the resin after application. When the resin to be applied is an ultraviolet curable resin, the resin is applied. The protective resin film 71 is formed by irradiating and curing the resin with ultraviolet rays later. Further, as the protective resin film 71, a resist used in a photoresist method can be used. The protective resin film 71 may be formed only on the surface of the groove 56a without forming the protective resin film 71 on the entire surface. However, it is easier to form the protective resin film on the entire surface, and polishing is performed in a polishing process described later. The surface can be prevented from tilting.

  When the protective resin film 71 is formed, the surface on which the protective resin film 71 is formed is any one of mechanical polishing, chemical polishing, and mechanical mechanical polishing. Polishing. Here, the degree of polishing is such that the protective resin film 71 and the carrier film 70 in a portion other than the groove 56a of the one surface 54a of the first substrate 54 are removed. That is, polishing is performed to such an extent that the protective resin film 71 and the carrier film 70 remain on the inner wall surface of the groove 56a, but polishing is not performed to smooth the one surface 54a of the first substrate 54 and remove the groove 56a. . Therefore, as shown in FIG. 6D, the first substrate 54 is exposed at a portion other than the groove 56a in the one surface 54a of the first substrate 54, and the protective resin film 71 is exposed at the groove 56a. By polishing at this time, a portion other than the groove 56a in the one surface 54a of the first substrate 54 may be mirror-finished. Thus, since the polishing is performed with the carrier film 70 covered with the protective resin film 71, the carrier film 70 formed in the groove 56a is damaged by abrasives, wear powder, and other foreign matters during polishing. There is no.

  Next, the protective resin film 71 remaining in the groove 56a is removed (FIG. 6E). As a method for removing the protective resin film 71, a method in which the first substrate 54 is immersed in a removing solution such as an alkaline solution to remove the protective resin film 71 with the removing solution, or an oxygen plasma treatment is performed on the first substrate 54. There is a method of removing the protective resin film 71 by doing so. In particular, the removal by the oxygen plasma treatment is a desirable method because the protective resin film 71 is selectively carbonized and removed because the carrier film 70 is chemically stable against oxygen plasma. The removal liquid is selected according to the type of the protective resin film 71.

  Next, the first substrate 54 is immersed in a catalyst dispersion in which a catalyst such as metal or metal oxide is dispersed or a catalyst solution in which the catalyst is dissolved (dip coating method). Since the exposed portion of the first substrate 54 is dense and the carrier film 70 has a larger surface area than the first substrate 54, the catalyst is preferentially supported on the carrier film 70 rather than the first substrate 54. Therefore, when the catalyst is supported on the support film 70, the support film 70 becomes the catalyst support film 59, and the catalyst support film 59 is formed only on the inner wall surface of the groove 56a as shown in FIG. 6 (f). Since the catalyst support film 59 is distributed on the surface of the porous support film 70, the surface area is larger than it appears. A catalyst dispersion or catalyst solution is prepared for each of the reforming reactor 42, the aqueous shift reactor 43, and the selective oxidation reactor 44. For the chemical reaction formula (1), for the aqueous shift reactor 43, for the chemical reaction formula (2), for the selective oxidation reactor 44, the chemical reaction formula (3) Use something to promote. In addition, if the catalyst dispersion or the catalyst solution is applied to the one surface 54a of the first substrate 54, the spin coating method, the roll coating method, the droplet discharge method (inkjet method), the dispenser, regardless of the dip coating method. A catalyst dispersion or catalyst solution may be applied to the surface 54a of the first substrate 54 by a method. In any coating method, the catalyst is preferentially supported on the carrier film 70 rather than the first substrate 54.

[Method 2]
In Method 1, polishing is performed after forming the protective resin film 71, and then the catalyst is supported on the carrier film 70. On the other hand, in Method 2, after the catalyst is supported on the carrier film 70 formed on one surface, the protective resin film 71 is formed, and then the polishing is performed.

  Specifically, first, as in the case of the above method 1, as shown in FIG. 7B, the surface 54a (including the inner wall surface of the groove 56a) on which the groove 56a of the first substrate 54 is formed is included. The carrier film 70 is formed on the entire surface.

