JP5304326B2 - Reactor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a reactor capable of preventing a leakage of a reactant such as fuel. <P>SOLUTION: By joining an upper substrate 102 to a lower substrate 103, a reforming channel part 162 is superposed on a reforming channel part 172 and a carbon monoxide removal flow passage part 165 is superposed on a carbon monoxide removal channel part 175. An electric heat pattern 106 is formed on the lower substrate 103 and a heater sealing substrate 120 is joined to the lower substrate 103, thereby the electric heat pattern 106 is stored in a burning channel part 121 of the heater sealing substrate 120. Lead wires 109, 110 are joined to both ends of the electric heat pattern 106, the lead wire 109 is passed through a passing groove 127, the lead wire 110 is passed through a passing groove 128, and a clearance of the passing grooves 128, 127 is sealed by a sealing agent 140. <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

  The present invention relates to a reaction apparatus for reacting a reactant, and more particularly to a small-sized reaction apparatus that performs hydrogen reforming.

  In recent years, fuel cells have attracted attention as clean power sources with high energy conversion efficiency, and have been widely put into practical use in fuel cell automobiles and electrified houses. Also, in portable electronic devices such as mobile phones and notebook personal computers, which are rapidly researched and developed for miniaturization, practical application of a power source using a fuel cell is being studied.

  Since the fuel cell generates electric energy by the electrochemical reaction of hydrogen, a fuel reformer that generates hydrogen from the fuel must be mounted on the portable electronic device in addition to the fuel cell. Since heat energy is required to generate hydrogen, a heater is provided in the fuel reformer, the heater electrode is formed on the surface of the fuel reformer, and the lead wire is connected to the electrode with a bonding wire. The heater is heated through the wire (for example, refer to Patent Document 1).

JP 2005-154215 A

By the way, since the heater is provided in the fuel reformer, it is necessary to lay some wiring from the heater to the electrode on the surface of the fuel reformer. Etc. may leak.
This invention is made | formed in view of the above point, and it aims at providing the reaction apparatus which can prevent the leakage of the reactants, such as a fuel.

In order to solve the above problems, a reaction apparatus according to claim 1 of the present invention provides:
A first substrate having a groove or a recess with which a reactant reacts, and an electrothermal pattern having a terminal portion;
A lead wire connected to the terminal portion of the electrothermal pattern;
A second substrate having a through groove for pulling out the lead wire to the outside;
A sealing agent for sealing the through groove;
With
The reaction includes a catalytic reaction using a catalyst supported in the groove or the recess,
The leads between said terminal portion and said sealing agent, have a bent portion,
The bent portion of the lead wire is housed in a terminal portion housing chamber having a gap between the first substrate and the second substrate .

  As described above, the bending portion of the lead wire disperses the stress, so that it is possible to prevent the lead wire from being poorly bonded. In particular, when the temperature difference between the non-reacting device and the reaction device is large, thermal expansion and thermal contraction are caused, and the bending portion relieves stress generated at this time, so that the bonding strength of the lead wire can be maintained.

In the reactor according to claim 2 ,
The electrothermal pattern is stored in an electrothermal pattern storage chamber between the first substrate and the second substrate.

In the reactor according to claim 3 ,
The terminal portion storage chamber is arranged so as not to overlap the groove or the recess.

  According to the present invention, leakage of reactants can be prevented.

It is a perspective view of a reactor. It is the perspective view which showed the reactor and the heater sealing substrate from the upper side. It is the perspective view which showed the reactor and the heater sealing substrate from the lower side. It is the top view which showed the joint surface of the reactor. It is a perspective view of a composite type micro reactor. It is sectional drawing of a composite type | mold micro reactor. It is arrow sectional drawing of the surface along the cutting line VII-VII of FIG. It is arrow sectional drawing of the surface along the cutting line VIII-VIII of FIG. It is arrow sectional drawing of the surface along the cutting line IX-IX of FIG. It is an arrow view of the joint surface along the cutting line XX of FIG. It is an enlarged view of the edge part periphery of the electrothermal pattern in sectional drawing of FIG. It is an expanded sectional view of the edge part periphery of the electrothermal pattern in a modification. It is an expanded sectional view of the edge part periphery of the electrothermal pattern in a modification. It is a block diagram of a power generator.

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

[First Embodiment]
A method for manufacturing the composite microreactor will be described.
As shown in FIG. 1, an electrothermal pattern 6, which is a heat generating electric resistor, is formed on the surface of the reactor 1. Specifically, an electrothermal film is formed on one flat surface 1a among a plurality of surfaces of the reactor 1, and these electrothermal films are processed by a photolithography method and an etching method. Thereby, the electrothermal pattern 6 is formed. The electric heating pattern 6 has a characteristic of generating heat when a predetermined voltage is applied, and has an electric resistance that changes depending on the temperature of the electric heating pattern 6 itself. Therefore, the electrothermal pattern 6 also functions as a temperature sensor that reads a change in temperature from a change in resistance value. The electrothermal pattern 6 includes a heat generation layer having gold (Au) with good reproducibility of resistance values, a diffusion suppression layer containing a refractory metal such as tungsten that is in contact with the heat generation layer and is difficult to thermally diffuse, and a diffusion suppression layer And an adhesion layer containing a metal such as tantalum, molybdenum, titanium, or chromium, which is interposed in order to improve adhesion between the reactor and the reactor 1. Further, when the reactor 1 is a conductive member, in order to electrically insulate the electrothermal pattern 6 from the reactor 1, it is sufficient that an insulating film is formed on the surface 1 a of the reactor 1. In the case of an insulating member, there is no need to further interpose an insulating film on the surface 1a.

  When the electrothermal pattern 6 is formed, both end portions of the electrothermal pattern 6 are made terminal portions 7 and 8 so that both end portions of the electrothermal pattern 6 are wider than other portions. The terminal portions 7 and 8 are substantially rectangular and near the edge of the surface 1a on which the electrothermal pattern 6 is formed.

  The reactor 1 is obtained by stacking and joining a plurality of substrates on which grooves or recesses are formed and covering the grooves or recesses with the substrates. By covering the groove or the concave portion with the substrate, the groove becomes a flow path serving as a reaction furnace at the joint portion between the substrates, or the concave portion becomes an internal space at the joint portion between the substrates. The main material of the reactor 1 can be appropriately selected from glass, ceramic, metal and the like.

  Depending on the use of the reactor 1, a catalyst may be supported on the wall of the groove or the recess of the reactor 1. For example, when the reactor 1 is used as a hydrogen reformer for reforming hydrogen supplied to a fuel cell, a reforming catalyst (for example, a Cu / ZnO system) is formed on the walls of grooves and recesses that define flow paths and internal spaces. Catalyst) and the reactor 1 is used as a carbon monoxide remover, a carbon monoxide selective oxidation catalyst (for example, platinum, ruthenium, palladium, rhodium) is supported on the wall surface of the groove or recess, and the reactor When 1 is used as a vaporizer, no catalyst is supported. These catalysts may be directly fixed to the reactor 1 or may be supported by a carrier such as aluminum oxide coated in a groove or a recess of the reactor 1.

Alternatively, a complex of reactors in which a plurality of types of catalysts are supported in grooves or recesses of the reactor 1 and the reactor 1 causes a plurality of types of reactions according to the type of catalyst may be used. For example, the reactor 1 becomes a reactor of a reformer in which a flow path generates hydrogen from fuel and water, and a subsequent flow path oxidizes carbon monoxide in the product generated by the reformer. The composite body which becomes a reactor of the carbon monoxide remover to be removed may be used.
In FIG. 1, the reactor 1 is obtained by joining two substrates 2 and 3, and the side surface of the reactor 1 is formed with an internal flow path, an inlet 4 and an outlet 5 leading to the internal space. ing. In this case, the substrate 3 corresponds to the first substrate, and a heater sealing substrate 20 described later corresponds to the second substrate.

