JP2005224765A - Reaction process using microreactor, and microreactor - Google Patents

Reaction process using microreactor, and microreactor Download PDF

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JP2005224765A
JP2005224765A JP2004038517A JP2004038517A JP2005224765A JP 2005224765 A JP2005224765 A JP 2005224765A JP 2004038517 A JP2004038517 A JP 2004038517A JP 2004038517 A JP2004038517 A JP 2004038517A JP 2005224765 A JP2005224765 A JP 2005224765A
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liquid
microreactor
gas
reaction
microchannel
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Yasunori Ichikawa
靖典 市川
Fumiko Shiraishi
文子 白石
Tomohide Kamiyama
友秀 上山
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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<P>PROBLEM TO BE SOLVED: To provide a microreactor capable of promoting a liquid-liquid reaction in which gas is produced as a by-product particularly in a minute micro flow passage, and to provide a reaction process using the microreactor. <P>SOLUTION: A plurality of liquids L1, L2 are subjected to the liquid-liquid reaction, in which the microreactor 10 is used and gas is produced as the by-product, by introducing the plurality of liquids L1, L2 through respective liquid supplying lines 28, 28, merging the liquids in the micro flow passage 26 while circulating each of the liquids L1, L2 as a laminar flow and diffusing the liquids L1, L2 toward the normal line of the contact interface between the liquids. In this case, a part or the whole of the wall of at least the micro flow passage 26 in the liquid supplying lines 28 and the micro flow passages 26 is formed from a gas-permeable member 18 through which a liquid does not pass but a gas passes and the gas being the by-product generated in the micro flow passage 26 is discharged to the outside of the micro flow passage 26 through the gas-permeable member 18. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

本発明はマイクロリアクターを用いた反応方法及びマイクロリアクターに係り、特に微細なマイクロ流路で副生ガスの発生を伴う液液反応を行うことが可能なマイクロリアクター、及びそれを用いた反応方法に関する。   The present invention relates to a reaction method and a microreactor using a microreactor, and more particularly to a microreactor capable of performing a liquid-liquid reaction accompanied by generation of by-product gas in a fine microchannel, and a reaction method using the same. .

複数の液体の液液反応の結果として副生ガスを発生する化学反応は多数知られている。例えば、磁気記録媒体を構成する磁性層に含有される金属微粒子の製造においては、金属微粒子を形成する液液反応で副生ガス（例えば水素ガス）の発生を伴う場合がある。   Many chemical reactions that generate by-product gas as a result of liquid-liquid reactions of a plurality of liquids are known. For example, in the production of metal fine particles contained in a magnetic layer constituting a magnetic recording medium, by-product gas (for example, hydrogen gas) may be generated in a liquid-liquid reaction that forms metal fine particles.

一方、特許文献１及び特許文献２に見られるように、反応生成物の生成物収率や純度を上げたり、危険性や爆発性の試薬を用いた反応を安全に実施したりするための反応装置として、流路幅が１ｍｍ以下の極めて微細なマイクロ流路を使用して複数の流体を反応させるマイクロリアクターが注目されている。このマイクロリアクターは、反応を行うマイクロ流路が上記の通りマイクロスケールのサイズであることに起因して、マイクロ流路を流れる流体は層流支配の流れとなり、これにより反応を行う液体同士は機械的な攪拌を行わなくてもマイクロ流路を層流状態となって流れながら分子の自発的挙動だけで拡散しながら反応を速やかに行うことができる。
特表２００１−５２１９１３号公報 特表２００１−５２１８１６号公報 On the other hand, as seen in Patent Document 1 and Patent Document 2, the reaction for increasing the product yield and purity of the reaction product, and for safely carrying out the reaction using dangerous or explosive reagents As a device, a microreactor that reacts a plurality of fluids using an extremely fine microchannel having a channel width of 1 mm or less has been attracting attention. In this microreactor, the fluid flowing through the microchannel becomes a laminar-dominated flow because the microchannel for performing the reaction has a micro-scale size as described above. Even without agitation, the reaction can be rapidly carried out while diffusing only by the spontaneous behavior of molecules while flowing in a laminar flow through the microchannel.
JP-T-2001-521913 JP-T-2001-521816

しかしながら、マイクロリアクターでは副生ガスの発生を伴う液液反応を行えないという問題がある。その理由は、１モルの副生ガスが生成されたとすると、その副生ガスの体積は２２．４Ｌの大きな体積になる為、微細なマイクロ流路を塞いでしまい均一な反応を行えないからである。即ち、副生ガスをマイクロ流路から効率的に除去できないと、発生した副生ガスの気泡がマイクロ流路に溜まって塊となるために、マイクロ流路の流れが気液混合相流、例えば図７に示すスラグ流が発生する。このスラグ流は気泡の塊Ｂと反応させるべき液体Ｌとがマイクロ流路２６の流れ方向に交互に存在する。この結果、液体Ｌの連続処理の流れを妨げたり、乱したりすることで連続処理の流れが不安定になって反応場が不均一になると共に、反応の平衡が反応促進側に進みにくくなる。また、反応のための液温制御を行う場合、副生ガスを連続処理の流れの中で効率的に除去できないと、気体は熱伝導率が小さいので、反応温度を精度良く制御できなくなる。   However, the microreactor has a problem that liquid-liquid reaction accompanied by generation of by-product gas cannot be performed. The reason is that if 1 mole of by-product gas is generated, the volume of the by-product gas becomes a large volume of 22.4 L, so that the micro-channel is blocked and a uniform reaction cannot be performed. is there. That is, if the by-product gas cannot be efficiently removed from the micro-channel, the generated by-product gas bubbles accumulate in the micro-channel and become lumps. The slag flow shown in FIG. 7 is generated. In this slag flow, the bubble mass B and the liquid L to be reacted are alternately present in the flow direction of the microchannel 26. As a result, the flow of continuous processing of the liquid L is disturbed or disturbed, the flow of continuous processing becomes unstable, the reaction field becomes non-uniform, and the reaction equilibrium does not easily proceed to the reaction promoting side. . In addition, when controlling the liquid temperature for the reaction, if the by-product gas cannot be efficiently removed in the flow of continuous processing, the gas has a low thermal conductivity, so the reaction temperature cannot be controlled with high accuracy.

非特許文献１（Wolfgang Ehrfeld他、「Microreactors 」、発行元：WILEY-VCH 、発行年月日:2000 年）の第８章（Gas/Liquid Microreactors) には、気液反応のマイクロリアクターとしてFalling-film ReactorやBubble-Column Reactor が開示されているが、このような装置は気液反応を行うための装置であり、液液反応で発生する副生ガスの除去に関しては何ら考慮されていない。従って、気液反応のマイクロリアクターを使用して副生ガスを伴う液液反応を適切に行うことはできない。   In Chapter 8 (Gas / Liquid Microreactors) of Non-Patent Document 1 (Wolfgang Ehrfeld et al., “Microreactors”, Publisher: WILEY-VCH, Date of Publication: 2000), Falling- Film Reactor and Bubble-Column Reactor are disclosed, but such an apparatus is an apparatus for performing a gas-liquid reaction, and no consideration is given to removal of by-product gas generated in the liquid-liquid reaction. Therefore, a liquid-liquid reaction involving by-product gas cannot be appropriately performed using a gas-liquid reaction microreactor.

このような事情から、マイクロリアクターで副生ガスを発生する化学反応を実施した例は聞いたことがなく、このことはマイクロリアクターを利用できる化学反応の種類を大幅に減少させることとなる。このことからマイクロリアクターでも副生ガスを発生する化学反応を実施できるようにすることが、大きな課題になっている。   Under such circumstances, there has never been an example in which a chemical reaction that generates a by-product gas in a microreactor has been carried out, and this greatly reduces the types of chemical reactions that can use the microreactor. For this reason, it has become a big issue to be able to carry out a chemical reaction that generates a by-product gas even in a microreactor.