  Next, as in the case where the catalyst is supported on the support film 70 in the method 1, one surface of the surface 54a of the first substrate 54 is dissolved in a catalyst dispersion in which a catalyst such as metal or metal oxide is dispersed or in a catalyst solution in which the catalyst is dissolved. When applied by dip coating or the like, the catalyst is supported on the carrier film 70, and the catalyst supporting film 72 is formed on one surface (including the inner wall surface of the groove 56a). Of course, the catalyst material promotes the chemical reaction formula (1) for the reforming reactor 42, and promotes the chemical reaction formula (2) for the aqueous shift reactor 43, selective oxidation. For the reactor 44, one that promotes the chemical reaction formula (3) is used.

  Next, the protective resin film 71 is placed on the entire surface of the catalyst support film 72 by a screen printing method, a roll coating method, a spin coating method, a dip coating method, a droplet discharge method (dispenser method, ink jet method), or other coating methods. A film is formed (FIG. 7D). The thickness of the protective resin film 71 may be at least twice the film thickness of the catalyst support film 72, and is more preferably thick enough to fill the groove 56a with the protective resin film 71. The protective resin film 71 may be formed only on the portion corresponding to the groove 56a without forming the protective resin film 71 on the entire surface.

  Next, polishing such as mechanical polishing, chemical polishing, and mechanical chemical polishing is performed on one surface 54a of the first substrate 54. Here, the degree of polishing is such that the protective resin film 71 and the catalyst-carrying film 72 are removed from the one surface 54a of the first substrate 54 other than the groove 56a. That is, polishing is performed to such an extent that the protective resin film 71 and the catalyst support film 72 remain on the inner wall surface of the groove 56a, and polishing is not performed to smooth the one surface 54a of the first substrate 54 and remove the groove 56a. . Accordingly, as shown in FIG. 7E, the first substrate 54 is exposed at a portion other than the groove 56a in the one surface 54a of the first substrate 54, and the protective resin film 71 is exposed at the groove 56a. The catalyst supporting film 72 remaining in the groove 56a becomes the catalyst supporting film 59 shown in FIG. The exposed portion of one surface 54a of the first substrate 54 may be mirror-finished by polishing at this time. Thus, since the catalyst carrying film 72 is covered with the protective resin film 71 and polished, the catalyst carrying film 72 formed in the groove 56a is damaged by polishing agent, wear powder, and other foreign matters during polishing. There is nothing to do.

  Next, as in the case of Method 1, the protective resin film 71 remaining in the groove 56a is removed by a removing solution or oxygen plasma (FIG. 7F).

  After performing the above method 1 or method 2, the first substrate 54 is cleaned. Next, as shown in FIGS. 6 (g) and 7 (g), the groove 56a of the first substrate 54 is formed in each of the evaporator 41, the reforming reactor 42, the aqueous shift reactor 43, and the selective oxidation reactor 44. The first substrate 54 is bonded to the second substrate 55 with the formed surface 54 a facing the second substrate 55. An example of the bonding method is an anodic bonding method. Thus, the micro flow channel 56 is formed, and the reaction vessel main body 50 is completed. In addition, since the method 1 and the method 2 are not performed on the reaction vessel main body 50 of the evaporator 41, the catalyst supporting film is not formed in the micro flow path 56.

  The twisted heater 51 is formed on the other surface 54b of the first substrate 54 by appropriately performing a film forming method such as a CVD method, a PVD method, or a sputtering method, a photolithography method, and an etching method.

  A through hole (not shown) is formed in a portion of the second substrate 55 corresponding to one end of the groove 56a, and a through hole (not shown) is formed in the other end of the groove 56a in the first substrate 54. Abbreviation). The through hole 57a formed in the second substrate 55 is for inserting the inflow pipe 57, and the through hole formed in the first substrate 54 is for inserting the outflow pipe 58.

  Next, for each of the evaporator 41, the reforming reactor 42, the aqueous shift reactor 43, and the selective oxidation reactor 44, the inflow pipe 57 is inserted into the through hole 57 a of the second substrate 55, and the through hole of the first substrate 54 is inserted. The outflow pipe 58 is inserted, and a lead wire is further connected to the heater 51. For the selective oxidation reactor 44, an air inflow pipe 60 is also connected to the micro flow path 56. Thereafter, when the reaction vessel body 50 is packaged with the heat insulation package 52 so that the inflow pipe 57, the outflow pipe 58, and the lead wires extend from the inside of the heat insulation package 52 to the outside, the evaporator 41, the reforming reactor 42, the aqueous solution The shift reactor 43 and the selective oxidation reactor 44 are completed. Next, the evaporator 41, the reforming reactor 42, the aqueous shift reactor 43 and the selective oxidation reactor 44 are stacked in order, and the outlet pipe 58 of the evaporator 41 is connected to the inlet pipe 57 of the reforming reactor 42. The outflow pipe 58 of the quality reactor 42 is connected to the inflow pipe 57 of the aqueous shift reactor 43, and the outflow pipe 58 of the aqueous shift reactor 43 is connected to the inflow pipe 57 of the selective oxidation reactor 44. Thus, the small reformer 40 is completed. When the small reformer 40, the casing 30, the fuel cell 91, and the like are assembled, the power generation module 3 is completed.