  The step of forming the electrothermal pattern 6 may be performed before or after the reactor 1 is assembled. That is, after the electrothermal pattern 6 is formed on the uppermost or lowermost substrate, the lowermost or uppermost substrate may be bonded, or after the lowermost or uppermost substrate is bonded, the bonding surface of the substrate The electrothermal pattern 6 may be formed on the opposite surface. The electrothermal pattern 6 is disposed so as to overlap a portion to be heated to a predetermined temperature.

  After the electrothermal pattern 6 is formed, a protective insulating film (for example, silicon nitride or silicon oxide) is covered on the electrothermal pattern 6 except for the terminal portions 7 and 8. And the end part of the lead wire 9 is arrange | positioned in the terminal part 7, it pressurizes with the electrode which pinched | interposed the insulating material from the top, and resistance welding is utilized using the resistance heat_generation | fever by energizing there. And the end part of the lead wire 10 is arrange | positioned in the terminal part 8, it pressurizes with the electrode which pinched | interposed the insulating material from the top, and resistance welding is utilized using the resistance heat_generation | fever by energizing there. As the lead wires 9 and 10, a Kovar wire, an iron nickel alloy wire, a dumet wire (iron nickel alloy core material covered with copper), or the like can be used. The step of joining the lead wires 9 and 10 may be before or after patterning the insulating film.

  On the other hand, a heater sealing substrate 20 as shown in FIGS. 2 and 3 is prepared. On one surface 20a of the heater sealing substrate 20, a zigzag groove 21 serving as an electrothermal pattern storage chamber is recessed by sandblasting or photolithography / etching. When forming the groove 21, one end of the groove 21 is connected to the edge of the heater sealing substrate 20, and the one end 21 a of the groove 21 is opened on one side end surface 20 b of the heater sealing substrate 20. Are connected to the edge of the heater sealing substrate 20, and the other end 21 b of the groove 21 is opened on the side end surface 20 b of the heater sealing substrate 20. Further, in the vicinity of the edge portion of the lower surface 20 a, two substantially rectangular terminal portion storage chambers 23 and 24 are recessed independently of the groove 21, and the terminal portion storage chambers 23 and 24 and the groove 21 communicate with each other. The communication grooves 25, 26 are recessed, the through grooves 27, 28 communicating between the terminal portion storage chambers 23, 24 and the edge surface of the heater sealing substrate 20 are recessed, and the end portions of the through grooves 27, 28 are formed. Is opened on the side end face 20c opposite to the side end face 20b of the heater sealing substrate 20. The widths of the communication grooves 25 and 26 are both slightly longer than the wiring width of the electrothermal pattern 6, sufficiently shorter than the widths of the terminal portion storage chambers 23 and 24, and sufficiently shorter than the widths of the terminal portions 7 and 8, respectively. The widths of the through grooves 27 and 28 are slightly longer than the wiring widths of the lead wires 9 and 10, respectively, sufficiently shorter than the widths of the terminal portion storage chambers 23 and 24, and sufficiently shorter than the widths of the terminal portions 7 and 8, respectively. Since the widths of the terminal storage chambers 23 and 24 are slightly longer than the widths of the terminal portions 7 and 8, respectively, and the lengths of the terminal storage chambers 23 and 24 are slightly longer than the lengths of the terminal portions 7 and 8, respectively. The storage chambers 23 and 24 can store the terminal portions 7 and 8 therein. The terminal portions 7 and 8 may be other than a rectangle such as an ellipse, and the terminal portion storage chambers 23 and 24 are shaped so long as they are slightly larger than the terminal portions 7 and 8 so as to accommodate the terminal portions 7 and 8. Is not limited. A group of recesses is formed by the groove 21, the terminal housing chambers 23 and 24, the communication grooves 25 and 26, and the through grooves 27 and 28. The main material of the heater sealing substrate 20 can be appropriately selected from glass, ceramic, metal and the like according to the reactor 1.

  The surface 20a on which the groove 21 is formed is a surface joined to the surface 1a on which the electrothermal pattern 6 of the reactor 1 is formed. As shown in FIG. 4, the terminal portion 7 is disposed inside the edge of the terminal portion storage chamber 23 when projected in a direction perpendicular to the bonding surface between the heater sealing substrate 20 and the reactor 1, and the terminal portion 8 Is arranged inside the edge of the terminal portion storage chamber 24, and the electric heating pattern 6, the groove 21, and the terminal portion storage chamber 23 so that the electric heating pattern 6 is arranged inside these edges from the groove 21 to the communication grooves 25 and 26. , 24, the communication grooves 25, 26, and the shapes of the through grooves 27, 28 are determined. The through grooves 27 and 28 do not have to be linear and may be bent.

  Next, a combustion catalyst (for example, platinum, ruthenium, palladium, rhodium) is supported on the wall surface of the groove 21. The combustion catalyst is a catalyst that burns fuel gas by oxidizing a combustion gas (for example, hydrogen gas, methanol gas, ethanol gas, dimethyl ether gas, etc.).

  Next, the surface 1a of the reactor 1 and the surface 20a of the heater sealing substrate 20 are bonded together to form a combustor including a combustion catalyst. The electric heating pattern 6 is accommodated in the groove 21, the communication grooves 25 and 26, the terminal portion 7 is accommodated in the terminal portion accommodating chamber 23, the terminal portion 8 is accommodated in the terminal portion accommodating chamber 24, and the lead wires 9 and 10 are inserted in the through grooves 27 and 28. The reactor 1 and the heater sealing substrate 20 are aligned so as to be fitted, and the electrothermal pattern 6 is covered with the heater sealing substrate 20. Then, the surface 1 a of the reactor 1 is bonded to the surface 20 a of the heater sealing substrate 20. As the bonding, anodic bonding, brazing, or the like can be appropriately selected according to the materials of the reactor 1 and the heater sealing substrate 20. By joining the heater sealing substrate 20 to the reactor 1, the groove 21, the terminal portion storage chambers 23 and 24, the communication grooves 25 and 26, and the through grooves 27 and 28 are covered. The lead wires 9 and 10 are bent in a bow shape, bent a plurality of times, or bent into a wave shape in the terminal portion storage chambers 23 and 24, whereby the lead wires 9 and 10 are bent in the terminal portion storage chambers 23 and 24. It is good to bend in By bending the lead wires 9 and 10 in this way, the length of the lead wires 9 and 10 from the terminal portions 7 and 8 to the left edge of the surface 20a is changed to a linear distance from the terminal portions 7 and 8 to the surface 20a. 1.5 times or more.

  Next, in a state where the inserted lead wires 9 and 10 are joined to the terminal portions 7 and 8, a sealing agent 40 (for example, a low melting point glass sealing agent) is formed in the openings of the through grooves 27 and 28 in the side end surface 20c. And the openings of the through grooves 27 and 28 are sealed with a sealing agent 40. When the sealing agent is injected, the openings of the through grooves 27 and 28 are completely closed by the sealing agent to ensure airtightness, and the lead wires 9 and 10 are connected when stress is applied to the lead wires 9 and 10. In order to maintain a space that can be easily bent, the terminal housing chambers 23 and 24 are not completely filled. As the sealing agent, a material substantially equal to the thermal expansion coefficient of the lead wires 9 and 10 is desirable. For example, when the lead wires 9 and 10 are Kovar wires, the sealing agent is preferably a low melting point glass sealing agent. If the reactor 1 is a metal, a material having a lower melting point than the metal of the reactor 1 whose expansion coefficient approximates that of the reactor 1 is preferable.