本発明は係る事情に鑑みてなされたもので、等価直径が例えば１ｍｍ以下の微細なマイクロ流路内の液液反応によって発生する副生ガスをマイクロ流路から効率的に脱ガスすることができるので、マイクロリアクターを用いて副生ガスが発生する液液反応を行っても、マイクロ流路における液体の流れを不安定化させることなく液液反応を行うことができるマイクロリアクターを用いた反応方法及びマイクロリアクターを提供することを目的とする。   The present invention has been made in view of such circumstances, and by-product gas generated by a liquid-liquid reaction in a fine microchannel having an equivalent diameter of, for example, 1 mm or less can be efficiently degassed from the microchannel. Therefore, a reaction method using a microreactor that can perform a liquid-liquid reaction without destabilizing the flow of the liquid in the microchannel even when performing a liquid-liquid reaction in which a by-product gas is generated using the microreactor And to provide a microreactor.

本発明の請求項１は前記目的を達成するために、複数の液体をそれぞれの液体供給路を通してマイクロ流路に合流させて、これらの液体を薄片状の層流として流通させつつ、液体同士をその接触界面の法線方向へ拡散して液液反応を行わせる薄片状流型のマイクロリアクターを用いて、副生ガスの発生を伴う液液反応を行うマイクロリアクターの反応方法において、前記液液反応の進行に伴って発生する副生ガスを、液体を通さずに気体を通す気体透過部材を介して前記マイクロ流路外に随時透過しながら前記液液反応を行わせることを特徴とする。   In order to achieve the above object, according to the first aspect of the present invention, a plurality of liquids are joined to the micro flow path through the respective liquid supply paths, and these liquids are circulated as a laminar laminar flow while In the reaction method of a microreactor in which a liquid-liquid reaction involving generation of by-product gas is performed using a flaky flow type microreactor that diffuses in the normal direction of the contact interface to perform a liquid-liquid reaction, The by-product gas generated with the progress of the reaction is allowed to perform the liquid-liquid reaction while being permeated through the gas passage member through the gas without passing through the liquid as needed.

本発明の請求項１は、薄片状流型のマイクロリアクターを用い、液液反応によりマイクロ流路に副生ガスの発生を伴う反応を行う方法である。   Claim 1 of the present invention is a method for performing a reaction involving generation of by-product gas in a microchannel by a liquid-liquid reaction using a flaky flow type microreactor.

マイクロリアクターの特徴として、マイクロ流路を流れる液体同士がその接触界面の法線方向へ拡散することで反応が進行するので、反応による副生ガスも反応の進行に伴って少しずつ発生する。従って、発生した副生ガスが集まってマイクロ流路を塞ぐような塊にならないうちに副生ガスを如何に速やかにマイクロ流路外に除去するかが重要になる。   As a feature of the microreactor, the reaction proceeds as liquids flowing through the microchannel diffuse in the normal direction of the contact interface, so that by-product gas due to the reaction is generated little by little as the reaction proceeds. Therefore, it is important how quickly the by-product gas is removed from the micro-channel before the generated by-product gas collects and forms a mass that blocks the micro-channel.

本発明の請求項１によれば、液液反応の進行に伴って発生する副生ガスを、液体を通さずに気体を通す気体透過部材を介してマイクロ流路外に随時透過しながら液液反応を行わせるようにしたので、等価直径が例えば１ｍｍ以下の微細なマイクロ流路を有するマイクロリアクターで副生ガスを発生する液液反応を行っても、マイクロ流路における液体の流れを不安定化させることなく液液反応を行うことができる。   According to the first aspect of the present invention, while the by-product gas generated with the progress of the liquid-liquid reaction passes through the gas passage member that allows the gas to pass through without passing through the liquid, the liquid liquid while passing through the microchannel as needed. Since the reaction is performed, the liquid flow in the microchannel is unstable even when a liquid-liquid reaction that generates by-product gas is performed in a microreactor having a microchannel with an equivalent diameter of 1 mm or less. Liquid-liquid reaction can be performed without making it.

本発明の請求項２は前記目的を達成するために、円環状なマイクロ流路に連通する複数の液体供給路を同心軸の多重筒構造にして、複数の液体を前記液体供給路を通して前記マイクロ流路に合流させることにより、これらの液体を同心軸状に積層させて該同心軸に直交する断面が円環状の層流として流通させつつ、液体同士をその接触界面の法線方向へ拡散して液液反応を行わせる円環状流型のマイクロリアクターを用いて、副生ガスの発生を伴う液液反応を行うマイクロリアクターの反応方法において、前記液液反応の進行に伴って発生する副生ガスを、液体を通さずに気体を通す気体透過部材を介して前記マイクロ流路外に随時透過しながら前記液液反応を行わせることを特徴とする。   According to a second aspect of the present invention, in order to achieve the above object, a plurality of liquid supply passages communicating with an annular microchannel are formed in a concentric multiple tube structure, and a plurality of liquids are passed through the liquid supply passage. By merging with the flow path, these liquids are stacked concentrically, and the liquids are diffused in the normal direction of the contact interface while the cross section orthogonal to the concentric axes is circulated as an annular laminar flow. In a reaction method of a microreactor that performs a liquid-liquid reaction accompanied by the generation of by-product gas using an annular flow type microreactor that performs a liquid-liquid reaction, a by-product generated as the liquid-liquid reaction proceeds The liquid-liquid reaction is performed while allowing gas to pass through the gas flow member through which gas passes without passing through the liquid as needed.

本発明の請求項２は、円環状流型のマイクロリアクターを用い、液液反応によりマイクロ流路に副生ガスの発生を伴う反応を行う方法である。この場合にも、液液反応の進行に伴って発生する副生ガスを、液体を通さずに気体を通す気体透過部材を介してマイクロ流路外に随時透過しながら液液反応を行わせることで、等価直径が例えば１ｍｍ以下の微細なマイクロ流路を有する環状型のマイクロリアクターで副生ガスが発生する液液反応を行っても、マイクロ流路における液体の流れを不安定化させることなく液液反応を行うことができる。   Claim 2 of the present invention is a method for performing a reaction accompanied by generation of by-product gas in a microchannel by a liquid-liquid reaction using an annular flow type microreactor. Also in this case, the liquid-liquid reaction is performed while the by-product gas generated with the progress of the liquid-liquid reaction is transmitted through the gas passage member through which the gas passes without passing through the liquid as needed. Thus, even when a liquid-liquid reaction in which by-product gas is generated is performed in an annular microreactor having a fine microchannel having an equivalent diameter of, for example, 1 mm or less, the liquid flow in the microchannel is not destabilized. A liquid-liquid reaction can be performed.

請求項３は請求項１又は２において、前記マイクロ流路の等価直径は１ｍｍ以下であることを特徴とする。   A third aspect of the present invention is characterized in that, in the first or second aspect, the equivalent diameter of the microchannel is 1 mm or less.

ここで、等価直径とは流路断面を円形に換算した場合の直径を言い、以下同じである。   Here, the equivalent diameter means a diameter when the cross section of the flow path is converted into a circle, and the same applies hereinafter.

これは、マイクロ流路の等価直径が小さければ小さいほど副生ガスによりマイクロ流路の流れが不安定化し易く、それだけ本発明が有効だからであり、特に本発明の有効なマイクロ流路の等価直径は５００μｍ以下である。   This is because the smaller the equivalent diameter of the micro-channel, the more easily the flow of the micro-channel is destabilized by by-product gas, and the present invention is more effective. In particular, the equivalent diameter of the effective micro-channel of the present invention. Is 500 μm or less.

請求項４は請求項１〜３の何れか１において、前記マイクロ流路側の第１の圧力が該マイクロ流路の外側の第２の圧力よりも大きくなるように、前記第１及び第２の圧力を相対的に制御することを特徴とする。   A fourth aspect of the present invention is the method according to any one of the first to third aspects, wherein the first pressure on the microchannel side is greater than the second pressure on the outside of the microchannel. The pressure is relatively controlled.