Next, the effect of this embodiment will be described.
In the method (1), when the carrier film 70 is formed on one surface 54a of the first substrate 54, the carrier film 70 is also formed on the inner wall surface of the groove 56a, and then when the protective resin film 71 is formed, the carrier film 70 is also formed on the groove 56a. A protective resin film 71 is formed. Thereafter, when the surface 54a is polished, the carrier film 70 and the protective resin film 71 are removed at portions other than the groove 56a, and the protective resin film 71 and the carrier film 70 remain in the groove 56a. Since the carrier film 70 is covered with the protective resin film 71, the undamaged carrier film 70 remains. Thereafter, when a catalyst dispersion or catalyst solution is applied to one surface 54a of the first substrate 54, the catalyst is supported on the carrier film 70 remaining in the groove 56a preferentially over the portion from which the metal oxide film has been removed. Therefore, unlike the conventional case, the catalyst is hardly formed in a portion deviated from the groove 56a. Further, since the carrier film 70 remaining in the groove 56 a is not damaged, the catalyst can be favorably supported on the carrier film 70. Even if the second substrate 55 is bonded to the one surface 54 a of the first substrate 54, the catalyst is not formed in a portion deviated from the groove 56 a, and therefore the bonding property between the first substrate 54 and the second substrate 55. Can be avoided.

  In addition, since the carrier film 70 is formed in the groove 56a and the catalyst is supported on the carrier film 70, the first substrate 54 and the second substrate 55 are not made of metal and are formed on the inner wall surface of the microchannel 56. The catalyst supporting film 59 can be provided, and the material of the first substrate 54 and the second substrate 55 need not be limited to metal.

  Furthermore, since the catalyst supporting film 59 can be provided on the inner wall surface of the microchannel 56 without providing a mask on one surface 54a of the portion other than the groove 56a of the first substrate 54, the catalyst supporting film 59 is masked. It is possible to avoid being damaged by the removal liquid.

  In the method (2), when a metal oxide film is formed on one surface 54a of the first substrate 54, a carrier film 70 is also formed on the inner wall surface of the groove, and then a catalyst dispersion or catalyst solution is applied to the surface 54a. When applied, the catalyst is supported on the carrier film 70 to form a catalyst supporting film 72 formed on the entire surface. Next, when the surface 54a is polished, the catalyst supporting film 72 and the protective resin film 71 are removed at portions other than the groove 56a, and the catalyst supporting film 59 remains together with the protective resin film 71 on the inner wall surface of the groove 56a. Therefore, the catalyst is not formed at a portion deviated from the groove 56a as in the prior art. Further, since the polishing is performed in a state where the catalyst supporting film 72 is covered with the protective resin film 71, the remaining catalyst supporting film 59 is hardly damaged.

Further, even if the second substrate 55 is bonded to the one surface 54a of the first substrate 54, the catalyst is not formed in a portion deviated from the groove 56a, so that the bondability between the first substrate 54 and the second substrate 55 is achieved. Can be avoided.
Further, as in the case of the method (1), the material of the first substrate 54 and the second substrate 55 does not have to be limited to metal, and the catalyst supporting film 59 is damaged by a mask removing liquid or the like. It can be avoided.

The present invention is not limited to the above-described embodiment, and various improvements and design changes may be made without departing from the spirit of the present invention.
For example, in the above embodiment, the groove 56a is formed in an arched cross-sectional shape. However, if the fluid flowing through the groove 56a is less likely to stay and the fluid can efficiently contact the catalyst supporting film 59, the groove 56a. The cross-sectional shape may be a triangular shape whose bottom is the apex, a square shape whose bottom is the base, or other shapes.

  In the above embodiment, the bonding surface of the second substrate 55 is flat, but a groove symmetrical to the groove 56a of the first substrate 54 is formed on the bonding surface of the second substrate 55 around the bonding surface. Also good. In this case, when the first substrate 54 and the second substrate 55 are joined, the groove 56 a of the first substrate 54 and the groove of the second substrate 55 overlap.

