以下に、本発明を実施するための最良の形態について図面を用いて説明する。但し、以下に述べる実施形態には、本発明を実施するために技術的に好ましい種々の限定が付されているが、発明の範囲を以下の実施形態および図示例に限定するものではない。
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.
図１は複合型マイクロ反応装置１００の外観斜視図であり、図２は一部破断して示した複合型マイクロ反応装置１００の略断面図である。
FIG. 1 is an external perspective view of the composite microreactor 100, and FIG. 2 is a schematic cross-sectional view of the composite microreactor 100 partially cut away.
図１及び図２に示すように、熱伝導性の低いガラス製の断熱パッケージ１５０は中空を有した六面体状の箱体であり、熱線となる赤外線に対して高い反射性の赤外線反射膜（例えば、Ａｕ、Ａｇ、Ａｌ）が断熱パッケージ１５０の内壁面に成膜され、さらに断熱パッケージ１５０の中空の圧力が真空圧に保たれ、例えば断熱パッケージ１５０内は１０Ｐａ以下、好ましくは１Ｐａ以下としてに保たれている。したがって後述する貫通孔１６６、貫通孔１７６、貫通孔１３６内も断熱パッケージ１５０内の圧力と同じになっている。このため熱輻射や外部への熱伝導を抑えることができる。なお断熱パッケージ１５０は、それ自体が赤外線に対して反射性のある金属製であってもよい。
As shown in FIGS. 1 and 2, the heat insulating package 150 made of glass having low thermal conductivity is a hexahedral box having a hollow shape, and is an infrared reflective film (for example, highly reflective to infrared rays that become heat rays). , Au, Ag, Al) is formed on the inner wall surface of the heat insulation package 150, and the hollow pressure of the heat insulation package 150 is kept at a vacuum pressure. For example, the heat insulation package 150 is kept at 10 Pa or less, preferably 1 Pa or less. I'm leaning. Accordingly, the pressures in the through holes 166, the through holes 176, and the through holes 136 described later are the same as the pressure in the heat insulating package 150. For this reason, heat radiation and heat conduction to the outside can be suppressed. The heat insulation package 150 may be made of a metal that is reflective to infrared rays.
また、供給排出部材１５１が断熱パッケージ１５０を貫通している。この供給排出部材１５１は、燃焼排ガス排出用の排ガス排出流路管２５１と、改質燃料ガス供給用の燃料供給流路管２５２と、生成ガス排出用の生成ガス排出流路管２５３と、一酸化炭素除去器に供給される酸素が導入される吸気流路管２５４と、燃焼ガスに混合される酸素が導入される吸気流路管２５５と、燃焼ガス供給用の燃焼ガス供給流路管２５６と、を有している。断熱パッケージ１５０外は大気圧となっているため、供給排出部材１５１は、断熱パッケージ１５０内部と外部でほぼ１気圧の差が生じており、この圧力差に基づく応力によって変形または破壊されないように円筒状のガラス管であることが好ましく、内径が１．０ｍｍ、外径が１．６ｍｍに設定している。
Further, the supply / discharge member 151 passes through the heat insulation package 150. The supply / exhaust member 151 includes an exhaust gas discharge channel pipe 251 for exhausting combustion exhaust gas, a fuel supply channel pipe 252 for supplying reformed fuel gas, a generated gas discharge channel pipe 253 for generating gas, An intake passage tube 254 into which oxygen supplied to the carbon oxide remover is introduced, an intake passage tube 255 into which oxygen mixed with the combustion gas is introduced, and a combustion gas supply passage tube 256 for supplying combustion gas And have. Since the outside of the heat insulation package 150 is at atmospheric pressure, the supply / discharge member 151 has a difference of almost 1 atm between the inside and the outside of the heat insulation package 150, and the cylinder is prevented from being deformed or destroyed by the stress based on this pressure difference. It is preferable that it is a glass tube having an inner diameter of 1.0 mm and an outer diameter of 1.6 mm.
また、リード線１０９〜１１２が断熱パッケージ１５０を貫通している。供給排出部材１５１、リード線１０９〜１１２が断熱パッケージ１５０を貫通した箇所は封着剤によってシーリングされている。封着剤は断熱パッケージ１５０と熱膨張係数を近づけるため、低融点ガラスを用いることが好ましく、リード線１０９〜１１２は低融点ガラスと熱膨張係数が近いコバール線が好ましいが、鉄ニッケル合金線または、鉄ニッケル合金の心材の周囲を銅層で被覆したジュメット線であってもよい。リード線１０９〜１１２の直径は、熱効率の観点から小さいことが好ましく０．２ｍｍに設定している。
Further, the lead wires 109 to 112 penetrate the heat insulating package 150. 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. Since the sealing agent has a thermal expansion coefficient close to that of the heat insulating package 150, it is preferable to use a low melting glass, and the lead wires 109 to 112 are preferably Kovar wires having a thermal expansion coefficient close to that of the low melting glass. Further, it may be a jumet wire in which the core of iron-nickel alloy is covered with a copper layer. The diameter of the lead wires 109 to 112 is preferably small from the viewpoint of thermal efficiency, and is set to 0.2 mm.
断熱パッケージ１５０内には、上から順に上基板１０２、中基板１０３、下基板１２０を接合した接合体１０１が断熱パッケージ１５０内に収容されている。上基板１０２、中基板１０３、下基板１２０はともに、封着剤や断熱パッケージ１５０と同等の熱膨張係数であることが好ましく、例えばガラス基板によって形成されている。なお、上基板１０２と中基板１０３を接合したものが改質器と一酸化炭素除去器の複合体とであり、中基板１０３に下基板１２０を接合したものが燃焼器である。
In the heat insulation package 150, the joined body 101 in which the upper substrate 102, the middle substrate 103, and the lower substrate 120 are joined in order from the top is accommodated in the heat insulation package 150. The upper substrate 102, the middle substrate 103, and the lower substrate 120 all preferably have the same thermal expansion coefficient as that of the sealant or the heat insulating package 150, and are formed of, for example, a glass substrate. A combination of the upper substrate 102 and the middle substrate 103 is a complex of a reformer and a carbon monoxide remover, and a combination of the lower substrate 120 and the middle substrate 103 is a combustor.
図３は、図２の切断線III−IIIに沿った面の矢視断面図である。図３に示すように、上基板１０２の両面のうち中基板１０３との接合面には、葛折り状の反応物流動溝が凹設されている。反応物流動溝は、燃料供給流路部１６１と、改質流路部１６２と、連通部１６３と、空気供給流路部１６４と、一酸化炭素除去流路部１６５とを有している。更に、上基板１０２の中央部において矩形状の貫通孔１６６が形成され、上基板１０２の中基板１０３との接合面が貫通孔１６６よりも左側の領域と貫通孔１６６よりも右側の領域に分けられ、改質流路部１６２は貫通孔１６６よりも左側の領域に形成され、一酸化炭素除去流路部１６５は貫通孔１６６よりも右側の領域に形成されている。上基板１０２は、例えば、右縁１０２ａ、左縁１０２ｄの長さが２７ｍｍ、前縁１０２ｂ、後縁１０２ｃの長さが４６ｍｍとなっている。
FIG. 3 is a cross-sectional view taken along the line III-III in FIG. As shown in FIG. 3, a convoluted reactant flow groove is recessed in the joint surface between the upper substrate 102 and the middle substrate 103. The reactant flow groove has a fuel supply flow channel portion 161, a reforming flow channel portion 162, a communication portion 163, an air supply flow channel portion 164, and a carbon monoxide removal flow channel portion 165. Further, a rectangular through hole 166 is formed at the center of the upper substrate 102, and the bonding surface with the middle substrate 103 of the upper substrate 102 is divided into a region on the left side of the through hole 166 and a region on the right side of the through hole 166. The reforming flow path portion 162 is formed in a region on the left side of the through hole 166, and the carbon monoxide removal flow path portion 165 is formed in a region on the right side of the through hole 166. In the upper substrate 102, for example, the length of the right edge 102a and the left edge 102d is 27 mm, and the length of the front edge 102b and the rear edge 102c is 46 mm.