  Next, pipes made of a material suitable for the reactor 1 such as glass, ceramic, and metal are fitted into the inlet 4 and the outlet 5, respectively, and pipes are fitted into the openings at both ends of the groove 21, respectively. Bonded to the vessel 1 and the heater sealing substrate 20. The pipe is a pipe for introducing a reaction material to be reacted in the reaction apparatus and a pipe for leading a product material generated by the reaction. Then, the reactor 1 and the heater sealing substrate 20 are placed in a heat insulating package made of glass, ceramic, metal, etc. in accordance with the material of the piping in a manufacturing apparatus furnace in an atmosphere reduced to 10 Pa or less, preferably 1 Pa or less. The pipe, which is accommodated and inserted into the opening of the inlet port 4, the outlet port 5 and the groove 21, is passed through the heat insulation package, and then the portion where the pipe penetrates the heat insulation package is sealed with a sealing agent, and the lead wire 9, 10 is also passed through the heat insulation package, and the portion where the lead wires 9 and 10 penetrate the heat insulation package is sealed with a sealing agent. For this reason, the pressure in the heat insulation package can be maintained at a reduced pressure of 10 Pa or less, desirably 1 Pa or less. Such a low-pressure atmosphere has low heat propagation properties, and has an effect of keeping the reactor 1 and the heater sealing substrate 20 warm. Further, if an infrared reflecting film having a higher reflectance than the heat insulating package in the infrared region such as Au, Ag, and Al is formed on the inner surface of the heat insulating package, the thermal efficiency is good.

In this composite microreactor, the electrothermal pattern 6 generates heat by applying a voltage between the lead wires 9 and 10. At this time, the combustion gas is combusted by the combustion catalyst by sending the combustion gas together with oxygen (air) from one of the one end portion 21a and the other end portion 21b to the flow path of the groove 21 through a pipe, thereby generating combustion heat. The combusted exhaust gas is discharged from the other of the one end 21a and the other end 21b. By sending the reactant into the inlet 4 through the piping, the reactant flows in the flow path and the internal space in the reactor 1, and the reactant is heated by the heat of the lead wires 9 and 10 and the heat of combustion in the groove 21. Reaction of the reactant occurs. For example, when the catalyst in the reactor 1 is a reforming catalyst and a mixture of methanol gas and water is supplied as a reactant, chemical reactions such as the following formulas (1) and (2) occur. Further, the catalyst in the reactor 1 is a carbon monoxide removal catalyst, and hydrogen gas, oxygen gas, carbon monoxide gas (produced by the reaction of the following formulas (1) and (2)) and the like as reactants. When supplied, carbon monoxide is selectively oxidized as shown in the following formula (3). Moreover, the reaction in the reactor 1 may be not only a chemical reaction but also a reaction accompanied by a state change. For example, when a catalyst is not supported in the reactor 1 and a liquid (for example, a mixture of water and methanol) is supplied as a reactant, the liquid evaporates. Further, as shown in the following equation (4), the combustion gas and oxygen are sent to the flow path formed by the groove 21 having the combustion catalyst supported on the surface, so that the combustion gas is burned by the combustion catalyst and combustion heat is generated.
CH ₃ OH + H ₂ O → 3H ₂ + CO ₂ (1)
2CH ₃ OH + H ₂ O → 5H ₂ + CO + CO ₂ (2)
2CO + O ₂ → 2CO ₂ (3)
2CH ₃ OH + 3O ₂ → 2CO ₂ + 4H ₂ O (4)

  As described above, according to the present embodiment, the electrothermal pattern 6 is formed on the joint surface 1 a of the reactor 1, and the heater sealing substrate 20 is accommodated in the groove 21 of the heater sealing substrate 20. Since it is joined to the reactor 1, the heat radiation emitted from the combustor provided so as to be in contact with the electric heating pattern 6 or the reactor 1 is directly propagated to the groove 21, or the infrared reflection provided on the inner surface of the heat insulation package. It is reflected by the film and propagates to the groove 21. Therefore, heat is efficiently used for reaction of reactants in the reactor 1 and combustion of combustion gas in the groove 21.

  Further, since the electrothermal pattern 6 formed on the surface of the reactor 1 is accommodated in the groove 21 and the communication grooves 25 and 26 of the heater sealing substrate 20, the degree of adhesion between the heater sealing substrate 20 and the reactor 1 is increased. . Further, since the through grooves 27 and 28 continue to the edge of the heater sealing substrate 20 and open at the edge, and the lead wires 9 and 10 pass through the through grooves 27 and 28, the heater sealing substrate 20 and the reactor 1. Is not reduced by the lead wires 9 and 10. Thus, since the adhesion degree of the heater sealing substrate 20 and the reactor 1 is high, the heat of the electrothermal pattern 6 and the combustion gas in the groove 21 do not leak.

  Further, since the openings at the ends of the through grooves 27 and 28 are sealed with the sealing agent, the heat generated by the electrothermal pattern 6 does not escape, and the heat is efficiently used for the reaction of the reactants in the reactor 1. Moreover, since combustion gas is supplied to the groove | channel 21, the heat | fever of the electrothermal pattern 6 is utilized also for catalytic combustion of combustion gas. In particular, since the electrothermal pattern 6 is exposed in the groove 21, the heat generated by the electrothermal pattern 6 can be efficiently used for catalytic combustion of combustion gas. Since the openings at the ends of the through grooves 27 and 28 are sealed with the sealing agent, the combustion gas supplied to the grooves 21 does not leak from the openings.

[Second Embodiment]
A second embodiment will be described.
FIG. 5 is an external perspective view of the composite microreactor 100 for reforming hydrogen supplied to the fuel cell, and FIG. 6 is a front sectional view of the composite microreactor 100 shown broken.

  As shown in FIGS. 5 and 6, the heat insulating package 150 made of glass or metal is a hexahedral box having a hollow, and the inner wall surface of the heat insulating package 150 is exposed to electromagnetic waves that are heat sources such as infrared rays. On the other hand, a reflective infrared reflective film (for example, Au, Ag, Al) having a higher reflectivity than that of the heat insulation package 150 is formed, and the hollow pressure of the heat insulation package 150 is kept at 10 Pa or less, preferably 1 Pa or less. I'm leaning.

  Further, a supply / discharge member 151 formed of the same material as that of the heat insulation package 150 penetrates the heat insulation package 150. The supply / discharge member 151 includes a fuel supply passage for supplying reformed fuel gas, two intake passages for supplying air, a combustion gas supply passage for supplying combustion gas, and a product gas discharge passage. A product gas discharge channel and an exhaust gas discharge channel for exhausting combustion exhaust gas are formed.

  Further, the lead wires 109 to 112 penetrate the heat insulating package 150. For the lead wires 109 to 112, Kovar wire, iron-nickel alloy wire or dumet wire is used. The portions where the supply / discharge member 151 and the lead wires 109 to 112 penetrate the heat insulating package 150 are sealed with a sealant.

  The heat insulation package 150 accommodates a reactor 101 formed by bonding a lower substrate 103 and an upper substrate 102 as a first substrate, and further a second substrate bonded to the lower surface of the reactor 101, that is, the lower surface of the lower substrate 103. The heater sealing substrate 120 is also accommodated in the heat insulation package 150. In addition, the reactor 101 becomes a complex of the reformer and the carbon monoxide remover, and the heater sealing substrate 120 bonded to the lower substrate 103 becomes the combustor. As described above, among the lead wires 109 to 112, the portion disposed in the combustor is heated by the combustor, whereas the portion exposed to the outside of the combustor, particularly from the heat insulating package 150, Since it is lower than the temperature heated by the combustor, the heat in the combustor tends to leak out of the combustor via the lead wires 109 to 112. For this reason, it is preferable that the diameter of the lead wires 109 to 112 is 0.2 mm or less from the viewpoint of thermal efficiency to reduce the heat capacity and the cross-sectional area.