  In the above embodiment, the case where the catalytic reactor manufactured by the method of the present invention is applied to the reforming reactor 42, the aqueous shift reactor 43 and the selective oxidation reactor 44 has been described as an example. The present invention may be applied to other reactors for carrying out the above, for example, a catalytic combustor that oxidizes and burns fuel and oxygen.

  In the above embodiment, the heater 51 is formed on the other surface 54 b of the first substrate 54, but it may be formed on the second substrate 55. In particular, a convoluted heater having a planar shape symmetrical to the groove 56 a around the bonding surface between the first substrate 54 and the second substrate 55 may be formed on the bonding surface of the second substrate 55. In this case, when the first substrate 54 and the second substrate 55 are joined, the heater of the second substrate 55 overlaps with the groove 56 a of the first substrate 54, and the heater is exposed to the microchannel 56.

  Further, by using a photolithographic method / etching method, a twisted carrier film having a planar shape symmetrical to the groove 56a is formed around the bonding surface between the first substrate 54 and the second substrate 55 as a second substrate 55. Alternatively, the catalyst may be preferentially supported on the carrier film formed on the second substrate 55 by applying a catalyst dispersion or catalyst solution to the bonding surface of the second substrate 55. In this case, when the first substrate 54 and the second substrate 55 are joined, the catalyst supporting film of the second substrate 55 overlaps with the groove 56 a of the first substrate 54, and the catalyst supporting film of the second substrate 55 becomes the microchannel 56. Will be exposed. Even in this case, since the catalyst hardly adsorbs to the portion of the second substrate 55 where the carrier film is not formed, it can be avoided that the bonding property between the first substrate 54 and the second substrate 55 becomes weak.

  Further, in both the method (1) and the method (2), the first substrate 54 itself is formed of a metal, and the first surface 54a of the first substrate 54 is oxidized after the formation of the groove 56a. The carrier film 70 may be formed on the surface layer of the surface 54a.

It is the perspective view which partially cut and showed the fuel storage module and power generation module of a fuel cell type power generation system. It is the block diagram which showed the basic composition of the said fuel cell type electric power generation system. It is the side view which fractured and showed the small reformer built in the above-mentioned power generation module. It is the perspective view which showed the reaction container main body of an evaporator, a reforming reactor, an aqueous shift reactor, and a selective oxidation reactor. FIG. 5A is a plan view showing one surface of the substrate used in the reaction vessel body, and FIG. 5B is a plan view showing the other surface of the substrate. It is drawing which showed the manufacturing procedure of the reaction container main body in order. It is drawing which showed the manufacturing procedure different from the case of FIG. 6 in order.

Explanation of symbols

40 ... Reforming apparatus 41 ... Evaporator 42 ... Reforming reactor (catalytic reactor)
43… Aqueous shift reactor (catalytic reactor)
44… Selective oxidation reactor (catalytic reactor)
54 ... First substrate 55 ... Second substrate 56 ... Micro flow path 56a ... Groove 59 ... Catalyst support film 70 ... Carrier film 71 ... Protective resin film (protective film)

Claims (5)

Forming a carrier film on the one surface of the first substrate having a groove formed on one surface;
Next, forming a protective film on the carrier film;
Next, the step of removing the protective film and the carrier film formed on the one surface other than the groove by polishing the one surface;
Next, removing the protective film remaining in the groove;
Next, a step of supporting the catalyst on the carrier film remaining in the groove by applying a catalyst-containing liquid containing the catalyst to the one surface;
The manufacturing method of the catalytic reactor characterized by including. Forming a carrier film on the one surface of the first substrate having a groove formed on one surface;
Next, a step of supporting the catalyst on the carrier film by applying a catalyst-containing liquid containing a catalyst to the one surface;
Next, a step of forming a protective film on the carrier film carrying the catalyst;
Next, the step of removing the protective film and the carrier film formed on the one surface other than the groove by polishing the one surface;
Next, removing the protective film remaining in the groove;
The manufacturing method of the catalytic reactor characterized by including.   The method for producing a catalytic reactor according to claim 1, wherein the carrier film is a metal oxide film.   The catalyst reactor according to any one of claims 1 to 3, further comprising a step of joining the second substrate to one surface of the first substrate after the step of removing the protective film. Production method. The method for producing a catalytic reactor according to any one of claims 1 to 4, wherein the protective film is a resin that is soluble in an alkaline solution.

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