燃料供給流路部１６１が上基板１０２の右縁１０２ａから前縁１０２ｂにかけて沿うように形成され、燃料供給流路部１６１の一端部が上基板１０２の右縁１０２ａまで連なり、燃料供給流路部１６１の他端部が改質流路部１６２の一端部に連なっている。改質流路部１６２は燃料供給流路部１６１よりも幅広な溝であって蛇行した状態に形成されている。連通部１６３は、燃料供給流路部１６１と同程度の幅の溝であって、貫通孔１６６の後ろ側において上基板１０２の後縁１０２ｃに沿って形成され、連通部１６３の一端部が改質流路部１６２の他端部に連なり、連通部１６３の他端部が空気供給流路部１６４及び一酸化炭素除去流路部１６５に合流している。空気供給流路部１６４は上基板１０２の右縁１０２ａから後縁１０２ｃにかけて沿うように形成され、空気供給流路部１６４の一端部が上基板１０２の右縁１０２ａまで連なり、空気供給流路部１６４の他端部が連通部１６３及び一酸化炭素除去流路部１６５に連なっている。一酸化炭素除去流路部１６５は蛇行した状態に形成され、一酸化炭素除去流路部１６５の一端部が上基板１０２の右縁１０２ａまで連なり、一酸化炭素除去流路部１６５の他端部が連通部１６３及び空気供給流路部１６４に連なっている。上基板１０２の右縁１０２ａには、供給排出部材１５１に嵌合する溝２０１，２０５，２０６が凹設されている。相対的に高温の改質流路部１６２に加えられた熱の一部が、連結伝熱部１０２ｅを介して相対的に低温の一酸化炭素除去流路部１６５に伝搬されて選択酸化反応に適した温度になるように設定されている。このときの改質反応の設定温度と選択酸化反応の設定温度の差は、改質流路部１６２と一酸化炭素除去流路部１６５との間の連結伝熱部１０２ｅの長さＹによって設定することができる。
The fuel supply flow path portion 161 is formed so as to extend from the right edge 102a to the front edge 102b of the upper substrate 102. One end portion of the fuel supply flow path portion 161 is connected to the right edge 102a of the upper substrate 102, and the fuel supply flow path portion The other end portion of 161 is connected to one end portion of the reforming flow path portion 162. The reforming flow path portion 162 is a groove wider than the fuel supply flow path portion 161 and is formed in a meandering state. The communication portion 163 is a groove having the same width as that of the fuel supply flow path portion 161 and is formed along the rear edge 102c of the upper substrate 102 on the rear side of the through-hole 166. One end portion of the communication portion 163 is modified. The other end of the communication portion 163 is joined to the air supply passage portion 164 and the carbon monoxide removal passage portion 165. The air supply channel portion 164 is formed so as to extend from the right edge 102a to the rear edge 102c of the upper substrate 102, and one end portion of the air supply channel portion 164 is connected to the right edge 102a of the upper substrate 102. The other end portion of 164 is connected to the communication portion 163 and the carbon monoxide removal flow path portion 165. The carbon monoxide removal channel 165 is formed in a meandering state, and one end of the carbon monoxide removal channel 165 is connected to the right edge 102 a of the upper substrate 102, and the other end of the carbon monoxide removal channel 165. Is connected to the communication part 163 and the air supply flow path part 164. Grooves 201, 205, and 206 that fit into the supply / discharge member 151 are recessed in the right edge 102 a of the upper substrate 102. Part of the heat applied to the relatively high temperature reforming flow path 162 is propagated to the relatively low temperature carbon monoxide removal flow path 165 via the coupled heat transfer section 102e, and undergoes a selective oxidation reaction. It is set to a suitable temperature. The difference between the set temperature of the reforming reaction and the set temperature of the selective oxidation reaction at this time is set by the length Y of the connected heat transfer section 102e between the reforming flow path section 162 and the carbon monoxide removal flow path section 165. can do.
また、上基板１０２に形成された反応物流動溝は、曲がった部分や幅が変わった部分の側面に入隅１１、出隅１２が形成されており、全ての入隅１１及び全ての出隅１２が丸めた状態に形成されている。なお、全ての入隅１１が丸めた状態でなくとも、これら入隅１１のうち少なくとも１つが丸めた状態であれば良い。全ての出隅１２が丸めた状態でなくとも、これら出隅１２のうち少なくとも１つが丸めた状態であれば良い。
The reactant flow grooves formed in the upper substrate 102 are formed with an entrance corner 11 and an exit corner 12 on the side surfaces of the bent portion and the width changed portion, and all the entrance corners 11 and all the exit corners are formed. 12 is formed in a rounded state. In addition, even if not all the corners 11 are rounded, it is sufficient that at least one of these corners 11 is rounded. Even if all the protruding corners 12 are not in a rounded state, it is sufficient that at least one of these protruding corners 12 is in a rounded state.
貫通孔１６６の内壁面における全ての入隅１３が丸めた状態に形成されている。
All the corners 13 on the inner wall surface of the through hole 166 are formed in a rounded state.
溝２０１，２０５，２０６の側面における全ての入隅も丸めた状態に形成されている。なお、溝２０１，２０５，２０６の側面における全ての入隅が丸めた状態でなくとも、これらの入隅のうち１つでも丸めた状態としても良い。
All the corners on the side surfaces of the grooves 201, 205, and 206 are also rounded. In addition, even if not all the corners in the side surfaces of the grooves 201, 205, and 206 are rounded, one of these corners may be rounded.
図４は、図２の切断線IV−IVに沿った面の矢視断面図である。図４に示すように、中基板１０３の両面のうち上基板１０２との接合面には、葛折り状の反応物流動溝が凹設されている。反応物流動溝は、燃料供給流路部１７１と、改質流路部１７２と、連通部１７３と、空気供給流路部１７４と、一酸化炭素除去流路部１７５とを有している。更に、中基板１０３の中央部において矩形状の貫通孔１７６が形成され、中基板１０３の上基板１０２との接合面が貫通孔１７６よりも左側の領域と貫通孔１７６よりも右側の領域に分けられ、改質流路部１７２は貫通孔１７６よりも左側の領域に形成され、一酸化炭素除去流路部１７５は貫通孔１７６よりも右側の領域に形成されている。中基板１０３は、上基板１０２と同一のサイズであり、複合型マイクロ反応装置１００の上方から平面視して接合された中基板１０３の右縁１０３ａ、前縁１０３ｂ、後縁１０３ｃ、左縁１０３ｄの位置がそれぞれ上基板１０２の右縁１０２ａ、前縁１０２ｂ、後縁１０２ｃ、左縁１０２ｄの位置に一致しており、貫通孔１７６の周縁の位置は、貫通孔１６６の周縁の位置と一致している。
FIG. 4 is a cross-sectional view taken along the line IV-IV in FIG. As shown in FIG. 4, a convoluted reactant flow groove is recessed in the joint surface between the middle substrate 103 and the upper substrate 102. The reactant flow groove has a fuel supply flow path section 171, a reforming flow path section 172, a communication section 173, an air supply flow path section 174, and a carbon monoxide removal flow path section 175. Further, a rectangular through hole 176 is formed at the center of the middle substrate 103, and the bonding surface of the middle substrate 103 with the upper substrate 102 is divided into a region on the left side of the through hole 176 and a region on the right side of the through hole 176. The reforming flow path portion 172 is formed in a region on the left side of the through hole 176, and the carbon monoxide removal flow path portion 175 is formed in a region on the right side of the through hole 176. The middle substrate 103 has the same size as the upper substrate 102, and the right edge 103a, the front edge 103b, the rear edge 103c, and the left edge 103d of the middle substrate 103 joined in plan view from above the composite microreactor 100. Are aligned with the positions of the right edge 102a, the front edge 102b, the rear edge 102c, and the left edge 102d of the upper substrate 102, respectively, and the position of the periphery of the through hole 176 is aligned with the position of the periphery of the through hole 166. ing.