  7 is a cross-sectional view of the upper substrate 102 taken along the cutting line VII-VII in FIG. As shown in FIG. 7, a fuel supply flow path portion 161 that is a groove or a recess, and a reforming flow path that serves as a reforming reactor, are formed on both surfaces of the upper substrate 102 on the joint surface with the lower substrate 103. The part 162, the communication groove 163, the air supply flow path part 164, and the carbon monoxide removal flow path part 165 serving as a carbon monoxide removal reaction furnace are recessed. Further, a rectangular through-hole 166 is formed through the central portion of the upper substrate 102 in the thickness direction. A plurality of ends such as grooves provided in the upper substrate 102 connected to the pipe are formed only on one edge 102 a of the upper substrate 102. The fuel supply flow path portion 161 is formed so as to extend from the edge 102a of the upper substrate 102 to the edge 102b adjacent to the edge 102a, and one end portion of the fuel supply flow path portion 161 is connected to the edge 102a of the upper substrate 102 to supply fuel. The other end portion of the flow path portion 161 is connected to one end portion of the reforming flow path portion 162. The reforming channel portion 162 is formed in a zigzag shape on the left side of the through hole 166. The communication groove 163 is formed along the edge 102 c facing the edge 102 b of the upper substrate 102 on the rear side of the through hole 166, and one end portion of the communication groove 163 is connected to the other end portion of the reforming channel portion 162. The other end of 163 merges with the air supply channel 164 and the carbon monoxide removal channel 165. The air supply channel portion 164 is formed so as to extend from the edge 102 a to the edge 102 c of the upper substrate 102, and one end portion of the air supply channel portion 164 is connected to the edge 102 a of the upper substrate 102. The end portion is connected to the communication groove 163 and the carbon monoxide removal flow path portion 165. The carbon monoxide removal flow path portion 165 is formed in a zigzag shape on the right side of the through-hole 166, and one end of the carbon monoxide removal flow path portion 165 is connected to the edge 102 a of the upper substrate 102, and the carbon monoxide removal flow path portion 165. Is connected to the communication groove 163 and the air supply flow path portion 164. Note that one end of the air supply channel 164 and one end of the carbon monoxide removal channel 165 are both fitted with a part of the supply / discharge member 151, and the supply / discharge is further discharged to the edge 102 a of the upper substrate 102. Grooves 201, 205, 206 that fit into the member 151 are recessed.

  FIG. 8 is a cross-sectional view of the lower substrate 103 taken along the cutting plane VIII-VIII in FIG. As shown in FIG. 8, the fuel supply flow path portion 171, which is a groove portion or a concave portion, and a reforming flow path serving as a reforming reactor are formed on both surfaces of the lower substrate 103 on the joint surface with the upper substrate 102. A part 172, a communication groove 173, an air supply flow path part 174, and a carbon monoxide removal flow path part 175 serving as a carbon monoxide removal reaction furnace are recessed. Further, a rectangular through hole 176 is formed at the center of the lower substrate 103. With respect to the joint surface between the lower substrate 103 and the upper substrate 102, the fuel supply channel portion 171 and the fuel supply channel portion 161 are plane-symmetric with each other, and similarly, the reforming channel portion 172 and the reforming channel portion 162 are The communication groove 173 and the communication groove 163 are plane-symmetric with each other, the air supply channel portion 174 and the air supply channel portion 164 are plane-symmetric with each other. The lower substrate 103 has edges 103a, 103b, 103c, and 103d corresponding to the edges 102a, 102b, 102c, and 102d of the upper substrate 102. One end of the carbon monoxide removal channel 165 continues to the edge 102a of the upper substrate 102, whereas one end of the carbon monoxide removal channel 175 corresponds to the lower edge 102a of the upper substrate 102. Except for not reaching the edge 103a of the substrate 103, the carbon monoxide removal channel 175 and the carbon monoxide removal channel 165 are plane-symmetric with each other. In addition, notches 211 to 216 that fit into the supply / discharge member 151 are recessed in the edge 103 a of the lower substrate 103. Although the fuel supply channel 171, the air supply channel 174, and the carbon monoxide removal channel 175 are not connected to the edge 103 a of the lower substrate 103, the end of the combustion supply channel 171 is near the notch 212. In addition, the end of the air supply channel 174 is near the notch 214, and the carbon monoxide removal channel 175 is near the notch 213.

  A reforming catalyst (for example, Cu / ZnO-based catalyst) is supported on the wall surfaces of the reforming flow path portions 162 and 172 using alumina as a carrier, and alumina is supported on the wall surfaces of the carbon monoxide removal flow path portions 165 and 175. A carbon monoxide selective oxidation catalyst (for example, platinum, ruthenium, palladium, rhodium) is supported as a carrier. These catalysts are formed by a wash coat method after applying an alumina sol.

  The upper substrate 102 is joined to the lower substrate 103, and the fuel supply channel portion 171 and the fuel supply channel portion 161 overlap each other. Similarly, the reforming channel portion 172 and the reforming channel portion 162 communicate with each other. The groove 173, the communication groove 163, the air supply channel 174 and the air supply channel 164, the carbon monoxide removal channel 175 and the carbon monoxide removal channel 165, the through-hole 176 and the through-hole 166 Are overlapping.

The upper substrate 102 and the lower substrate 103 are made of, for example, a glass material, and in particular, a glass material containing an alkali metal (for example, Na, Li, etc.) that becomes a mobile ion with a thermal expansion coefficient of about 33 × 10 ⁻⁷ / ° C. . When the upper substrate 102 and the lower substrate 103 are bonded by an anodic bonding method, one of the bonding surfaces of the upper substrate 102 and the lower substrate 103 is bonded to oxygen atoms contained in the other glass for anodic bonding. An anodic bonding film having a metal film or a silicon film to be formed is formed by a vapor deposition method (for example, a sputtering method or a vapor deposition method). Note that one of the upper substrate 102 and the lower substrate 103 may be made of metal or silicon instead of a glass material. On the upper substrate 102, an edge 102d facing the edge 102a and a chamfered edge 102e formed by notching a corner between the edge 102c are formed, and an anodic bonding film is formed on the bonding surface of the lower substrate 103. In the case where the film is formed, the anodic bonding film is partially exposed by the chamfered edge 102e, so that it is easy to connect to the electrode terminal to which a voltage is applied during anodic bonding. Thereby, the upper substrate 102 and the lower substrate 103 can be easily anodic bonded.

  Of the reactor 101 that is a joined body of the upper substrate 102 and the lower substrate 103, a reforming channel portion 162 located on the left side of the through holes 166 and 176 and a channel surrounded by the reforming channel portion 172. The portion becomes a reformer in which a reforming reaction for generating hydrogen from a mixture of fuel and water is performed, and the carbon monoxide removal flow path portion 165 and the carbon monoxide removal flow located on the right side of the through holes 166 and 176. The portion in the flow path surrounded by the path portion 175 becomes a carbon monoxide remover that removes carbon monoxide contained in the product produced by the reformer by preferentially oxidizing it. Specifically, the reforming reaction for generating hydrogen from the mixture of fuel and water is performed in the channel surrounded by the reforming channel unit 162 and the reforming channel unit 172, and the carbon monoxide removal channel unit. In the channel surrounded by 165 and the carbon monoxide removal channel section 175, carbon monoxide contained in the product generated during the reforming reaction is oxidized.