気体透過部材の気体透過性能や液液反応を行う液体の組成（例えば乳化剤を含む液体）によっては、液液反応によってマイクロ流路に発生した副生ガスが気体透過部材をスムーズに透過しにくい場合がある。請求項４では、マイクロ流路側の第１の圧力が該マイクロ流路の外側の第２の圧力よりも大きくなるように、第１及び第２の圧力を相対的に制御するようにしたので、気体透過部材の気体透過性能や液液反応を行う液体の組成に影響されずに副生ガスをスムーズに気体透過部材を透過させることができる。これにより、等価直径が例えば１ｍｍ以下の微細なマイクロ流路を有するマイクロリアクターで副生ガスを発生する液液反応を行っても、マイクロ流路における液体の流れを一層不安定化させることなく液液反応を行うことができる。   Depending on the gas permeation performance of the gas permeable member and the composition of the liquid that performs the liquid-liquid reaction (for example, a liquid containing an emulsifier), the by-product gas generated in the microchannel due to the liquid-liquid reaction is difficult to smoothly pass through the gas permeable member There is. In claim 4, since the first pressure and the second pressure are relatively controlled so that the first pressure on the microchannel side becomes larger than the second pressure outside the microchannel, By-product gas can be smoothly permeated through the gas permeable member without being affected by the gas permeable performance of the gas permeable member and the composition of the liquid that performs the liquid-liquid reaction. As a result, even if a liquid-liquid reaction that generates a by-product gas is performed in a microreactor having a micro-channel having an equivalent diameter of, for example, 1 mm or less, the liquid flow in the micro-channel is not further destabilized. A liquid reaction can be performed.

本発明の請求項５は前記目的を達成するために、複数の液体をそれぞれの液体供給路を通してマイクロ流路に合流させてこれらの液体を薄片状の層流として流通させつつ、液体同士をその接触界面の法線方向へ拡散して液液反応を行わせるマイクロリアクターにおいて、前記液体供給路及び前記マイクロ流路のうちの少なくともマイクロ流路の流路壁の一部又は全部が、液体は通さずに気体を通す気体透過部材で形成されていることを特徴とする。   According to a fifth aspect of the present invention, in order to achieve the above object, a plurality of liquids are joined to the micro flow path through the respective liquid supply paths, and these liquids are circulated as a laminar laminar flow while In the microreactor in which the liquid-liquid reaction is performed by diffusing in the normal direction of the contact interface, at least a part or all of the channel wall of the microchannel is not allowed to pass through the liquid supply channel and the microchannel. It is formed by the gas permeable member which lets gas pass through.

本発明の請求項５は、薄片状流型のマイクロリアクターの場合であり、液体供給路及びマイクロ流路のうちの少なくともマイクロ流路を形成する流路壁の一部又は全部が気体透過部材で形成されている。これにより、液液反応によりマイクロ流路に発生した副生ガスは気体透過部材を透過し、マイクロ流路外に排出される。薄片状流型のマイクロリアクターの場合、マイクロ流路で発生した副生ガスが液体中を浮上してマイクロ流路を形成する流路壁の上面に溜まることから、流路壁の上面部を気体透過部材で構成することが好ましい。流路壁の上面部のように流路壁の一部を気体透過部材で構成する場合には軟質材料でも問題なので、気体透過性を有する高分子膜、例えばゴアテックス膜（商標）を好適に使用することができる。   Claim 5 of the present invention is a case of a flaky flow type microreactor, and at least a part or all of the flow path wall forming the micro flow path among the liquid supply path and the micro flow path is a gas permeable member. Is formed. Thereby, the by-product gas generated in the microchannel by the liquid-liquid reaction permeates the gas permeable member and is discharged out of the microchannel. In the case of a flaky flow type microreactor, the by-product gas generated in the microchannel floats in the liquid and accumulates on the upper surface of the channel wall forming the microchannel. It is preferable to comprise a transmissive member. When a part of the flow path wall is made of a gas permeable member, such as the upper surface of the flow path wall, a soft material is also a problem. Therefore, a polymer film having gas permeability, such as Gore-Tex Membrane (trademark) is preferably used. Can be used.

本発明の請求項６は前記目的を達成するために、円環状のマイクロ流路に連通する複数の液体供給路を同心軸の多重円筒構造にして、複数の液体を前記液体供給路を通して前記マイクロ流路に合流させることにより、これらの液体を同心軸状に積層させて該同心軸に直交する断面が円環状の層流として流通させつつ、液体同士をその接触界面の法線方向へ拡散して副生ガスを伴う液液反応を行わせる円環状流型のマイクロリアクターにおいて、前記液体供給路及び前記マイクロ流路のうちの少なくとも円環状のマイクロ流路の流路壁の一部又は全部が、液体は通さずに気体を通す気体透過部材で形成されていることを特徴とする。   According to a sixth aspect of the present invention, in order to achieve the above object, a plurality of liquid supply paths communicating with an annular micro flow path are formed in a concentric multi-cylindrical structure, and a plurality of liquids are passed through the liquid supply path. By merging with the flow path, these liquids are stacked concentrically, and the liquids are diffused in the normal direction of the contact interface while the cross section orthogonal to the concentric axes is circulated as an annular laminar flow. In the annular flow type microreactor in which a liquid-liquid reaction involving by-product gas is performed, at least a part or all of the channel wall of the annular microchannel among the liquid supply channel and the microchannel The liquid permeable member allows gas to pass through without passing through the liquid.

本発明の請求項６は、円環状流型のマイクロリアクターの場合であり、液体供給路及びマイクロ流路のうちの少なくとも円環状のマイクロ流路を形成する流路壁の一部又は全部が気体透過部材で形成されている。これにより、液液反応によりマイクロ流路に発生した副生ガスは気体透過部材を透過し、マイクロ流路外に排出される。円環状流型のマイクロリアクターの場合、円環状のマイクロ流路で発生した副生ガスが近くの気体透過部材を直ちに透過する構造の方が好ましいので、流路壁の全体を気体透過部材で構成することが好ましい。このように、流路壁全体を気体透過部材とする場合には高分子膜のような軟質材は使用できないので、マイクロマシンニング技術により、液体は通さないが気体は通す極めて微細な穴を開けた金属材料やプラスチック樹脂材料等の硬質材料を気体透過部材として使用することが好ましい。硬質材料の気体透過部材の場合には、マイクロ流路の流路壁全体を気体透過部材で構成することが可能であるので、円環状流型のマイクロリアクターの場合に好適である。いずれにしても本発明はこのような技術の進歩如何にかかわらず、液液反応によりマイクロ流路に発生する副生ガスだけを透過させる気体透過部材であればどのようなものでもよい。   Claim 6 of the present invention is a case of an annular flow type microreactor, and at least a part or all of the flow path wall forming the circular micro flow path of the liquid supply path and the micro flow path is gas. It is formed of a transmissive member. Thereby, the by-product gas generated in the microchannel by the liquid-liquid reaction permeates the gas permeable member and is discharged out of the microchannel. In the case of an annular flow type microreactor, it is preferable that the by-product gas generated in the annular micro flow channel is immediately transmitted through a nearby gas permeable member, so the entire flow channel wall is constituted by a gas permeable member. It is preferable to do. In this way, when the entire flow path wall is used as a gas permeable member, a soft material such as a polymer film cannot be used. Therefore, by micromachining technology, a very fine hole that does not allow liquid but allows gas to pass is opened. It is preferable to use a hard material such as a metal material or a plastic resin material as the gas permeable member. In the case of a gas permeable member made of a hard material, the entire flow channel wall of the micro flow channel can be constituted by the gas permeable member, which is suitable for an annular flow type microreactor. In any case, the present invention may be any gas permeable member that allows only the by-product gas generated in the microchannel by the liquid-liquid reaction to permeate regardless of the progress of such technology.