中基板１０３と上基板１０２の接合面に関して、燃料供給流路部１７１と燃料供給流路部１６１は互いに面対称であり、同様に、改質流路部１７２と改質流路部１６２が、連通部１７３と連通部１６３が、空気供給流路部１７４と空気供給流路部１６４が、一酸化炭素除去流路部１７５と一酸化炭素除去流路部１６５が、貫通孔１７６と貫通孔１６６が互いに面対称である。また、中基板１０３の右縁１０３ａには、供給排出部材１５１の排ガス排出流路管２５１に嵌合するノッチ２１１と、燃料供給流路管２５２に嵌合するノッチ２１２と、生成ガス排出流路管２５３に嵌合するノッチ２１３と、吸気流路管２５４に嵌合するノッチ２１４と、吸気流路管２５５に嵌合するノッチ２１５と、燃焼ガス供給流路管２５６に嵌合するノッチ２１６が形成されている。燃料供給流路部１７１、空気供給流路部１７４、一酸化炭素除去流路部１７５は中基板１０３の右縁１０３ａまで連なっていないが、燃料供給流路部１７１の端部がノッチ２１１の近くに、空気供給流路部１７４の端部がノッチ２１４の近くに、一酸化炭素除去流路部１７５がノッチ２１３の近くにある。
With respect to the joint surface between the middle 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. Similarly, the reforming channel portion 172 and the reforming channel portion 162 are The communication part 173 and the communication part 163 are the air supply channel part 174 and the air supply channel part 164, the carbon monoxide removal channel part 175 and the carbon monoxide removal channel part 165 are the through hole 176 and the through hole 166. Are plane-symmetric with each other. Further, at the right edge 103a of the middle substrate 103, a notch 211 that fits into the exhaust gas discharge passage pipe 251 of the supply / discharge member 151, a notch 212 that fits into the fuel supply passage pipe 252, and a generated gas discharge passage A notch 213 fitted to the pipe 253, a notch 214 fitted to the intake flow pipe 254, a notch 215 fitted to the intake flow pipe 255, and a notch 216 fitted to the combustion gas supply flow pipe 256. Is formed. The fuel supply channel 171, the air supply channel 174, and the carbon monoxide removal channel 175 are not connected to the right edge 103 a of the middle substrate 103, but the end of the fuel supply channel 171 is near the notch 211. In addition, the end of the air supply flow path 174 is near the notch 214, and the carbon monoxide removal flow path 175 is near the notch 213.
また、中基板１０３に形成された反応物流動溝の側面における全ての入隅２１が丸めた状態に形成され、反応物流動溝の側面における全ての出隅２２が丸めた状態に形成されている。なお、全ての入隅２１が丸めた状態でなくとも、これら入隅２１のうち少なくとも１つが丸めた状態であれば良い。全ての出隅２２が丸めた状態でなくとも、これら出隅２２のうち少なくとも１つが丸めた状態であれば良い。
Further, all the entrance corners 21 on the side surface of the reactant flow groove formed in the middle substrate 103 are formed in a rounded state, and all the output corners 22 on the side surface of the reactant flow groove are formed in a rounded state. . In addition, even if not all the corners 21 are rounded, it is sufficient that at least one of the corners 21 is rounded. Even if all the protruding corners 22 are not in a rounded state, it is sufficient that at least one of these protruding corners 22 is in a rounded state.
貫通孔１７６の内壁面における全ての入隅２３が丸めた状態に形成されている。
All the entrance corners 23 on the inner wall surface of the through hole 176 are formed in a rounded state.
ノッチ２１３〜２１５の内側面における全ての入隅も丸めた状態に形成されている。なお、ノッチ２１３〜２１５の内側面における全ての入隅が丸めた状態でなくとも、これらの入隅のうち１つでも丸めた状態としても良い。
All the corners on the inner side surfaces of the notches 213 to 215 are also rounded. In addition, even if not all the corners on the inner side surfaces of the notches 213 to 215 are rounded, one of these corners may be rounded.
改質流路部１６２，１７２の壁面には、アルミナを担体として改質触媒（例えば、Ｃｕ／ＺｎＯ系触媒）が担持され、一酸化炭素除去流路部１６５，１７５の壁面には、アルミナを担体として一酸化炭素選択酸化触媒（例えば、白金）が担持されている。なお、これら触媒は、アルミナゾルを塗布した後にウォッシュコート法で形成したものである。
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) is supported as a carrier. These catalysts are formed by a wash coat method after applying an alumina sol.
上基板１０２が中基板１０３に接合されており、燃料供給流路部１７１と燃料供給流路部１６１が重なっており、同様に、改質流路部１７２と改質流路部１６２が、連通部１７３と連通部１６３が、空気供給流路部１７４と空気供給流路部１６４が、一酸化炭素除去流路部１７５と一酸化炭素除去流路部１６５が、貫通孔１７６と貫通孔１６６とが重なっている。
The upper substrate 102 is joined to the middle substrate 103, and the fuel supply channel 171 and the fuel supply channel 161 are overlapped. Similarly, the reforming channel 172 and the reforming channel 162 communicate with each other. Part 173 and communication part 163, air supply channel part 174 and air supply channel part 164, carbon monoxide removal channel part 175 and carbon monoxide removal channel part 165, through-hole 176 and through-hole 166 Are overlapping.
上基板１０２と中基板１０３は熱伝導性を低くするためにガラス材料からなり、特に可動イオンとなるアルカリ金属（例えば、Ｎａ、Ｌｉ等）を含有したガラス材料からなる。また、上基板１０２と中基板１０３が陽極接合法により接合するために、上基板１０２と中基板１０３のどちらか一方の接合面には金属膜又はシリコン膜が気相成長法（例えば、スパッタリング法、蒸着法）により成膜されている。なお、上基板１０２と中基板１０３のうちのどちらか一方がガラス材料ではなく金属又はシリコンからなるものとしても良い。これにより、上基板１０２と中基板１０３が陽極接合により接合することができる。
The upper substrate 102 and the middle substrate 103 are made of a glass material in order to lower the thermal conductivity, and in particular, are made of a glass material containing an alkali metal (for example, Na, Li, etc.) that becomes mobile ions. In addition, since the upper substrate 102 and the middle substrate 103 are bonded by an anodic bonding method, a metal film or a silicon film is formed on the bonding surface of either the upper substrate 102 or the middle substrate 103 by a vapor deposition method (for example, a sputtering method). , Vapor deposition method). Note that one of the upper substrate 102 and the middle substrate 103 may be made of metal or silicon instead of a glass material. Thereby, the upper substrate 102 and the middle substrate 103 can be bonded by anodic bonding.