  FIG. 9 is a view showing a joint surface with the heater sealing substrate 120 among both surfaces of the lower substrate 103, and is a view taken along the line IX-IX in FIG. As shown in FIG. 9, an electrothermal pattern 106 and an electrothermal pattern 136 are formed on the joint surface of the lower substrate 103 with the heater sealing substrate 120. Further, the electrothermal pattern 106 overlaps with the reforming flow path portion 172 and the electrothermal pattern 136 overlaps with the carbon monoxide removal flow path portion 175 as projected in a direction perpendicular to the surface on which the electrothermal pattern 106 is formed. The terminal portions 107 and 108 at both ends of the electric heating pattern 106 are wider than the other portions, and the terminal portions 137 and 138 at both ends of the electric heating pattern 136 are wider than the other portions. The terminal portions 107 and 108 are in the vicinity of the edge 103d facing the edge 103a, the terminal portions 137 and 138 are in the vicinity of the edge 103a, and the distance from the terminal portions 107 and 108 to the edge 103d is 2 to 4 mm. By shortening the distance from 137, 138 to the edge 103a to 2 to 4 mm, the electrothermal pattern 106 can be widely drawn on the joint surface of the lower substrate 103 with the heater sealing substrate 120. The lead wire 109 is joined to the terminal portion 107, the lead wire 110 is joined to the terminal portion 108, the lead wire 111 is joined to the terminal portion 137, and the lead wire 112 is joined to the terminal portion 138. As a joining method, the lead wire is disposed so as to be in contact with the terminal portion, and then the terminal portion is formed by pressurizing with an electrode sandwiching an insulating material and resistance welding using resistance heating generated by energizing the electrode. 107 and 108 are electrically connected to lead wires 109 and 110, respectively. Then, after the lead wire 111 and the lead wire 112 are arranged so as to be in contact with the terminal portion 137 and the terminal portion 138, respectively, a voltage is applied to the lead wire 111 and the lead wire 112, and the electric heating pattern 136 and the terminal portions 137 and 138 are connected. The terminal portions 137 and 138 are joined so as to be electrically connected to the lead wires 111 and 112 by resistance welding that is energized and heated, respectively. The electrothermal patterns 106 and 136 are covered with a protective insulating film except for the portions of the terminal portions 107, 108, 137 and 138. Note that the electrothermal pattern 106 and the electrothermal pattern 136 apply stress to the lower substrate 103 during film formation, and if the stress is too large, the lower substrate 103 is distorted and bonding becomes difficult. The thickness of the electrothermal pattern 106 and the electrothermal pattern 136 is preferably as thin as 600 nm or less including the thickness of the insulating film in order to suppress the stress applied to the lower substrate 103. The terminal portions 107 and 108 are preferably 1 mm × 3 mm in length and width for ease of joining, and the terminal portions 137 and 138 have a width and length of 1 mm × 3 mm. Is desirable. When the lower substrate 103 has conductivity such as a metal plate, an insulating film is formed under the electrothermal patterns 106 and 136. This insulating film is not formed on the bonding surface of the lower substrate 103 with the heater sealing substrate 120. The thickness of the portion of the lower substrate 103 where the reforming channel portion 172 is provided is set to about 0.2 mm to 0.3 mm.

  FIG. 10 is a cross-sectional view taken along the line XX in FIG. As shown in FIG. 10, of both surfaces of the heater sealing substrate 120, the bonding surface with the lower substrate 103 is a groove or a recess, and is an electric heating pattern storage chamber that stores the electric heating pattern 106. A combustion flow path portion 121, a terminal portion storage chamber 123, 124 independent of the combustion flow passage portion 121, and a communication groove 125 communicating between the combustion flow passage portion 121 and the terminal portion storage chambers 123, 124. 126, through-grooves 127 and 128 for leading the lead wires to the outside, a heater housing groove 129 that is an electric heating pattern storage chamber for storing the electric heating pattern 136, a combustion fuel supply flow path section 131, and an air supply flow path section 132 The communication groove 133 and the exhaust gas discharge flow path 134 are recessed. The heater sealing substrate 120 has edges 120a, 120b, 120c, and 120d corresponding to the edges 103a, 103b, 103c, and 103d of the lower substrate 103. Further, a rectangular through hole 156 is formed at the center of the heater sealing substrate 120. In addition, grooves 222, 223, and 224 that fit into the supply / discharge member 151 are recessed in the edge 120 a of the heater sealing substrate 120. The heater sealing substrate 120 is provided with through grooves 141 and 142 communicating from both ends of the heater housing groove 129 to the edge 120 a of the heater sealing substrate 120. The combustion channel 121, the terminal housing chambers 123 and 124, the communication grooves 125 and 126, the through grooves 127 and 128, the heater storage groove 129, the combustion fuel supply channel 131, the air supply channel 132, and the communication groove 133, the depth of the exhaust gas discharge passage 134 is preferably about 5 μm. The upper substrate 102, the lower substrate 103, and the heater sealing substrate 120 have the same shape and the same dimensions, and the position of the edge 102a of the upper substrate 102 is the position of the edge 103a of the lower substrate 103, the edge of the heater sealing substrate 120. The position of the edge 102b of the upper substrate 102 is aligned with the position of the edge 103b of the lower substrate 103 and the position of the edge 120b of the heater sealing substrate 120, and the position of the edge 102c of the upper substrate 102. Are aligned with the position of the edge 103c of the lower substrate 103 and the position of the edge 120c of the heater sealing substrate 120, and the position of the edge 102d of the upper substrate 102 is the position of the edge 103d of the lower substrate 103 and the heater sealing substrate 120. Is aligned with the position of the edge 120d.

  The exhaust gas discharge flow path 134 is formed so as to extend from the edge 120a to the edge 120b of the heater sealing substrate 120, and one end of the exhaust gas discharge flow path 134 is connected to the edge 120a of the heater sealing substrate 120. The other end portion of the portion 134 is connected to one end portion of the combustion flow path portion 121. The combustion channel 121 is formed in a zigzag shape on the left side of the through hole 156. The communication groove 133 is formed on one side of the peripheral edge of the through-hole 156 so as to extend from the edge 120 c to the edge 120 a of the heater sealing substrate 120, and one end portion of the communication groove 133 is connected to the other end portion of the combustion flow path portion 121. The other end of the communication groove 133 joins the combustion fuel supply flow path 131 and the air supply flow path 132. The other end of the combustion fuel supply flow path 131 is connected to the edge 120a of the heater sealing substrate 120, and the other end of the air supply flow path 132 is connected to the edge 120a of the heater sealing substrate 120. The terminal portion storage chambers 123 and 124 are recessed in the vicinity of the edge 120d of the heater sealing substrate 120, and the terminal portion storage chambers 123 and 124 and the combustion flow path portion 121 communicate with each other through the communication grooves 125 and 126. 124 and the edge 120 d of the heater sealing substrate 120 communicate with each other through the through grooves 127 and 128, and the end portions of the through grooves 127 and 128 are open on the side end surface of the heater sealing substrate 120. Thus, the combustion channel 121, the terminal housing chambers 123 and 124, the communication grooves 125 and 126, the through grooves 127 and 128, the combustion fuel supply channel 131, the air supply channel 132, the communication groove 133, and the exhaust gas discharge A set of recesses is formed by the flow path part 134.