請求項７は請求項５又は６において、前記マイクロ流路の等価直径は１ｍｍ以下であることを特徴とする。これは、マイクロ流路の等価直径が小さければ小さいほど副生ガスによりマイクロ流路の流れが不安定化し易く、それだけ本発明が有効だからであり、特に本発明の有効なマイクロ流路の等価直径は５００μｍ以下である。   A seventh aspect is characterized in that, in the fifth or sixth aspect, the equivalent diameter of the microchannel is 1 mm or less. This is because the smaller the equivalent diameter of the micro-channel, the more easily the flow of the micro-channel is destabilized by by-product gas, and the present invention is more effective. In particular, the equivalent diameter of the effective micro-channel of the present invention. Is 500 μm or less.

請求項８は請求項５〜７の何れか１において、前記気体透過部材を挟んで前記マイクロ流路反対側に形成され、前記液体供給路及び前記マイクロ流路のうちの少なくともマイクロ流路の流れ方向に沿った空洞部と、前記マイクロ流路側の第１の圧力が前記空洞部側の第２の圧力よりも大きくなるように、前記第１及び第２の圧力を相対的に制御する圧力制御手段と、を備えたことを特徴とする。   An eighth aspect of the present invention is the method according to any one of the fifth to seventh aspects, wherein the flow path is formed on the opposite side of the microchannel with the gas permeable member interposed therebetween. Pressure control for relatively controlling the first and second pressures so that the cavity along the direction and the first pressure on the microchannel side are larger than the second pressure on the cavity side Means.

気体透過部材の気体透過性能や液液反応を行う液体の組成（例えば乳化剤を含む液体）によって、副生ガスが気体透過部材をスムーズに透過しにくい場合であっても、圧力制御手段でマイクロ流路側の第１の圧力が空洞部側の第２の圧力よりも大きくなるようにすることで、副生ガスのスムーズな透過を達成することができる。   Even if the by-product gas is difficult to smoothly pass through the gas permeable member due to the gas permeable performance of the gas permeable member or the composition of the liquid that performs liquid-liquid reaction (for example, a liquid containing an emulsifier), By allowing the first pressure on the road side to be greater than the second pressure on the cavity portion side, smooth permeation of by-product gas can be achieved.

請求項９は請求項８において、前記圧力制御手段は、前記空洞部を吸引して該空洞部を減圧する吸引方式であることを特徴とする。   A ninth aspect of the present invention according to the eighth aspect is characterized in that the pressure control means is a suction system that sucks the cavity and depressurizes the cavity.

請求項１０は請求項８において、前記圧力制御手段は、前記空洞部に高速気流を発生させてピトー管現象を生じさせる気体流方式であることを特徴とする。   A tenth aspect of the present invention is characterized in that, in the eighth aspect, the pressure control means is a gas flow system that generates a pitot tube phenomenon by generating a high-speed air flow in the cavity.

請求項１１は請求項８において、前記圧力制御手段は、前記副生ガスが前記気体透過部材を透過する際の圧力損失以上の圧力を前記マイクロ流路側に加える加圧方式であることを特徴とする。   An eleventh aspect of the present invention is characterized in that, in the eighth aspect, the pressure control means is a pressurization method in which a pressure equal to or higher than a pressure loss when the by-product gas permeates the gas permeable member is applied to the microchannel side. To do.

請求項８〜１１は、マイクロ流路側の第１の圧力が空洞部側の第２の圧力よりも大きくなるようにする圧力制御手段の各種の態様を示したものである。   The eighth to eleventh aspects show various aspects of the pressure control means for making the first pressure on the microchannel side larger than the second pressure on the cavity side.

請求項１２は請求項５において、前記マイクロリアクターの装置本体を本体部材と蓋部材とで構成し、前記液体供給路から前記マイクロ流路の終端に至る液体流路及び前記空洞部の両方を前記本体部材に形成し、前記液体流路と前記空洞部との間に前記気体透過部材を設けたことを特徴とする。   A twelfth aspect of the present invention is the method according to the fifth aspect, wherein the main body of the microreactor is composed of a main body member and a lid member, and both the liquid flow path extending from the liquid supply path to the end of the micro flow path and the hollow portion are provided in the microreactor. It is formed in a main body member, and the gas permeable member is provided between the liquid channel and the cavity.

請求項１２は、液体流路を気体透過部材で仕切って一部を空洞部として兼用するように装置本体を構成した場合である。   A twelfth aspect of the present invention is a case where the apparatus main body is configured so that the liquid flow path is partitioned by the gas permeable member and a part is also used as a hollow portion.

請求項１３は請求項５において、前記マイクロリアクターの装置本体を本体部材と蓋部材とで構成し、前記液体供給路から前記マイクロ流路の終端に至る液体流路を前記本体部材に形成し、前記空洞部を前記蓋部材に形成し、本体部材と蓋部材とで前記気体透過部材を挟むことを特徴とする。   Claim 13 is the structure of claim 5, wherein the microreactor main body is composed of a main body member and a lid member, and a liquid flow path from the liquid supply path to the end of the micro flow path is formed in the main body member. The hollow portion is formed in the lid member, and the gas permeable member is sandwiched between the main body member and the lid member.

請求項１３によれば、液体流路を本体部材に形成し、空洞部を蓋部材に形成し、本体部材と蓋部材とで気体透過部材を挟むようにしたので、マイクロ流路を形成する流路壁の上面部を簡単に気体透過部材で形成することができ、請求項１１に比べて装置本体の製作が容易になる。   According to the thirteenth aspect, the liquid channel is formed in the main body member, the cavity is formed in the lid member, and the gas permeable member is sandwiched between the main body member and the lid member. The upper surface portion of the road wall can be easily formed of a gas permeable member, and the manufacture of the apparatus main body is facilitated as compared with the eleventh aspect.

請求項１４は請求項５〜１３の何れか１において、前記マイクロリアクターの装置本体を形成する材料は、金属、ガラス、セラミックス、プラスチック樹脂、シリコンの何れかであることを特徴とする。   A fourteenth aspect is characterized in that, in any one of the fifth to thirteenth aspects, the material forming the device body of the microreactor is any one of metal, glass, ceramics, plastic resin, and silicon.

請求項１４に示す材料が微細なマイクロ流路を形成する微細加工に適しているからである。また、マイクロ流路の流れ状態を観察できるように、透明ガラスや透明プラスチック樹脂を使用するのが一層好ましい。   This is because the material shown in claim 14 is suitable for microfabrication that forms a fine microchannel. Further, it is more preferable to use transparent glass or transparent plastic resin so that the flow state of the microchannel can be observed.

以上説明したように、本発明のマイクロリアクターを用いた反応方法及びマイクロリアクターによれば、等価直径が例えば１ｍｍ以下の微細なマイクロ流路内の液液反応によって発生する副生ガスをマイクロ流路から効率的に脱ガスすることができるので、液液反応に伴って副生ガスが発生する化学反応をマイクロリアクターで行っても、マイクロ流路における液体の流れを不安定化させることなく液液反応を行うことができる。   As described above, according to the reaction method and microreactor using the microreactor of the present invention, the by-product gas generated by the liquid-liquid reaction in the microchannel having an equivalent diameter of, for example, 1 mm or less is microchannel. Therefore, even if a chemical reaction in which a by-product gas is generated in a liquid-liquid reaction is performed in a microreactor, the liquid flow in the microchannel is not destabilized. The reaction can be performed.

以下、添付図面に従って、本発明に係るマイクロリアクターを用いた反応方法及びマイクロリアクターの最良の実施の形態について説明する。   Hereinafter, a reaction method using a microreactor according to the present invention and a best embodiment of the microreactor will be described with reference to the accompanying drawings.