上基板１０２と中基板１０３の接合体のうち、貫通孔１６６，１７６よりも左側の部分が、燃料と水の混合気から水素を生成する改質器となり、貫通孔１６６，１７６よりも右側の部分が、その改質器で生成された生成物の中に含まれる一酸化炭素を優先的に酸化させることで除去する一酸化炭素除去器となる。
上基板１０２と中基板１０３の接合体では、燃料供給流路管２５２から供給される燃料（水を含んでいてもよい）が、燃料供給流路部１６１、１７１によって形成された流路に流れ、改質流路部１７１、１７２によって形成された流路に送られる。改質流路部１７１、１７２内の流路で改質された流体は、連通部１６３、１７３によって形成された流路に流れる。吸気流路管２５４から取り込まれる空気は、空気供給流路部１６４、１７４に流れ、連通部１６３、１７３によって形成された流路との合流部分で、改質された流体と混合される。混合された流体は、合流部分で分岐された一酸化炭素除去流路部１６５、１７５によって形成された流路に流れる際に微量に含まれている一酸化炭素が除去され、生成ガス排出流路管２５３から複合型マイクロ反応装置１００の外部に排出される。
Of the joined body of the upper substrate 102 and the middle substrate 103, a portion on the left side of the through holes 166, 176 becomes a reformer that generates hydrogen from a mixture of fuel and water, and is located on the right side of the through holes 166, 176. The portion becomes a carbon monoxide remover that removes carbon monoxide contained in the product produced by the reformer by preferentially oxidizing it.
In the joined body of the upper substrate 102 and the middle substrate 103, the fuel (which may contain water) supplied from the fuel supply flow channel tube 252 flows into the flow channel formed by the fuel supply flow channel parts 161 and 171. , And sent to the flow path formed by the reforming flow path portions 171 and 172. The fluid modified in the flow paths in the reforming flow path portions 171 and 172 flows into the flow paths formed by the communication portions 163 and 173. The air taken in from the intake passage pipe 254 flows into the air supply passage portions 164 and 174, and is mixed with the reformed fluid at the joining portion with the passage formed by the communication portions 163 and 173. When the mixed fluid flows in the flow path formed by the carbon monoxide removal flow path portions 165 and 175 branched at the joining portion, carbon monoxide contained in a trace amount is removed, and the product gas discharge flow path It is discharged from the tube 253 to the outside of the composite microreactor 100.
図５は、図２の切断線V−Vに沿った面の矢視断面図である。図５に示すように、下基板１２０の両面のうち中基板１０３との接合面には、葛折り状の反応物流動溝が凹設されている。反応物流動溝は、燃焼燃料供給流路部１３１と、空気供給流路部１３２と、連通部１３３と、排ガス排出流路部１３４と、燃焼流路部１３５と、リード線接続部１３７，１３７と、リード線接続部１３８，１３８と、燃焼流路部１４０と、を有している。更に、下基板１２０の中央部において矩形状の貫通孔１３６が形成され、下基板１２０の中基板１０３との接合面が貫通孔１３６よりも左側の領域と貫通孔１３６よりも右側の領域に分けられ、燃焼流路部１３５は貫通孔１３６よりも左側の領域に形成されている。下基板１２０は、中基板１０３と同一のサイズであり、複合型マイクロ反応装置１００の上方から平面視して接合された下基板１２０の右縁１２０ａ、前縁１２０ｂ、後縁１２０ｃ、左縁１２０ｄの位置がそれぞれ中基板１０３の右縁１０３ａ、前縁１０３ｂ、後縁１０３ｃ、左縁１０３ｄの位置に一致しており、貫通孔１３６の周縁の位置は、貫通孔１７６の周縁の周縁の位置と一致している。
また、下基板１２０の右縁１２０ａには、供給排出部材１５１に嵌合する溝２２２，２２３，２２４が凹設されている。リード線接続部１３７，１３７は、一端が燃焼流路部１３５に連通し、他端が左縁１２０ｄにまで連通している。リード線接続部１３８，１３８は、一端が燃焼流路部１４０に連通し、他端が右縁１２０ａにまで連通している。
FIG. 5 is a cross-sectional view taken along the line VV in FIG. As shown in FIG. 5, a convoluted reactant flow groove is recessed in the joint surface of the lower substrate 120 with the middle substrate 103. The reactant flow grooves include the combustion fuel supply flow path 131, the air supply flow path 132, the communication part 133, the exhaust gas discharge flow path 134, the combustion flow path 135, and the lead wire connection parts 137 and 137. And lead wire connecting portions 138 and 138 and a combustion flow path portion 140. Further, a rectangular through hole 136 is formed at the center of the lower substrate 120, and the bonding surface with the middle substrate 103 of the lower substrate 120 is divided into a region on the left side of the through hole 136 and a region on the right side of the through hole 136. The combustion channel part 135 is formed in a region on the left side of the through hole 136. The lower substrate 120 has the same size as that of the middle substrate 103, and the right edge 120a, the front edge 120b, the rear edge 120c, and the left edge 120d of the lower substrate 120 joined in plan view from above the composite microreactor 100. Are aligned with the positions of the right edge 103a, the front edge 103b, the rear edge 103c, and the left edge 103d of the middle substrate 103, respectively, and the position of the periphery of the through hole 136 is the same as the position of the periphery of the periphery of the through hole 176. Match.
In addition, grooves 222, 223, and 224 that fit into the supply / discharge member 151 are recessed in the right edge 120 a of the lower substrate 120. One end of each of the lead wire connecting portions 137 and 137 communicates with the combustion flow path portion 135 and the other end communicates with the left edge 120d. One end of each of the lead wire connecting portions 138 and 138 communicates with the combustion flow path portion 140 and the other end communicates with the right edge 120a.
排ガス排出流路部１３４が下基板１２０の右縁１２０ａから前縁１２０ｂにかけて沿うように形成され、排ガス排出流路部１３４の一端部が下基板１２０の右縁１２０ａまで連なり、排ガス排出流路部１３４の他端部が燃焼流路部１３５の一端部に連なっている。燃焼流路部１３５は、蛇行した状態に形成されている。連通部１３３は貫通孔１６６の後ろ側において下基板１２０の後縁１２０ｃから右縁１２０ａにかけて沿うように形成され、連通部１３３の一端部が燃焼流路部１３５の他端部に連なり、連通部１３３の他端部が燃焼燃料供給流路部１３１及び空気供給流路部１３２に合流している。燃焼燃料供給流路部１３１の他端部が下基板１２０の右縁１２０ａまで連なり、空気供給流路部１３２の他端部が下基板１２０の右縁１２０ａまで連なる。
The exhaust gas discharge flow path part 134 is formed so as to extend from the right edge 120a to the front edge 120b of the lower substrate 120, and one end of the exhaust gas discharge flow path part 134 is connected to the right edge 120a of the lower substrate 120. The other end portion of 134 is connected to one end portion of the combustion flow path portion 135. The combustion flow path part 135 is formed in the meandering state. The communication portion 133 is formed on the rear side of the through hole 166 so as to extend from the rear edge 120c to the right edge 120a of the lower substrate 120. One end portion of the communication portion 133 is connected to the other end portion of the combustion flow path portion 135, and the communication portion The other end of 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 right edge 120a of the lower substrate 120, and the other end of the air supply flow path 132 is connected to the right edge 120a of the lower substrate 120.
接合面に関して、燃焼流路部１３５と改質流路部１７２は互いにほぼ面対称である。燃焼流路部１３５の壁面には、アルミナを担体として燃焼触媒（例えば、白金）が担持されている。
With respect to the joining surface, the combustion channel portion 135 and the reforming channel portion 172 are substantially plane-symmetric with respect to each other. A combustion catalyst (for example, platinum) is supported on the wall surface of the combustion flow path portion 135 using alumina as a carrier.