  The groove 206, the notch 216, and the combustion fuel supply flow path 131 serve as a combustion fuel supply port by overlapping the upper substrate 102, the lower substrate 103, and the heater sealing substrate 120. The groove 205, the notch 215, the air supply flow The passage portion 132 becomes an air supply port of the combustor by overlapping the upper substrate 102, the lower substrate 103, and the heater sealing substrate 120, and one end portion of the air supply passage portion 164, the notch 214, and the groove 224 are formed on the upper portion. By superposing the substrate 102, the lower substrate 103, and the heater sealing substrate 120, an air supply port of the carbon monoxide remover is formed, and one end of the carbon monoxide removal flow path portion 165, the notch 213, and the groove 223 are formed on the upper substrate. 102, the lower substrate 103, and the heater sealing substrate 120 are overlapped to form a hydrogen discharge port, and one end portion of the fuel supply passage portion 161, a notch 212. The groove 222 becomes a fuel supply port by overlapping the upper substrate 102, the lower substrate 103, and the heater sealing substrate 120. One end of the groove 201, the notch 211, and the exhaust gas discharge passage portion 134 By overlapping the substrate 103 and the heater sealing substrate 120, an exhaust gas exhaust port of the combustor is obtained. The supply / exhaust member 151 includes piping sections 151a, 151b, and 151c inserted into the combustion fuel supply port, the air supply port of the combustor, the air supply port of the carbon monoxide remover, the hydrogen discharge port, and the exhaust gas discharge port of the combustor, respectively. , 151d, 151e are provided. The piping portions 151a, 151b, 151c, 151d, and 151e have an inner diameter of 0.8 mm to 1.2 mm and an outer diameter in the thickness direction of 1.4 mm to 1.6 mm.

The heater housing groove 129 is formed in a zigzag shape on the right side of the through hole 156, and one end portion of the heater housing groove 129 is in contact with the other end portion of the heater housing groove 129. It continues to the edge 120a.
With respect to the joining surface, the combustion channel 121 and the reforming channel 172 are substantially plane-symmetric with each other, and the heater housing groove 129 and the carbon monoxide removal channel 175 are substantially plane-symmetric.

  A combustion catalyst (for example, platinum) is supported on the wall surface of the combustion flow path 121 using alumina as a carrier.

The heater sealing substrate 120 is also made of a glass material containing an alkali metal (for example, Na, Li, etc.) that becomes a mobile ion. Further, since the heater sealing substrate 120 and the lower substrate 103 are bonded by an anodic bonding method, a metal film or a silicon film is formed on the bonding surface of one of the heater sealing substrate 120 and the lower substrate 103 by a vapor deposition method ( For example, the film is formed by sputtering or vapor deposition. When Pyrex (registered trademark) glass is used as the material for the heater sealing substrate 120, the upper substrate 102, and the lower substrate 103, the coefficient of thermal expansion is 33 × 10 ⁻⁷ / ° C. The heater sealing substrate 120 is formed with a chamfered edge 120e formed by notching a corner between the edge 120d facing the edge 120a and the edge 120b, and an anodic bonding film on the bonding surface of the lower substrate 103. When this film is formed, this anodic bonding film is partially exposed by the chamfered edge 120e, so that it is easy to easily connect to an electrode terminal to which a voltage is applied during anodic bonding.

  In a state where the lower substrate 103 and the heater sealing substrate 120 are joined, the electrothermal pattern 106 is stored in the combustion flow path portion 121 and the communication grooves 125 and 126, the terminal portion 107 is stored in the terminal portion storage chamber 123, and the terminal portion 108 is accommodated in the terminal portion accommodating chamber 124, and the lead wires 109 and 110 are fitted in the through grooves 127 and 128. The electric heating pattern 136 is accommodated in the heater accommodating groove 129, and the lead wires 111 and 112 are fitted into the end portions of the heater accommodating groove 129 via the through grooves 142 and 141. As shown in FIG. 11, the lead wire 110 has a bent portion 110 a that is bent in an arc shape in the terminal portion storage chamber 124, and the lead wire 109 is also bent in an arc shape in the terminal portion storage chamber 123. Part 109a. In this way, the lead wires 109 and 110 are bent so as to bend in a direction different from the longitudinal direction of the lead wires 109 and 110, whereby the edge 103d from which the lead wires 109 and 110 are led out from the terminal portions 107 and 108, The lengths of the lead wires 109 and 110 up to 120d are 1.1 to 5.0 times, preferably 1.5 times the linear distance from the terminal portions 107 and 108 to the edges 103d and 120d.

  Further, as shown in FIG. 11, the sealant 140 is formed around the lead wire 110 at the opening of the through groove 128, the opening of the through groove 128 is blocked by the sealant 140, and the lead wire 110 and the through groove 128 are closed. Is sealed with a sealant 140. Similarly, a sealing agent is formed around the lead wire 109 at the opening of the through groove 127, the opening of the through groove 127 is closed with the sealing agent, and a gap between the lead wire 109 and the through groove 127 is sealed. Is sealed by. For this reason, since the flow path by the combustion flow path part 121 is closed from the through grooves 127 and 128, the fluid in the combustion flow path part 121 does not leak from the through grooves 127 and 128. As the sealing agent, it is preferable to approximate the expansion coefficient of either the lower substrate 103 or the heater sealing substrate 120. If both the lower substrate 103 and the heater sealing substrate 120 are formed of a glass material, A low-melting-point glass sealant may be used, and the brazing material may be a metal as long as it is made of a metal. When the lead wires 111 and 112 are connected to the terminal portions 137 and 138 and the through grooves 141 and 142 are sealed with a sealing agent, the lead wires 111 and 112 are also respectively formed in the heater housing grooves. It is preferable to have a bent portion that is bent so as to bend in a direction different from the longitudinal direction of the lead wires 111 and 112 in 129. At this time, the length of the lead wires 111 and 112 from each end of the electric heating pattern 136 to the edges 103a and 120a from which the lead wires 111 and 112 are led out is from the respective ends of the electric heating pattern 136 to the edges 103a and 120a. 1.1 times to 5.0 times, preferably 1.5 times the linear distance. Since it becomes difficult to disperse the stress when the bent portion is located at a sealing location with the sealing agent, it is preferable that the bending portion is provided at a location other than the sealing location.

  Note that the shapes of the terminal portion storage chamber 124, the through groove 128, and the communication groove 126 may be modified as shown in FIG. In FIG. 12, a through groove 128 and a communication groove 126 are connected at the diagonal of the terminal portion storage chamber 124. The lead wire 110 has a bent portion 110a that is bent and bent at two locations in a U shape. In FIG. 13, the through groove 128 has an L shape, and the lead wire 110 has a bent portion 110 a that is bent and bent in an L shape in the through groove 128. Thus, the through groove 128 and the communication groove 126 are not located on the same straight line as shown in FIG. Similarly, the terminal portion storage chamber 123, the through groove 127, and the communication groove 125 may have the same shape as the terminal portion storage chamber 124, the through groove 128, and the communication groove 126 of FIGS.

  Also, the lead wires 111 and 112 may have bent portions that are bent and bent at two locations in a U-shape, similar to the shape shown in FIG. 12, or similar to the shape shown in FIG. The through grooves 141 and 142 may be bent, and the lead wires 111 and 112 may have bent portions that are bent and bent in the through grooves 142 and 141.