図１は本発明に係るマイクロリアクターの第１の実施の形態を概念的に示した斜視図であり、薄片状流型のマイクロリアクター１０の場合である。図２（Ａ）はマイクロリアクター本体（以下、装置本体１２という）の上面図、図２（Ｂ）は断面図、図２（Ｃ）は下面図である。   FIG. 1 is a perspective view conceptually showing a first embodiment of a microreactor according to the present invention, which is a case of a flaky flow type microreactor 10. 2A is a top view of the microreactor body (hereinafter referred to as the apparatus body 12), FIG. 2B is a cross-sectional view, and FIG. 2C is a bottom view.

図１に示すように、薄片状流型のマイクロリアクター１０は、主として、気体透過部材１８を備えた装置本体１２と、副生ガスの発生を伴う液液反応を行う液体Ｌ１、Ｌ２を液体供給管１４、１４を介して装置本体１２に供給する液体供給手段１６、１６と、気体透過部材１８の気体透過性能を向上させる圧力制御手段４６とで構成される。尚、本実施の形態では２種類の液体Ｌ１、Ｌ２で液液反応を行う例で説明する。   As shown in FIG. 1, a flaky flow microreactor 10 mainly supplies a main body 12 having a gas permeable member 18 and liquids L1 and L2 for performing a liquid-liquid reaction accompanied by by-product gas generation. The liquid supply means 16 and 16 which supply to the apparatus main body 12 via the pipes 14 and 14 and the pressure control means 46 which improves the gas permeation performance of the gas permeation member 18 are comprised. In the present embodiment, an example in which a liquid-liquid reaction is performed with two types of liquids L1 and L2 will be described.

図２に示すように、装置本体１２は、本体部材２２と蓋部材２４とで平板状の気体透過部材１８をサンドイッチ状にした状態で互いに接着剤で接合し、その外側を上板２０と下板２１とで挟み込み、上板２０と下板２１の４角に形成されたボルト穴に通したボルト２３とナット２５とを締め付けることにより組み立てられる。本体部材２２には２種類の液体Ｌ１、Ｌ２の液液反応を行うマイクロ流路２６と該マイクロ流路２６に液体Ｌ１、Ｌ２を合流させる２本の液体供給路２８、２８とから成るＹ字型液体流路３０が形成される。一方、蓋部材２４にはＹ字型液体流路３０に対向してＹ字型空洞部３６が形成され、Ｙ字型液体流路３０とＹ字型空洞部３６とは気体透過部材１８によって仕切られる。即ち、Ｙ字型液体流路３０を形成する流路壁の上面部が気体透過部材１８によって構成され、気体透過部材１８の上側にＹ字型空洞部３６が形成されている。尚、本実施の形態では、気体透過部材１８の上側にＹ字型空洞部３６を形成して、後記するようにＹ字型空洞部３６を減圧してマイクロ流路２６で発生した副生ガスが気体透過部材１８を透過し易いように構成したが、気体透過部材１８の気体透過性能が優れており、減圧空洞部としてのＹ字型空洞部３６を設ける必要がない場合には、気体透過部材１８が大気に開放された構造の装置本体１２でもよい。その場合には、マイクロ流路２６で発生した副生ガスは気体透過部材１８を透過して大気に直接放出される。また、本実施の形態では、液体供給路２８とマイクロ流路２６とからなるＹ字型液体流路３０の上面部全体に気体透過部材１８を設けることで説明したが、副生ガスが発生するマイクロ流路２６の上面部のみに気体透過部材１８を設けるようにしてもよい。   As shown in FIG. 2, the apparatus main body 12 is bonded to each other with an adhesive in a state where the plate-like gas permeable member 18 is sandwiched between the main body member 22 and the lid member 24, and the outside is joined to the upper plate 20 and the lower plate 20. It is assembled by clamping between the plate 21 and tightening a bolt 23 and a nut 25 that are passed through bolt holes formed at four corners of the upper plate 20 and the lower plate 21. The main body member 22 has a Y-shape comprising a microchannel 26 for performing a liquid-liquid reaction of two types of liquids L1 and L2 and two liquid supply channels 28 and 28 for joining the liquids L1 and L2 to the microchannel 26. A mold liquid channel 30 is formed. On the other hand, a Y-shaped cavity 36 is formed in the lid member 24 so as to face the Y-shaped liquid flow path 30, and the Y-shaped liquid flow path 30 and the Y-shaped cavity 36 are partitioned by the gas permeable member 18. It is done. That is, the upper surface portion of the flow channel wall forming the Y-shaped liquid flow channel 30 is configured by the gas permeable member 18, and the Y-shaped cavity portion 36 is formed above the gas permeable member 18. In the present embodiment, a Y-shaped cavity portion 36 is formed on the upper side of the gas permeable member 18, and the Y-shaped cavity portion 36 is decompressed as will be described later, and a by-product gas generated in the microchannel 26. However, if the Y-shaped cavity 36 as the decompression cavity is not required to be provided, the gas transmission member 18 can be used. The apparatus main body 12 having a structure in which the member 18 is open to the atmosphere may be used. In that case, the by-product gas generated in the micro flow channel 26 passes through the gas permeable member 18 and is directly released to the atmosphere. In the present embodiment, the gas permeable member 18 is provided on the entire upper surface of the Y-shaped liquid flow path 30 including the liquid supply path 28 and the micro flow path 26, but by-product gas is generated. The gas permeable member 18 may be provided only on the upper surface of the microchannel 26.

装置本体１２を製作する上で、最も重要なポイントは如何に気体透過性能の良い気体透過部材１８を使用するかであり、近年の高分子技術の進歩により例えばゴアテックス膜（商標）のような気体透過性能の良い膜が市販されており、このような膜を使用することができる。また、近年のマイクロマシンニング技術の進歩により、液体は通さないが気体は通す極めて微細な穴を金属やプラスチック樹脂等の硬質材料に開けることが可能になってきており、このような技術を使用して硬質材料を用いて気体透過部材１８を製作することも可能である。いずれにしても本発明はこのような技術の進歩如何にかかわらず、液液反応によりマイクロ流路２６に発生する副生ガスだけを透過させる気体透過部材１８であればどのようなものでもよい。   In manufacturing the apparatus main body 12, the most important point is how to use the gas permeable member 18 having a good gas permeable performance. Membranes with good gas permeation performance are commercially available, and such membranes can be used. Also, due to recent advances in micromachining technology, it has become possible to open extremely fine holes that do not allow liquids to pass but allow gas to pass through hard materials such as metals and plastic resins. It is also possible to manufacture the gas permeable member 18 using a hard material. In any case, the present invention may be any gas permeable member 18 that allows only the by-product gas generated in the microchannel 26 by the liquid-liquid reaction to permeate regardless of the progress of such technology.

装置本体１２の内部に形成されるマイクロ流路２６は、等価直径が１ｍｍ（１０００μｍ）以下、好ましくは５００μｍ以下のマイクロチャンネル状の微細流路であることが好ましい。また、マイクロ流路２６は、径方向断面の形状が四角形状のものが一般的であるが四角形状に限定するものではない。そして、液体供給路２８、２８を２本で構成する場合には、１本の液体供給路２８の等価直径はマイクロ流路２６の半分になるように設計することが好ましい。例えば、径方向断面が四角形状のマイクロ流路２６の幅を５００μｍ、深さを２００μｍとした場合には、１本の液体供給路２８の幅を２５０μｍ、深さを２００μｍとする。また、マイクロ流路２６の長さＬ（図２参照）は、液液反応が終了するに足る長さに設定され、液液反応の種類によって異なる。   The microchannel 26 formed inside the apparatus main body 12 is preferably a microchannel-shaped microchannel having an equivalent diameter of 1 mm (1000 μm) or less, preferably 500 μm or less. In addition, the micro flow path 26 is generally rectangular in cross-section in the radial direction, but is not limited to a quadrangular shape. When the two liquid supply paths 28 and 28 are configured, it is preferable to design the equivalent diameter of one liquid supply path 28 to be half that of the micro flow path 26. For example, when the width of the microchannel 26 having a quadrangular radial cross section is 500 μm and the depth is 200 μm, the width of one liquid supply path 28 is 250 μm and the depth is 200 μm. Further, the length L (see FIG. 2) of the micro flow channel 26 is set to a length sufficient to complete the liquid-liquid reaction, and varies depending on the type of the liquid-liquid reaction.