下基板１２０も特に可動イオンとなるアルカリ金属（例えば、Ｎａ、Ｌｉ等）を含有したガラス材料からなる。また、下基板１２０と中基板１０３が陽極接合法により接合するために、下基板１２０と中基板１０３のどちらか一方の接合面には金属膜又はシリコン膜が気相成長法（例えば、スパッタリング法、蒸着法）により成膜されている。なお、下基板１２０、上基板１０２及び中基板１０３の材料としてパイレックス（登録商標）ガラスを用いた場合、熱膨張率は３３×１０-7／℃である。
The lower substrate 120 is also made of a glass material containing an alkali metal (for example, Na, Li, etc.) that becomes a mobile ion. In addition, since the lower substrate 120 and the middle 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 lower substrate 120 and the middle substrate 103 by a vapor deposition method (for example, a sputtering method). , Vapor deposition method). When Pyrex (registered trademark) glass is used as the material of the lower substrate 120, the upper substrate 102, and the middle substrate 103, the thermal expansion coefficient is 33 × 10 −7 / ° C.
また、中基板１０３の両面のうち下基板１２０との接合面には、電熱パターン１０６及び電熱パターン１３９が形成されている。また、電熱パターン１０６の形成面に対して垂直な方向に投影視して、電熱パターン１０６が改質流路部１７２に重なり、電熱パターン１３９が一酸化炭素除去流路部１７５に重なっている。そして、中基板１０３と下基板１２０が接合された状態では、電熱パターン１０６は、一端部１０６ｂ及び他端部１０６ａを除いて燃焼流路部１３５に収納され、一端部１０６ｂ及び他端部１０６ａがリード線接続部１３７，１３７に収納されている。電熱パターン１０６の一端部１０６ｂはリード線接続部１３７でリード線１０９に接合され、電熱パターン１０６の他端部１０６ａはリード線接続部１３７でリード線１１０に接合され、接合後、リード線接続部１３７，１３７の各他端は低融点ガラスを含む封着剤１１３，１１３によって封止されるので、燃焼流路部１３５内の流体が左縁１２０ｄから漏洩することはない。中基板１０３と下基板１２０が接合された状態では、電熱パターン１３９は、一端部１３９ｂ及び他端部１３９ａを除いて電熱パターン配置溝１４０に収納され、一端部１０６ｂ及び他端部１０６ａがリード線接続部１３８，１３８に収納されている。電熱パターン１３９の一端部１３９ｂにリード線１１１が接合され、電熱パターン１３９の他端部１３９ａにリード線１１２が接合されている。
In addition, an electrothermal pattern 106 and an electrothermal pattern 139 are formed on the joint surface of the middle substrate 103 with the lower substrate 120. Further, the electrothermal pattern 106 overlaps with the reforming flow path portion 172 and the electrothermal pattern 139 overlaps with the carbon monoxide removal flow path portion 175 as viewed in a direction perpendicular to the formation surface of the electrothermal pattern 106. In the state where the middle substrate 103 and the lower substrate 120 are joined, the electrothermal pattern 106 is stored in the combustion flow path portion 135 except for the one end portion 106b and the other end portion 106a, and the one end portion 106b and the other end portion 106a are The lead wire connecting portions 137 and 137 are accommodated. One end portion 106b of the electrothermal pattern 106 is joined to the lead wire 109 by the lead wire connecting portion 137, and the other end portion 106a of the electrothermal pattern 106 is joined to the lead wire 110 by the lead wire connecting portion 137. Since the other ends of 137 and 137 are sealed by the sealing agents 113 and 113 containing low melting point glass, the fluid in the combustion flow path portion 135 does not leak from the left edge 120d. In the state where the middle substrate 103 and the lower substrate 120 are joined, the electrothermal pattern 139 is accommodated in the electrothermal pattern placement groove 140 except for the one end 139b and the other end 139a, and the one end 106b and the other end 106a are connected to the lead wire. It is accommodated in the connecting portions 138 and 138. The lead wire 111 is joined to one end portion 139b of the electric heating pattern 139, and the lead wire 112 is joined to the other end portion 139a of the electric heating pattern 139.
貫通孔１３６の横幅が８ｍｍ、連結伝熱部１２０e、１０２e、１０３eの幅を３ｍｍ、上基板、中基板、下基板の合計の厚みが２．８ｍｍのとき、貫通孔１６６，１７６と、一酸化炭素除去流路部１６５，１７５との間の距離Ｘａおよび、貫通孔１３６と電熱パターン配置溝１４０との間の距離Ｚａが１ｍｍ以上ある場合、右縁１０２a、１０３a、１２０ａ側の二つの入隅１３、２３、３３の曲率半径は１ｍｍ以上で十分な強度を示すことが確認された。貫通孔１６６，１７６と燃料供給流路部１６１，１７１との間の距離Ｘｂおよび、貫通孔１３６と排ガス排出流路部１３４との間の距離Ｚｂが１ｍｍ以上ある場合、前縁１０２b，１０３b、１２０ｂ側の二つの入隅１３，２３、３３の曲率半径は１ｍｍ以上で十分な強度を示すことが確認された。貫通孔１６６，１７６と連通部１６３，１７３との距離Ｘｃおよび、貫通孔１３６と連通部１３３との間の距離Ｚｃが１ｍｍ以上ある場合、後縁１０２ｃ、１０３ｃ、１２０ｃ側の二つの入隅１３，２３、３３の曲率半径は１ｍｍ以上で十分な強度を示すことが確認された。貫通孔１６６，１７６と改質流路部１６２，１７２との間の距離Ｘｄおよび、貫通孔１３６と燃焼流路部１３５との間の距離Ｚｄが１ｍｍ以上ある場合、左縁１０２ｄ，１０３ｄ、１２０ｄ側の二つの入隅１３，２３、３３の曲率半径は１ｍｍ以上で十分な強度を示すことが確認された。
ただし、これら貫通孔１６６，１７６、１３６の入隅１３，２３、３３の曲率半径が４ｍｍを越えると、改質流路部１６２，１７２と一酸化炭素除去流路部１６５，１７５との間の連結伝熱部１０２ｅ、1０３ｅ、および、燃焼流路部１３５と電熱パターン配置溝１４０との間の連結伝熱部１２０ｅの断面積が増大してしまい、改質流路部１６２，１７２、燃焼流路部１３５から一酸化炭素除去流路部１６５，１７５、電熱パターン配置溝１４０に熱伝搬しやすく改質流路部１６２、１７２と一酸化炭素除去流路部１６５、１７５との温度差が小さくなりやすい構造となってしまうために、改質流路部１６２、１７２での改質反応に要する温度範囲（２５０℃〜３５０℃）に対して一酸化炭素除去流路部１６５、１７５での選択酸化反応に要する温度範囲（１００℃〜１８０℃）に設定するためには、貫通孔１６６，１７６、１３６の入隅１３、２３、３３が直角の場合に比べて、連結伝熱部１０２e、１０３e、１２０ｅの長さＹを２割以上長くしなければならず、装置が大きくなってしまう。
したがって、複合型マイクロ反応装置１００が２７ｍｍ×４６ｍｍの寸法であれば、貫通孔１６６，１７６、１３６の入隅１３、２３、３３の曲率半径は１ｍｍ以上４ｍｍ以下が好ましい。距離Ｘａ〜Ｘｄ及び距離Ｚａ〜Ｚｄは、１ｍｍより短くすると、損壊しやすくなるため１ｍｍ以上あることが好ましい。入隅１３，２３，３３が全て同じ曲率半径である必要はなく、左側と右側で異なっていても良い。
上述のように、連結伝熱部１０２ｅ、連結伝熱部１０３ｅ及び連結伝熱部１２０ｅでは、左側と右側で温度勾配が大きく、換言すれば熱膨張の差、冷却収縮の差が大きく、応力が貫通孔１６６、貫通孔１７６、貫通孔１３６の角に集中しやすい。また通穴１６６、貫通孔１７６、貫通孔１３６が基板１０２，１０３，１２０に対して貫通しているために最も機械強度が弱く損壊しやすい。特にガラスの場合、金属に比べて柔軟性がないので歪みによりヒビが入りやすい。このため、入隅１３，２３，３３が直角ではなく丸みを帯びさせることで応力を分散し破損しにくいようにすることができる。
When the lateral width of the through hole 136 is 8 mm, the width of the connecting heat transfer portions 120e, 102e, and 103e is 3 mm, and the total thickness of the upper substrate, the middle substrate, and the lower substrate is 2.8 mm, the through holes 166 and 176 When the distance Xa between the carbon removal flow path portions 165 and 175 and the distance Za between the through hole 136 and the electric heating pattern placement groove 140 are 1 mm or more, the two corners on the right edge 102a, 103a, 120a side It was confirmed that the radii of curvature of Nos. 13, 23, and 33 show a sufficient strength when the radius is 1 mm or more. When the distance Xb between the through holes 166, 176 and the fuel supply flow path portions 161, 171 and the distance Zb between the through hole 136 and the exhaust gas discharge flow path portion 134 are 1 mm or more, the leading