For example, the lead wires 109 and 110 have a linear shape without a bending portion made of a Kovar wire having a thermal expansion coefficient of about 50 × 10 ⁻⁷ / ° C., and the sealant has a thermal expansion coefficient of 33 × 10 ⁻⁷ / ° C. In the case where the low melting point glass sealing agent is used, when the composite microreactor 100 is heated to about 300 ° C. for reaction, the stress due to the thermal expansion of the lead wires 109 and 110 causes the heat of the low melting point glass sealing agent. Since the stress is greater than the stress due to expansion, stress distortion concentrates on the sealing portion of the lead wires 109 and 110 with the sealing agent, and the lead wires 109 and 110 may be detached from the sealing agent. Since the lead wires 109 and 110 have a bent portion, the thermal stress is dispersed, and even if the lead wires 109 and 110 are heated to 350 ° C., the lead wires 109 and 110 are not detached from the sealing agent. Similar results were obtained with the structures shown in FIGS.

The lower substrate 103 is thin at a portion where the reforming channel portion 172 is provided, and the reforming channel portion 172 is formed wider than the carbon monoxide removal channel portion 175, so that the strength against external stress is increased. However, if the terminal portions 107 and 108 are disposed on the back surface of the reforming flow path portion 172, they are destroyed or deformed by the pressure during resistance welding. For this reason, the terminal portions 107 and 108 are provided on the back surface portion outside the reforming channel portion 172, specifically, in the lower substrate 103, the terminal portion storage chamber 123 of the heater sealing substrate 120 bonded to the back surface. It arrange | positions in the position corresponding to 124. FIG. Since the portion of the lower substrate 103 corresponding to the terminal portion storage chambers 123 and 124 is sufficiently thick, the lower substrate 103 can be prevented from being broken or deformed by the pressure during resistance welding. If the terminal storage chambers 123 and 124 are too large, the distance from the reforming channel 172 to the edge 103d becomes long, and the channel of the reforming channel 172 becomes relatively small. If it is too small, the terminal portions 107 and 108 become small and difficult to weld. Therefore, the terminal portion is 1 mm × 3 mm, and the distance from the reforming flow path portion 172 to the edge 103d is 2 mm to 4 mm.
The lead wires 109 and 110 may have a plurality of bent portions.

Next, a method for manufacturing the composite microreaction apparatus 100 will be described.
First, the upper substrate 102, the lower substrate 103, and the heater sealing substrate 120 are prepared, and a metal film or a silicon film is formed on these bonding surfaces by a vapor deposition method as necessary. Next, an electrothermal film is formed on the lower surface of the lower substrate 103, and the electrothermal pattern 106, 136 is patterned by processing the shape of the electrothermal film by a photolithography etching method. Then, the electrothermal patterns 106 and 136 are covered with an insulating film except for the terminal portions 107, 108, 137, and 138. Next, the upper substrate 102 is provided with a fuel supply flow channel portion 161, a reforming flow channel portion 162, a communication groove 163, an air supply flow channel portion 164, and a carbon monoxide removal flow channel portion 165, all of which are grooves or recesses. Then, a through hole 166 and grooves 201, 205, and 206 are formed. The lower substrate 103 is also formed with a fuel supply channel 171, a reforming channel 172, a communication groove 173, an air supply channel 174, and a carbon monoxide removal channel 175, all of which are grooves or recesses. Further, a through hole 176 and notches 211 to 216 are formed. In addition, the heater sealing substrate 120 is provided with a combustion channel 121, terminal housing chambers 123 and 124, communication grooves 125 and 126, through grooves 127 and 128, a heater housing groove 129, a combustion fuel supply channel 131, and an air supply. The flow path portion 132, the communication groove 133, the exhaust gas discharge flow path portion 134, the through grooves 141, 142 and the grooves 222, 223, 224 are formed, and the through hole 156 is further formed.

  Next, alumina sol is applied to the reforming flow path portion 162 and the reforming flow path portion 172, and a reforming catalyst is formed by a wash coat method. Further, an alumina sol is applied to the carbon monoxide removal flow path portion 165 and the carbon monoxide removal flow path portion 175, and a carbon monoxide removal catalyst is formed by a wash coat method. Further, an alumina sol is applied to the combustion flow path portion 121, and a combustion catalyst is formed by a wash coat method.

  Next, the upper substrate 102 and the lower substrate 103 are bonded by an anodic bonding method. Next, a lead wire 109 having a bent portion is joined to the terminal portion 107 by resistance welding, a lead wire 110 having a bent portion is joined to the terminal portion 108 by resistance welding, and the lead wire 111 is resistance to the terminal portion 137. The lead wire 112 is joined to the terminal portion 138 by resistance welding.

Next, the lower substrate 103 and the heater sealing substrate 120 are bonded together, the lower substrate 103 and the heater sealing substrate 120 are aligned, and the electrothermal patterns 106 and 136 are covered with the heater sealing substrate 120. That is, the electrothermal pattern 106 is accommodated in the combustion flow path portion 121, the communication grooves 125 and 126, the terminal portion 107 is accommodated in the terminal portion accommodating chamber 123, the terminal portion 108 is accommodated in the terminal portion accommodating chamber 124, and the lead grooves 127 and 128 are lead. The wires 109 and 110 are fitted, the electric heating pattern 136 is accommodated in the heater accommodating groove 129, and the lead wires 111 and 112 are fitted in the through grooves 142 and 141 communicating with the heater accommodating groove 129. Then, the heater sealing substrate 120 is bonded to the lower substrate 103 by anodic bonding.
Next, the opening of the through grooves 127 and 128 is sealed by injecting a sealing agent into the through grooves 127 and 128. When the sealing agent is injected into the through grooves 141 and 142, the lead wires 111 and 112 have bent portions.

  Next, the supply / discharge member is supplied to the opening (the groove 201, the notch 211, and the end portion of the exhaust gas discharge flow path portion 134 overlap each other) on the right end surface of the joined body of the upper substrate 102, the lower substrate 103, and the heater sealing substrate 120. 151, the reformed fuel gas supply fuel supply flow path is connected to the fuel supply flow path section 161, one air supply intake flow path is connected to the air supply flow path section 164, and the other air The supply intake flow path is connected to the air supply flow path section 132, the combustion gas supply combustion gas supply flow path is connected to the combustion fuel supply flow path section 131, and the product gas discharge flow path for generating gas discharge is connected. Connected to the carbon monoxide removal flow path 165, the exhaust gas discharge flow path for exhausting combustion exhaust gas is connected to the exhaust gas discharge flow path 134.

Next, the heat insulation package 150 is prepared, and an infrared reflection film is formed on the inner surface of the heat insulation package 150. Then, the assembly of the upper substrate 102, the lower substrate 103, and the heater sealing substrate 120 is accommodated in the heat insulation package 150 in a manufacturing apparatus furnace in an atmosphere reduced to 10 Pa or less, preferably 1 Pa or less, and the supply / discharge member 151 is accommodated. Is passed through the heat insulation package 150, and the lead wires 109, 110, 111, and 112 are passed through the heat insulation package 150. And the penetration location of the supply / discharge member 151 and the lead wires 109, 110, 111, and 112 is sealed with a sealing agent, and the atmosphere in the heat insulation package 150 is reduced to 10 Pa or less, preferably 1 Pa or less.

  In the composite microreactor 100, when a voltage is applied between the lead wires 109 and 110, the electrothermal pattern 106 generates heat, and when a voltage is applied between the lead wires 111 and 112, the electrothermal pattern 136 generates heat. At this time, if combustion gas (for example, hydrogen gas, methanol gas, ethanol gas, dimethyl ether gas) is sent to the combustion fuel supply flow path 131 and air (oxygen) is sent to the air supply flow path 132, the combustion gas and air The air-fuel mixture flows through the combustion flow passage 121, the combustion gas is burned by the combustion catalyst, and combustion heat is generated. Further, when a mixture of fuel (for example, methanol, ethanol, dimethyl ether) and water is supplied to the fuel supply channel 161, the mixture reacts with the reforming catalyst when the mixture is flowing through the reforming channel 162. Hydrogen gas is generated, and a small amount of carbon monoxide gas is also generated (refer to the above formulas (1) and (2) when the fuel is methanol). When air is supplied to the air supply flow path portion 164, it flows through the carbon monoxide removal flow path portion 165 in a state where hydrogen gas, carbon monoxide gas, air, and the like are mixed. At this time, a selective oxidation reaction in which the carbon monoxide gas is preferentially oxidized by the carbon monoxide removal catalyst occurs, and the carbon monoxide gas is removed. Then, a gas containing hydrogen gas or the like is discharged from the carbon monoxide removal flow path portion 165.