かかるマイクロオーダーの微細なＹ字型液体流路３０やＹ字型空洞部３６を有する装置本体１２を製作するには微細加工技術が使用される。微細加工技術としては、例えば次のようなものがある。
(1) Ｘ線リソグラフィと電気メッキを組み合わせたＬＩＧＡ技術
(2) ＥＰＯＮ ＳＵ８を用いた高アスペクト比フォトリソグラフィ法
(3) 機械的マイクロ切削加工（ドリル径がマイクロオーダのドリルを高速回転するマイクロドリル加工等）
(4) Ｄｅｅｐ ＲＩＥによるシリコンの高アスペクト比加工法
(5) Ｈｏｔ Ｅｍｂｏｓｓ加工法
(6) 光造形法
(7) レーザー加工法
(8) イオンビーム法
また、装置本体１２を製作するのための材料としては、耐熱、耐圧及び耐溶剤性、加工容易性等の要求に応じて、金属、ガラス、セラミックス、プラスチック、シリコン、及びテフロン等を好適に使用できる。装置本体１２の製作においては、Ｙ字型液体流路３０やＹ字型空洞部３６の製作は勿論重要であるが、気体透過部材１８を挟んで蓋部材２４を本体部材２２に接合する接合技術も重要である。蓋部材２４の接合方法は、高温加熱による材料の変質や変形によるＹ字型液体流路３０やＹ字型空洞部３６の破壊を伴わず寸法精度を保った精密な方法が望ましく、製作材料との関係から固相接合（例えば、圧接接合や拡散接合等）や液相接合（例えば、溶接、共晶接合、はんだ付け、接着等）を選択することが好ましい。例えば、材料としてシリコンを使用する場合にシリコン同士を接合するシリコン直接接合や、ガラス同士を接合する融接、シリコンとガラスを接合する陽極接合、金属同士を接合する拡散接合等がある。セラミックスの接合については、金属のようにメカニカルなシール技術以外の接合技術が必要であり、アルミナに対してglass solderなる接合剤をスクリーン印刷で８０μｍに印刷し、圧力をかけずに４４０〜５００°Ｃで処理する方法がある。また、研究段階ではあるが、新しい接合技術として、表面活性化接合、水素結合を用いた直接結合、ＨＦ（フッ化水素）水溶液を用いた接合等がある。 In order to manufacture the apparatus main body 12 having such micro-order fine Y-shaped liquid flow paths 30 and Y-shaped cavities 36, a fine processing technique is used. Examples of microfabrication techniques include the following.
(1) LIGA technology combining X-ray lithography and electroplating
(2) High aspect ratio photolithography using EPON SU8
(3) Mechanical micro-machining (micro-drilling that rotates a drill with a drill diameter of micro-order at high speed)
(4) High aspect ratio processing of silicon by deep RIE
(5) Hot Emboss processing method
(6) Stereolithography
(7) Laser processing method
(8) Ion beam method Further, as a material for manufacturing the apparatus main body 12, metal, glass, ceramics, plastic, silicon, and the like according to the requirements of heat resistance, pressure resistance and solvent resistance, ease of processing, etc. Teflon or the like can be suitably used. In manufacturing the apparatus main body 12, it is of course important to manufacture the Y-shaped liquid flow path 30 and the Y-shaped cavity 36, but a joining technique for joining the lid member 24 to the main body member 22 with the gas permeable member 18 interposed therebetween. It is also important. The lid member 24 is preferably joined by a precise method that maintains dimensional accuracy without breaking the Y-shaped liquid flow path 30 or the Y-shaped cavity 36 due to material alteration or deformation due to high-temperature heating. From this relationship, it is preferable to select solid phase bonding (for example, pressure bonding or diffusion bonding) or liquid phase bonding (for example, welding, eutectic bonding, soldering, adhesion, etc.). For example, when silicon is used as a material, there are silicon direct bonding for bonding silicon, fusion bonding for bonding glasses, anodic bonding for bonding silicon and glass, diffusion bonding for bonding metals, and the like. Joining ceramics requires joining techniques other than mechanical sealing techniques, such as metal, and a glass solder bonding agent is printed on alumina to 80 μm by screen printing, and 440 to 500 ° without applying pressure. There is a method of processing with C. Although it is in the research stage, new bonding techniques include surface activated bonding, direct bonding using hydrogen bonding, bonding using an HF (hydrogen fluoride) aqueous solution, and the like.

また、図２に示すように、本体部材２２に形成された液体供給路２８、２８の端部位置にはそれぞれ液体Ｌ１、Ｌ２の液体導入口３４、３４が下板２１を貫通して形成され、液体導入口３４、３４に液体供給管１４、１４が連結される。これにより、液体供給手段１６、１６から液体Ｌ１、Ｌ２が装置本体１２に供給される。また、マイクロ流路２６の端部位置には液液反応による反応生成液ＬＭを排出させる液体排出口３２が下板２１を貫通して形成される。一方、蓋部材２４に形成されたＹ字型空洞部３６の３つの端部位置には、それぞれ開口３８、３９、４１が上板２０を貫通して形成され、この開口３８、３９、４１にそれぞれ短管３８Ａ、３９Ａ、４１Ａが連結される。   Further, as shown in FIG. 2, liquid inlets 34 and 34 for the liquids L <b> 1 and L <b> 2 are formed through the lower plate 21 at the end positions of the liquid supply paths 28 and 28 formed in the main body member 22. The liquid supply pipes 14 and 14 are connected to the liquid inlets 34 and 34. As a result, the liquids L 1 and L 2 are supplied from the liquid supply means 16 and 16 to the apparatus main body 12. In addition, a liquid discharge port 32 through which the reaction product liquid LM generated by the liquid-liquid reaction is discharged is formed through the lower plate 21 at the end position of the microchannel 26. On the other hand, openings 38, 39, 41 are formed through the upper plate 20 at three end positions of the Y-shaped cavity 36 formed in the lid member 24. Short pipes 38A, 39A and 41A are connected to each other.

本発明のマイクロリアクター１０で使用する液体供給手段１６としては、液体Ｌ１、Ｌ２の供給圧力制御を兼ね備えた連続流動方式型のシリンジポンプを好適に使用することができ、以下シリンジポンプ１６の例で説明する。マイクロリアクターの場合、液体Ｌ１、Ｌ２をマイクロ流路２６に導入する流体制御技術が必要であり、特にマイクロオーダーの微細なマイクロ流路２６での液体や気体の挙動は、マクロスケールとは異なる性質をもつため、マイクロスケールに適した流体制御方式を適用しなくてはならない。連続流動方式は、装置本体１２の内部や装置本体１２に至る流路内は全て液体Ｌ１、Ｌ２で満たされ、外部に用意したシリンジポンプ１６によって、流体全体を駆動する方式であり、マイクロ流路２６に供給する液体Ｌ１、Ｌ２の供給圧力、供給流量を任意に制御することができる。   As the liquid supply means 16 used in the microreactor 10 of the present invention, a continuous flow type syringe pump having the supply pressure control of the liquids L1 and L2 can be preferably used. explain. In the case of a microreactor, a fluid control technique for introducing the liquids L1 and L2 into the microchannel 26 is required. In particular, the behavior of the liquid and gas in the microchannel 26 that is micro order is different from the macro scale. Therefore, a fluid control system suitable for the micro scale must be applied. The continuous flow system is a system in which the inside of the apparatus main body 12 and the inside of the flow path reaching the apparatus main body 12 are filled with the liquids L1 and L2, and the entire fluid is driven by the syringe pump 16 prepared outside. The supply pressure and supply flow rate of the liquids L1 and L2 supplied to H.26 can be arbitrarily controlled.