edges 102b, 103b, It was confirmed that the radius of curvature of the two corners 13, 23, 33 on the 120b side is 1 mm or more and shows sufficient strength. When the distance Xc between the through holes 166 and 176 and the communication portions 163 and 173 and the distance Zc between the through hole 136 and the communication portion 133 are 1 mm or more, the two corners 13 on the rear edges 102c, 103c, and 120c side , 23, and 33 have a curvature radius of 1 mm or more, and it was confirmed that sufficient strength was exhibited. When the distance Xd between the through holes 166 and 176 and the reforming flow path parts 162 and 172 and the distance Zd between the through hole 136 and the combustion flow path part 135 are 1 mm or more, the left edges 102d, 103d, and 120d It was confirmed that the curvature radii of the two corners 13, 23 and 33 on the side were 1 mm or more and showed sufficient strength.
However, if the curvature radii of the corners 13, 23, and 33 of the through holes 166, 176, and 136 exceed 4 mm, there is a gap between the reforming flow path portions 162 and 172 and the carbon monoxide removal flow path portions 165 and 175. The cross-sectional area of the coupled heat transfer sections 102e and 103e and the coupled heat transfer section 120e between the combustion flow path section 135 and the electric heating pattern placement groove 140 increases, and the reforming flow path sections 162 and 172, the combustion flow The temperature difference between the reforming channel portions 162 and 172 and the carbon monoxide removing channel portions 165 and 175 is small because heat can easily propagate from the channel portion 135 to the carbon monoxide removing channel portions 165 and 175 and the electric heating pattern placement groove 140. In order to become a structure that tends to occur, the selection in the carbon monoxide removal flow path portions 165 and 175 with respect to the temperature range (250 ° C. to 350 ° C.) required for the reforming reaction in the reforming flow path portions 162 and 172 Necessary for oxidation reaction In order to set the temperature range (100 ° C. to 180 ° C.), the connecting heat transfer portions 102e, 103e, and 120e are compared with the case in which the corners 13, 23, and 33 of the through holes 166, 176, and 136 are at right angles. The length Y must be increased by 20% or more, and the apparatus becomes large.
Therefore, if the composite microreactor 100 has a size of 27 mm × 46 mm, the radius of curvature of the corners 13, 23, 33 of the through holes 166, 176, 136 is preferably 1 mm or more and 4 mm or less. If the distances Xa to Xd and the distances Za to Zd are shorter than 1 mm, the distances Xa to Xd are preferably 1 mm or more because they are easily damaged. The entering corners 13, 23, and 33 do not have to have the same radius of curvature, and may be different on the left side and the right side.
As described above, in the connected heat transfer unit 102e, the connected heat transfer unit 103e, and the connected heat transfer unit 120e, the temperature gradient is large between the left side and the right side, in other words, the difference in thermal expansion and the difference in cooling shrinkage are large, and the stress is high. It tends to concentrate on the corners of the through hole 166, the through hole 176, and the through hole 136. Further, since the through-hole 166, the through-hole 176, and the through-hole 136 penetrate the substrate 102, 103, 120, the mechanical strength is weakest and is easily damaged. In particular, in the case of glass, since it is not flexible compared to metal, it is liable to crack due to distortion. For this reason, by making the corners 13, 23 and 33 round rather than perpendicular, the stress can be dispersed and not easily damaged.
次に、複合型マイクロ反応装置１００の製造方法について説明する。
まず、上基板１０２、中基板１０３、下基板１２０を準備し、これらの接合面の一方に必要に応じて金属膜又はシリコン膜を気相成長法により成膜する。中基板１０３の下面には、電熱膜を成膜し、その電熱膜をフォトリソグラフィー・エッチング法により形状加工することによって、電熱パターン１０６，１３９をパターニングする。そして、電熱パターン１０６，１３９の両端部を除いて電熱パターン１０６，１３９を絶縁膜によって被覆する。次に、上基板１０２に、燃料供給流路部１６１、改質流路部１６２、連通部１６３、空気供給流路部１６４、一酸化炭素除去流路部１６５、貫通孔１６６及び溝２０１，２０５，２０６をフォトリソグラフィー法およびサンドブラスト法またはエッチング法により形成する。燃料供給流路部１６１、改質流路部１６２、連通部１６３、空気供給流路部１６４、一酸化炭素除去流路部１６５、貫通孔１６６及び溝２０１，２０５，２０６を形成するに際しては、入隅１１、出隅１２、入隅１３を丸めるよう形成する。
Next, a method for manufacturing the composite microreaction apparatus 100 will be described.
First, the upper substrate 102, the middle substrate 103, and the lower substrate 120 are prepared, and a metal film or a silicon film is formed on one of the bonding surfaces as needed by a vapor deposition method. An electrothermal film is formed on the lower surface of the middle substrate 103, and the electrothermal patterns 106 and 139 are patterned by processing the shape of the electrothermal film by a photolithography etching method. The electrothermal patterns 106 and 139 are covered with an insulating film except for both ends of the electrothermal patterns 106 and 139. Next, on the upper substrate 102, the fuel supply flow path part 161, the reforming flow path part 162, the communication part 163, the air supply flow path part 164, the carbon monoxide removal flow path part 165, the through hole 166, and the grooves 201 and 205. , 206 are formed by photolithography and sandblasting or etching. When forming the fuel supply flow path part 161, the reforming flow path part 162, the communication part 163, the air supply flow path part 164, the carbon monoxide removal flow path part 165, the through-hole 166, and the grooves 201, 205, 206, The entrance corner 11, the exit corner 12, and the entrance corner 13 are formed to be rounded.