  Note that an air-fuel mixture of fuel (for example, methanol, ethanol, dimethyl ether) and air (oxygen) may be supplied to the fuel supply channel 161. In this case, the fuel undergoes a partial oxidation reforming reaction to generate hydrogen gas. In this case, the catalyst supported on the wall surfaces of the reforming flow path portions 162 and 172 is a partial oxidation reforming catalyst. Two types of catalysts may be supported on the reforming flow path portions 162 and 172, and the partial oxidation reforming reaction and the steam reforming reaction (the above formula (1)) may be combined.

The use of the composite microreaction apparatus 100 will be described.
This composite microreaction apparatus 100 can be used in a power generation apparatus 900 as shown in FIG. The power generation device 900 includes a fuel package 901 that stores fuel and water in a liquid state, a vaporizer 902 that vaporizes fuel and water supplied from the fuel package 901, a composite microreactor 100, and a composite microreactor. And a fuel cell 903 that generates electrical energy from hydrogen gas supplied from the reactor 101 of the reactor 100. The fuel and water vaporized by the vaporizer 902 flow into the fuel supply flow path portions 161 and 171, and hydrogen gas and the like flowing out from the carbon monoxide removal flow path portions 165 and 175 are supplied to the fuel electrode of the fuel cell 903. Air is supplied to the oxygen electrode 903, and electric energy is generated by an electrochemical reaction in the fuel cell 903. Here, not all of the hydrogen gas supplied to the fuel electrode of the fuel cell 903 may react, and when there is residual hydrogen gas, the hydrogen gas is supplied to the combustion fuel supply flow path 131 (combustor 145). It may be supplied.

  In such a second embodiment, the electrothermal pattern 106 is formed on the lower surface of the lower substrate 103, and the electrothermal pattern 106 is accommodated in the combustion flow path portion 121 of the heater encapsulating substrate 120. Is bonded to the lower substrate 103 and the through grooves 127 and 128 are sealed, so that heat generated from the electrothermal pattern 106 is trapped in the combustion flow path portion 121. Therefore, the heat generated by the electric heating pattern 106 is efficiently used for the reforming reaction of the fuel in the reforming flow path portions 162 and 172 and the combustion of the combustion gas in the combustion flow path portion 121.

  Further, since the electrothermal pattern 106 is accommodated in the combustion flow path portion 121, the communication grooves 125 and 126 of the heater sealing substrate 120, the degree of adhesion between the heater sealing substrate 120 and the lower substrate 103 is increased. Further, since the through grooves 127 and 128 continue to the edge of the heater sealing substrate 120 and open at the edge, and the lead wires 109 and 110 pass through the through grooves 127 and 128, the heater sealing substrate 120 and the lower substrate 103. Is not lowered by the lead wires 109 and 110. Similarly, since part of the lead wires 111 and 112 and the electrothermal pattern 136 are accommodated in the heater accommodating groove 129, the adhesion between the lower substrate 103 and the heater sealing substrate 120 is increased. Thus, since the adhesion degree of the heater sealing substrate 120 and the lower substrate 103 is high, the heat of the electrothermal pattern 106 and the combustion gas in the combustion flow path portion 121 do not leak.

  In addition, since the openings at the ends of the through grooves 127 and 128 are sealed with the sealing agent, the heat generated by the electrothermal pattern 106 does not escape, and the heat is used for the fuel reforming reaction in the reforming flow path portions 162 and 172. It is used efficiently. Moreover, since combustion gas is supplied to the combustion flow path part 121, the heat of the electrothermal pattern 106 is also used for catalytic combustion of the combustion gas. In particular, since the electric heating pattern 106 is exposed in the combustion flow path portion 121, the electric heat of the electric heating pattern 106 can be efficiently used for catalytic combustion of the combustion gas. And since the opening of the end of the through-grooves 127 and 128 is sealed with the sealing agent, the combustion gas supplied to the combustion flow path part 121 does not leak from the opening.

Further, when the opening of the heater housing groove 129 at the edge of the heater sealing substrate 120 is not closed by the sealing agent, even if the gas in the heater housing groove 129 expands / contracts due to a temperature change, the heater housing groove The atmospheric pressure in 129 does not change extremely. Therefore, the lifetime of the heater sealing substrate 120 and the lower substrate 103 can be extended.
In the above embodiment, the reforming flow path section and the carbon monoxide removal flow path section are formed on both the upper substrate 102 and the lower substrate 103. However, the present invention is not limited to this, and the reforming flow path is formed only on the upper substrate 102. The channel portion and the carbon monoxide removal flow path portion may be formed, or the reforming flow path portion and the carbon monoxide removal flow path portion may be formed only on the lower substrate 103.

  Moreover, in the said embodiment, although the electrothermal pattern 106,136 was accommodated in the reforming flow path part 172, the carbon monoxide removal flow path part 175 using the heater sealing substrate 120, it is not restricted to this, and an electrothermal pattern At least one of 106 and 136 may be provided on one of the upper substrate 102 and the lower substrate 103. In this case, one or the other of the upper substrate 102 and the lower substrate 103 is provided separately from the reforming flow path portion and in a terminal portion storage chamber corresponding to the terminal portion storage chambers 123 and 124, and the communication grooves 125 and 126. Correspondingly, a communication groove for routing the electrothermal pattern in the reforming flow path part to the terminal part accommodated in the terminal part storage chamber, and a through groove corresponding to the through grooves 127 and 128 are provided. In particular, when the strength against external stress is remarkably weakened by the reforming channel portion, the reforming channel portion may be formed only on one of the upper substrate 102 and the lower substrate 103, and the electrothermal pattern may be formed only on the other. .

1 Reactor 6, 106 Electrothermal pattern 9, 10, 109, 110, 111, 112 Lead wire 20 Heater sealing substrate 21 Groove 25, 26, 125, 126 Communication groove 23, 24, 123, 124 Terminal storage chamber 27, 28, 127, 128 Through-grooves 162, 172 Reformation flow path sections 165, 175 Carbon monoxide removal flow path sections 121 Fuel flow path sections 131 Combustion fuel supply flow path sections 132 Air supply flow path sections 133 Communication grooves 134 Exhaust gas discharge flow Road

Claims (3)

A first substrate having a groove or a recess with which a reactant reacts, and an electrothermal pattern having a terminal portion;
A lead wire connected to the terminal portion of the electrothermal pattern;
A second substrate having a through groove for pulling out the lead wire to the outside;
A sealing agent for sealing the through groove;
With
The reaction includes a catalytic reaction using a catalyst supported in the groove or the recess,
The leads between said terminal portion and said sealing agent, have a bent portion,
The reaction apparatus according to claim 1, wherein the bent portion of the lead wire is accommodated in a terminal portion accommodating chamber having a gap between the first substrate and the second substrate . The electric heating pattern, the reaction apparatus according to claim 1, characterized in that it is housed in the heating pattern storage chamber between the first substrate and the second substrate. The reaction apparatus according to claim 1, wherein the terminal portion storage chamber is disposed so as not to overlap the groove or the recess.

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