図１に示すように、Ｙ字型空洞部３６の圧力を制御する圧力制御手段４６は、主として、Ｙ字型空洞部３６を減圧する真空ポンプやアスピレータ等の吸引手段４４と、Ｙ字型空洞部３６の圧力を測定する圧力計４５と、圧力計４５の測定値に基づいて吸引手段４４の吸引力を調整するバルブ４３の開度をコントロールするコントローラ４７とで構成される。即ち、装置本体１２の短管３８Ａ、３９Ａ、４１Ａのうち、短管３８Ａ、３９Ａは大気に開放された状態にされると共に、短管４１Ａには吸引管４２を介して吸引手段４４が連結される。そして、圧力計４５で測定されたＹ字型空洞部３６の圧力がコントローラ４７に入力される。このように構成された圧力制御手段４６によれば、吸引手段４４を駆動すると、短管３８Ａ、３９ＡからＹ字型空洞部３６に吸い込まれたエアは短管４１Ａを通って排気されるので、Ｙ字型空洞部３６には図２の矢印３３で示す高速の気流が発生し、ピトー管現象により気体透過部材１８の微細な穴にＹ字型液体流路３０側からＹ字型空洞部３６側への気体透過力を発生させることができる。気流の速度はバルブ４３の開度によって調整する。気体透過部材１８の気体透過性能にもよるが、気流の速度は気体透過部材１８による副生ガスのスムーズな透過を補助する程度でよく、Ｙ字型空洞部３６の穏やかな減圧が好ましい。従って、圧力制御手段４６としてアスピレータを使用することも好ましい。圧力制御手段４６で使用するバルブ４３としては、１０ミリ秒以下、より好ましくは５ミリ秒以下のレベルの応答速度で開閉動作を行ってバルブ開度を調整することのできるサーボバルブを使用することが好ましい。これにより、吸引手段４４の吸引力を一定に維持することができるので、Ｙ字型空洞部３６に発生する気流速度を一定に維持することができる。   As shown in FIG. 1, the pressure control means 46 for controlling the pressure of the Y-shaped cavity 36 mainly includes a suction means 44 such as a vacuum pump or an aspirator for decompressing the Y-shaped cavity 36, and a Y-shaped cavity. A pressure gauge 45 that measures the pressure of the unit 36 and a controller 47 that controls the opening of the valve 43 that adjusts the suction force of the suction means 44 based on the measurement value of the pressure gauge 45. That is, of the short pipes 38A, 39A, 41A of the apparatus main body 12, the short pipes 38A, 39A are opened to the atmosphere, and the short pipe 41A is connected to the suction means 44 via the suction pipe 42. The Then, the pressure of the Y-shaped cavity 36 measured by the pressure gauge 45 is input to the controller 47. According to the pressure control means 46 configured as described above, when the suction means 44 is driven, the air sucked into the Y-shaped cavity 36 from the short pipes 38A and 39A is exhausted through the short pipe 41A. A high-speed air flow indicated by an arrow 33 in FIG. 2 is generated in the Y-shaped cavity 36, and the Y-shaped cavity 36 from the Y-shaped liquid flow path 30 side into the fine hole of the gas permeable member 18 due to the Pitot tube phenomenon. The gas permeability to the side can be generated. The speed of the airflow is adjusted by the opening degree of the valve 43. Although depending on the gas permeation performance of the gas permeable member 18, the velocity of the air flow may be sufficient to assist the smooth permeation of the by-product gas by the gas permeable member 18, and a gentle pressure reduction of the Y-shaped cavity 36 is preferable. Therefore, it is also preferable to use an aspirator as the pressure control means 46. As the valve 43 used in the pressure control means 46, a servo valve capable of adjusting the valve opening by performing an opening / closing operation at a response speed of 10 milliseconds or less, more preferably 5 milliseconds or less is used. Is preferred. As a result, the suction force of the suction means 44 can be kept constant, so that the air velocity generated in the Y-shaped cavity 36 can be kept constant.

圧力制御手段４６は、上記したＹ字型空洞部３６の一端側から他端側への気体流を発生させる気体流方式に限定されるものではなく、短管３８Ａ、３９Ａを閉塞させた状態で吸引手段４４を駆動してＹ字型空洞部３６の圧力を減圧する吸引方式、あるいは副生ガスが気体透過部材１８を透過する際の圧力損失以上の圧力をＹ字型液体流路３０側に加える加圧方式も採用することができる。Ｙ字型液体流路３０の加圧は後記する液体供給手段１６によって制御することができる。この加圧方式の場合、短管３８Ａ、３９Ａ、４１Ａを大気に開放してＹ字型空洞部３６を大気圧状態にしてもよく、あるいは気流方式や吸引方式を併用してＹ字型空洞部３６を減圧してもよい。   The pressure control means 46 is not limited to the gas flow method for generating a gas flow from one end side to the other end side of the Y-shaped cavity 36 described above, and the short pipes 38A and 39A are closed. The suction means 44 is driven to reduce the pressure of the Y-shaped cavity 36, or a pressure higher than the pressure loss when the by-product gas permeates the gas permeable member 18 is applied to the Y-shaped liquid channel 30 side. An applied pressure method can also be employed. The pressurization of the Y-shaped liquid channel 30 can be controlled by the liquid supply means 16 described later. In the case of this pressurization method, the short pipes 38A, 39A, 41A may be opened to the atmosphere so that the Y-shaped cavity 36 is brought into an atmospheric pressure state, or the Y-shaped cavity is combined with an airflow method or a suction method. 36 may be depressurized.

本実施の形態では特に示さないが、マイクロリアクター１０での液液反応の温度を制御する温度制御手段を設けることが好ましい。マイクロリアクター１０において反応を行う際の温度制御方法には、古典的な方法として、温水、冷水をマイクロリアクター内に供給する方法がある。この他にも、従来から行われている温度制御方法には、金属抵抗線やPolysilicon などのヒータ構造をマイクロリアクターに作り込む方法などがあり、金属抵抗線やPolysilicon などのヒータ構造の場合には、加熱についてはこれを使用し、冷却については自然冷却でサーマルサイクルを行うことで温度を制御する。この場合の温度のセンシングについては、金属抵抗線の場合には同じ抵抗線をもう一つ作り込んでおき、その抵抗値の変化に基づいて温度検出を行い、Polysilicon の場合には、熱電対を用いて温度検出を行う方法が一般的に採用されている。また、近年においては、ペルチェ素子を用いた温度制御機能を装置本体１２内に組み込むことで、反応の際の温度制御を精度良く行うことも試みられている。いずれにしても、温度制御そのものは、従来からの温度制御技術でもペルチェ素子に代表される新規な温度制御技術でも可能であり、用途や装置本体１２の材料等に応じた加熱・冷却機構と温度センシング機構の選択、ならびに外部制御系の構成を組み合わせて最適な方法を選択することが重要である。   Although not particularly shown in the present embodiment, it is preferable to provide a temperature control means for controlling the temperature of the liquid-liquid reaction in the microreactor 10. As a temperature control method for carrying out the reaction in the microreactor 10, there is a classic method of supplying hot water and cold water into the microreactor. In addition to this, conventional temperature control methods include a method in which a heater structure such as a metal resistance wire or Polysilicon is built into a microreactor. In the case of a heater structure such as a metal resistance wire or Polysilicon, This is used for heating and the temperature is controlled by performing a thermal cycle with natural cooling for cooling. For temperature sensing in this case, in the case of a metal resistance wire, make another same resistance wire, detect the temperature based on the change in the resistance value, and in the case of Polysilicon, use a thermocouple. A method for detecting the temperature by using this method is generally employed. In recent years, an attempt has been made to accurately control the temperature during the reaction by incorporating a temperature control function using a Peltier element into the apparatus main body 12. In any case, the temperature control itself can be performed by a conventional temperature control technique or a new temperature control technique represented by a Peltier element. The heating / cooling mechanism and temperature according to the application and the material of the apparatus main body 12 can be used. It is important to select the optimum method by combining the selection of the sensing mechanism and the configuration of the external control system.