中基板１０３にも、燃料供給流路部１７１、改質流路部１７２、連通部１７３、空気供給流路部１７４、一酸化炭素除去流路部１７５、貫通孔１７６及びノッチ２１１〜２１６をフォトリソグラフィー法およびサンドブラスト法またはエッチング法により形成する。燃料供給流路部１７１、改質流路部１７２、連通部１７３、空気供給流路部１７４、一酸化炭素除去流路部１７５、貫通孔１７６及びノッチ２１１〜２１６を形成するに際しては、入隅２１、出隅２２，入隅２３を丸めるよう形成する。
The intermediate substrate 103 also has a fuel supply channel 171, a reforming channel 172, a communication unit 173, an air supply channel 174, a carbon monoxide removal channel 175, a through hole 176, and notches 211 to 216. It is formed by lithography and sandblasting or etching. When forming the fuel supply channel 171, the reforming channel 172, the communication unit 173, the air supply channel 174, the carbon monoxide removal channel 175, the through-hole 176 and the notches 211 to 216, 21, the outgoing corner 22 and the incoming corner 23 are formed to be rounded.
また、下基板１２０に、燃焼燃料供給流路部１３１、空気供給流路部１３２、連通部１３３、排ガス排出流路部１３４、貫通孔１３６、燃焼流路部１３５、リード線接続部１３７，１３７、リード線接続部１３８，１３８、電熱パターン配置溝140及び溝２２２，２２３，２２４をフォトリソグラフィー法およびサンドブラスト法またはエッチング法により形成する。燃焼燃料供給流路部１３１、空気供給流路部１３２、連通部１３３、排ガス排出流路部１３４、貫通孔１３６、燃焼流路部１３５及び溝２２２，２２３，２２４を形成するに際しては、入隅３１、出隅３２、入隅３３を丸めるよう形成する。
In addition, the lower substrate 120 is provided with a combustion fuel supply channel 131, an air supply channel 132, a communication unit 133, an exhaust gas discharge channel 134, a through hole 136, a combustion channel 135, and lead wire connection units 137 and 137. The lead wire connecting portions 138 and 138, the electrothermal pattern arrangement grooves 140, and the grooves 222, 223 and 224 are formed by a photolithography method, a sand blast method, or an etching method. When forming the combustion fuel supply flow path part 131, the air supply flow path part 132, the communication part 133, the exhaust gas discharge flow path part 134, the through hole 136, the combustion flow path part 135, and the grooves 222, 223, and 224 31, the exit corner 32, and the entrance corner 33 are formed to be rounded.
次に、改質流路部１６２及び改質流路部１７２にアルミナゾルを塗布し、更にウォッシュコート法により改質触媒を形成する。また、一酸化炭素除去流路部１６５及び一酸化炭素除去流路部１７５にアルミナゾルを塗布し、更にウォッシュコート法により一酸化炭素除去触媒を形成する。また、燃焼流路部１３５にアルミナゾルを塗布し、更にウォッシュコート法により燃焼触媒を形成する。
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, alumina sol is applied to the combustion flow path portion 135, and a combustion catalyst is formed by a wash coat method.
次に、電熱パターン１０６の両端部それぞれにリード線１０９，１１０を接合し、電熱パターン１３９の両端部それぞれにリード線１１１，１１２を接合する。その後、上基板１０２及び中基板１０３を陽極接合法により接合する。
Next, lead wires 109 and 110 are bonded to both ends of the electrothermal pattern 106, and lead wires 111 and 112 are bonded to both ends of the electrothermal pattern 139. Thereafter, the upper substrate 102 and the middle substrate 103 are bonded by an anodic bonding method.
次に、中基板１０３と下基板１２０を貼りあわせ、中基板１０３と下基板１２０の位置合わせを行って電熱パターン１０６を燃焼流路部１３５に収容し、中基板１０３に下基板１２０を陽極接合法により接合する。
Next, the middle substrate 103 and the lower substrate 120 are bonded together, the middle substrate 103 and the lower substrate 120 are aligned, the electrothermal pattern 106 is accommodated in the combustion flow path portion 135, and the lower substrate 120 is anode-contacted to the middle substrate 103. Join by law.
その後、左縁１２０ｄ側のリード線接続部１３７，１３７の開放端を封着剤１１３，１１３によって封止する。
Thereafter, the open ends of the lead wire connecting portions 137 and 137 on the left edge 120d side are sealed with sealants 113 and 113, respectively.
次に、上基板１０２、中基板１０３、下基板１２０の接合体の右端面の開口（溝２０１、ノッチ２１１、排ガス排出流路部１３４の端部を重なり部分等）に供給排出部材１５１を嵌め込み、封着剤でシーリングする。それにより、改質燃料ガス供給用の部材２５２を燃料供給流路部１６１に繋がるように接続され、１つの空気供給用の部材２５４を空気供給流路部１６４に繋がるよう接続され、もう１つの空気供給用の部材２５５を空気供給流路部１３２に繋がるよう接続され、燃焼ガス供給用の部材２５６を燃焼燃料供給流路部１３１に繋がるよう接続され、生成ガス排出用の部材２５３を一酸化炭素除去流路部１６５に繋がるよう接続され、燃焼排ガス排出用の部材２５１を排ガス排出流路部１３４に繋がるよう接続される。
Next, the supply / discharge member 151 is fitted into the opening (the groove 201, the notch 211, the end portion of the exhaust gas discharge flow path portion 134 overlapped) of the right end surface of the joined body of the upper substrate 102, the middle substrate 103, and the lower substrate 120. Seal with sealant. Accordingly, the reformed fuel gas supply member 252 is connected so as to be connected to the fuel supply flow path portion 161, and one air supply member 254 is connected so as to be connected to the air supply flow path portion 164. The air supply member 255 is connected to the air supply flow path 132, the combustion gas supply member 256 is connected to the combustion fuel supply flow path 131, and the product gas discharge member 253 is oxidized. It is connected so as to be connected to the carbon removal flow path part 165, and is connected so as to connect the member 251 for exhausting combustion exhaust gas to the exhaust gas discharge flow path part 134.
次に、断熱パッケージ１５０を準備し、その断熱パッケージ１５０の内面に赤外線反射膜を成膜する。そして、上基板１０２、中基板１０３、下基板１２０の接合体を断熱パッケージ１５０内に収容し、供給排出部材１５１を断熱パッケージ１５０に貫通させ、リード線１０９，１１０，１１１，１１２を断熱パッケージ１５０に貫通させる。そして、供給排出部材１５１、リード線１０９，１１０，１１１，１１２の貫通箇所を封着剤でシーリングする。
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. The joined body of the upper substrate 102, the middle substrate 103, and the lower substrate 120 is accommodated in the heat insulation package 150, the supply / discharge member 151 is passed through the heat insulation package 150, and the lead wires 109, 110, 111, and 112 are connected to the heat insulation package 150. To penetrate. And the penetration part of the supply / discharge member 151 and the lead wires 109, 110, 111, and 112 is sealed with a sealing agent.
複合型マイクロ反応装置１００においては、リード線１０９，１１０の間に電圧を印加すると電熱パターン１０６が発熱し、リード線１１１，１１２の間に電圧を印加すると電熱パターン１３９が発熱する。このとき、燃焼ガス（例えば、水素ガス、メタノールガス、エタノールガス、ジメチルエーテルガス）を燃焼燃料供給流路部１３１に送り込み、空気（酸素）を空気供給流路部１３２に送り込むと、燃焼ガスと空気の混合気が燃焼流路部１３５を流動し、燃焼ガスが燃焼触媒により燃焼し、燃焼熱が発する。また、燃料（例えば、メタノール、エタノール、ジメチルエーテル）と水の混合気を燃料供給流路部１６１に供給すると、混合気が改質流路部１６２を流れているときに改質触媒により反応して水素ガスが生成され、僅かながら一酸化炭素ガスも生成される（燃料がメタノールの場合には、下記化学式（１）、（２）を参照。）。空気供給流路部１６４に空気を供給すると、水素ガス、一酸化炭素ガス、空気等が混合した状態で一酸化炭素除去流路部１６５を流れる。このとき、一酸化炭素ガスが一酸化炭素除去触媒により優先的に酸化する選択酸化反応が起こり、一酸化炭素ガスが除去される（下記化学式（３）参照。）。そして、水素ガス等を含むガスが一酸化炭素除去流路部１６５から排出される。
ＣＨ3ＯＨ＋Ｈ2Ｏ→３Ｈ2＋ＣＯ2・・・（１）
Ｈ2＋ＣＯ2→Ｈ2O＋ＣＯ・・・（２）
２ＣＯ＋Ｏ2→２ＣＯ2・・・（３）
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 139 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 path portion 135, 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 (when the fuel is methanol, refer to the following chemical formulas (1) and (2)). 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 (see the following chemical formula (3)). Then, a gas containing hydrogen gas or the like is discharged from the carbon monoxide removal flow path portion 165.
CH 3 OH + H 2 O → 3H 2 + CO 2 (1)
H 2 + CO 2 → H 2 O + CO (2)
2CO + O 2 → 2CO 2 (3)
貫通孔１３６，１６６，１７６よりも左側の部分の温度が３００℃以上になるように、貫通孔１３６，１６６，１７６よりも右側の部分は左側の部分よりも低くなるように、電熱パターン１０６，１３９の発熱量や燃焼ガスの燃焼熱量を調整すると良い。ここで、貫通孔１３６，１６６，１７６が形成されているので、貫通孔１３６，１６６，１７６よりも右側の部分と左側の部分の温度差が生じるようになっている。
The electrothermal pattern 106, so that the portion on the right side of the through holes 136, 166, and 176 is lower than the portion on the left side so that the temperature of the portion on the left side of the through holes 136, 166, and 176 is 300 ° C. or higher. It is preferable to adjust the heat generation amount of 139 and the combustion heat amount of the combustion gas. Here, since the through holes 136, 166, and 176 are formed, a temperature difference between the right side portion and the left side portion of the through holes 136, 166, and 176 is generated.
なお、燃料（例えば、メタノール、エタノール、ジメチルエーテル）と空気（酸素）の混合気を燃料供給流路部１６１に供給するようにしても良い。この場合、燃料が部分酸化改質反応を起こして水素ガスが生成されるが、その場合、改質流路部１６２，１７２の壁面に担持させる触媒は部分酸化改質触媒とする。改質流路部１６２，１７２の担持させる触媒を２種類にし、部分酸化改質反応と水蒸気改質反応（上記式（１））を組み合わせても良い。
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 a partial oxidation reforming reaction and a steam reforming reaction (the above formula (1)) may be combined.
複合型マイクロ反応装置１００の用途について説明する。
この複合型マイクロ反応装置１００は、図６に示すような発電装置９００に用いることができる。この発電装置９００は、燃料と水を液体の状態で貯留した燃料パッケージ９０１と、燃料パッケージ９０１から供給された燃料と水を気化させる気化器９０２と、複合型マイクロ反応装置１００と、複合型マイクロ反応装置１００から供給された水素ガスにより電気エネルギーを生成する燃料電池９０３とを備える。気化器９０２で気化した燃料と水は燃料供給流路部１６１，１７１（改質器）に流れ込み、一酸化炭素除去流路部１６５，１７５（一酸化炭素除去器）から流れ出た水素ガス等は燃料電池９０３の燃料極に供給され、燃料電池９０３の酸素極には空気が供給され、燃料電池９０３における電気化学反応により電気エネルギーが生成される。ここで、燃料電池９０３の燃料極に供給された水素ガスは全てが反応するわけでなく、残留した水素ガスもあるので、その水素ガスが燃焼燃料供給流路部１３１（燃焼器）に供給される。
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 100. The fuel and water vaporized in the vaporizer 902 flow into the fuel supply flow path portions 161 and 171 (reformers), and hydrogen gas and the like flowing out from the carbon monoxide removal flow path portions 165 and 175 (carbon monoxide remover) Air is supplied to the fuel electrode of the fuel cell 903, air is supplied to the oxygen electrode of the fuel cell 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 reacts and some hydrogen gas remains, so that the hydrogen gas is supplied to the combustion fuel supply flow path 131 (combustor). The
このような本実施形態においては、上基板１０２、中基板１０３、下基板１２０の接合体１０１が燃焼熱や電熱によって加熱されると、接合体１０１が膨張する。特に貫通孔１３６，１６６，１７６によって右側の部分と左側の部分の温度差が生じ、に貫通孔１３６，１６６，１７６よりも左側の部分が右側の部分よりも膨張する。このような膨張により入隅１３，２３，３３に応力が集中するので、入隅１３，２３，３３を丸めた状態に形成すると、入隅１３，２３，３３に集中する応力を分散させることができる。そのため、接合体１０１の損傷や破壊を防止することができる。
In this embodiment, when the joined body 101 of the upper substrate 102, the middle substrate 103, and the lower substrate 120 is heated by combustion heat or electric heat, the joined body 101 expands. In particular, the temperature difference between the right part and the left part is caused by the through holes 136, 166, and 176, and the left part of the through holes 136, 166, and 176 expands more than the right part. Since stress concentrates on the corners 13, 23, and 33 due to such expansion, if the corners 13, 23, and 33 are formed in a rounded state, stress concentrated on the corners 13, 23, and 33 can be dispersed. it can. Therefore, damage and destruction of the bonded body 101 can be prevented.
また、上基板１０２、中基板１０３、下基板１２０の接合体１０１が真空圧の断熱パッケージ１５０に収容されているため、膨張するような力が接合体に作用し、接合体内部に形成された入隅１１，２１，３１や出隅１２，２２，３２に応力が集中する。それら入隅１１，２１，３１や出隅１２，２２，３２を丸めた状態に形成すると、入隅１１，２１，３１や出隅１２，２２，３２に集中する応力を分散させ、接合体１０１の損傷や破壊を防止することができる。
In addition, since the joined body 101 of the upper substrate 102, the middle substrate 103, and the lower substrate 120 is accommodated in the heat insulating package 150 having a vacuum pressure, an expanding force acts on the joined body and is formed inside the joined body. Stress concentrates on the entrance corners 11, 21, 31 and the exit corners 12, 22, 32. When the entrance corners 11, 21, 31 and the exit corners 12, 22, 32 are formed in a rounded state, the stress concentrated on the entrance corners 11, 21, 31 and the exit corners 12, 22, 32 is dispersed, and the joined body 101. Can be prevented from being damaged or destroyed.
また、中基板１０３の下面に電熱パターン１０６が形成され、その電熱パターン１０６が下基板１２０の燃焼流路部１３５に収容された状態で下基板１２０が中基板１０３に接合されているので、電熱パターン１０６から発した熱が燃焼流路部１３５内に籠もる。そのため、電熱パターン１０６で発した熱が、改質流路部１６２，１７２内における燃料の改質反応や、燃焼流路部１３５内における燃焼ガスの燃焼に効率よく用いられる。
In addition, since the electrothermal pattern 106 is formed on the lower surface of the middle substrate 103, and the lower substrate 120 is joined to the middle substrate 103 in a state where the electrothermal pattern 106 is accommodated in the combustion flow path portion 135 of the lower substrate 120, Heat generated from the pattern 106 is trapped in the combustion flow path portion 135. Therefore, the heat generated by the electrothermal 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 135.