次に、上記の如く構成された薄片状流型のマイクロリアクター１０を用いて副生ガスの発生を伴う液液反応を行う本発明の反応方法を説明する。   Next, the reaction method of the present invention in which a liquid-liquid reaction accompanied by generation of by-product gas is performed using the flaky flow type microreactor 10 configured as described above.

シリンジポンプ１６、１６から液体供給路２８、２８に供給された液体Ｌ１、Ｌ２は、合流部４０で１本のマイクロ流路２６に合流し、薄片状の層流として流通しつつ、液体Ｌ１、Ｌ２同士がその接触界面の法線方向へ拡散して液液反応を行う。かかる液液反応によって副生ガスが発生し、発生した副生ガスの気泡はマイクロ流路２６に溜まって塊となるために、マイクロ流路２６には気液混相流状態のスラグ流が発生する。これにより、反応させるべき液体Ｌ１、Ｌ２の連続処理の流れが妨げられたり、乱されたりすることで連続処理の流れが不安定になって反応場が不均一になると共に、反応の平衡が反応促進側に進みにくくなる。また、反応のための液温制御を行う場合、副生ガスを連続処理の流れの中で効率的に除去できないと、気体は熱伝導率が小さいので、反応温度を精度良く制御できなくなる。   The liquids L1 and L2 supplied from the syringe pumps 16 and 16 to the liquid supply paths 28 and 28 merge into the single microchannel 26 at the junction 40 and flow as a laminar laminar flow, while the liquids L1 and L2 are circulated. L2s diffuse in the normal direction of the contact interface to perform a liquid-liquid reaction. By-product gas is generated by the liquid-liquid reaction, and bubbles of the generated by-product gas are accumulated in the micro flow path 26 and become a lump, so that a slag flow in a gas-liquid mixed phase state is generated in the micro flow path 26. . As a result, the flow of the continuous processing of the liquids L1 and L2 to be reacted is hindered or disturbed, the flow of the continuous processing becomes unstable, the reaction field becomes non-uniform, and the reaction equilibrium is It becomes difficult to advance to the promotion side. In addition, when controlling the liquid temperature for the reaction, if the by-product gas cannot be efficiently removed in the flow of continuous processing, the gas has a low thermal conductivity, so the reaction temperature cannot be controlled with high accuracy.

そこで、本発明の薄片状流型のマイクロリアクター１０によれば、Ｙ字型液体流路３０を形成する流路壁の上面部を、液体は通さないが気体は通す気体透過部材１８で構成し、液液反応に伴ってマイクロ流路２６に発生する副生ガスだけを気体透過部材１８を介してＹ字型空洞部３６に透過させながら液液反応を行わせるようにした。これにより、図３に示すように、液体Ｌ１、Ｌ２による液液反応で発生した副生ガスの気泡４８は液体中を浮上して気体透過部材１８を透過し、Ｙ字型空洞部３６に排出される。Ｙ字型空洞部３６に排出された副生ガスはＹ字型空洞部３６を流れる気流に伴われて短管４１Ａから装置本体１２外に排出される。   Therefore, according to the flaky flow type microreactor 10 of the present invention, the upper surface portion of the flow channel wall forming the Y-shaped liquid flow channel 30 is constituted by the gas permeable member 18 that does not allow liquid to pass but allows gas to pass. The liquid-liquid reaction is performed while only the by-product gas generated in the microchannel 26 accompanying the liquid-liquid reaction is transmitted through the gas-permeable member 18 to the Y-shaped cavity 36. As a result, as shown in FIG. 3, the by-product gas bubbles 48 generated by the liquid-liquid reaction with the liquids L <b> 1 and L <b> 2 float up in the liquid, pass through the gas permeable member 18, and are discharged into the Y-shaped cavity 36. Is done. The by-product gas discharged to the Y-shaped cavity 36 is discharged from the short tube 41 </ b> A to the outside of the apparatus main body 12 along with the airflow flowing through the Y-shaped cavity 36.

このように本発明によれば、等価直径が例えば１ｍｍ以下の微細なマイクロ流路２６内の液液反応によって発生する副生ガスをマイクロ流路２６から効率的に脱ガスすることができるので、液液反応に伴って副生ガスが発生する化学反応をマイクロリアクターで行っても、マイクロ流路２６における液体Ｌ１、Ｌ２の流れを不安定化させることなく液液反応を行うことができる。従って、反応の平衡が反応促進側に進み易くなると共に、反応温度を精度良く制御し易くなる。   As described above, according to the present invention, the by-product gas generated by the liquid-liquid reaction in the fine microchannel 26 having an equivalent diameter of, for example, 1 mm or less can be efficiently degassed from the microchannel 26. Even if a chemical reaction in which a by-product gas is generated with the liquid-liquid reaction is performed in the microreactor, the liquid-liquid reaction can be performed without destabilizing the flow of the liquids L1 and L2 in the microchannel 26. Accordingly, the equilibrium of the reaction can easily proceed to the reaction promoting side, and the reaction temperature can be easily controlled with high accuracy.

また、図２における装置本体１２では、Ｙ字型液体流路３０を本体部材２２に形成し、Ｙ字型空洞部３６を蓋部材２４に形成したが、図４のようにＹ字型液体流路３０とＹ字型空洞部３６の両方を本体部材２２に形成してもよい。即ち、図４に示すように、本体部材２２にＹ字型の一体空間を形成し、この一体空間を気体透過部材１８で上空間と下空間とに仕切ることによりＹ字型液体流路３０とＹ字型空洞部３６とを形成する方法である。この場合には、Ｙ字型空洞部３６の幅（Ｗ１）をＹ字型液体流路３０の幅（Ｗ２）よりも一回り大きくすることでＹ字型液体流路３０とＹ字型空洞部３６との境界に段差４９を形成し、この段差４９に気体透過部材１８を嵌め込んで接着剤等により接合するとよい。   2, the Y-shaped liquid flow path 30 is formed in the main body member 22, and the Y-shaped cavity 36 is formed in the lid member 24. However, as shown in FIG. Both the passage 30 and the Y-shaped cavity 36 may be formed in the main body member 22. That is, as shown in FIG. 4, a Y-shaped integrated space is formed in the main body member 22, and the integrated space is partitioned into an upper space and a lower space by the gas permeable member 18, thereby This is a method of forming the Y-shaped cavity 36. In this case, the Y-shaped liquid channel 30 and the Y-shaped cavity are made larger by making the width (W1) of the Y-shaped cavity 36 larger than the width (W2) of the Y-shaped liquid channel 30. A step 49 may be formed at the boundary with 36, and the gas permeable member 18 may be fitted into the step 49 and bonded by an adhesive or the like.

次に、図５に従って本発明のマイクロリアクターの第２の実施の形態である、円環状流型のマイクロリアクター６０の場合について説明する。第２の実施の形態の場合も液液反応を行う液体を２種類の液体Ｌ１、Ｌ２を使用した場合で説明する。   Next, the case of an annular flow type microreactor 60, which is a second embodiment of the microreactor of the present invention, will be described with reference to FIG. In the case of the second embodiment as well, the liquid in which the liquid-liquid reaction is performed will be described using two types of liquids L1 and L2.

図５に示すように、薄片状流型のマイクロリアクター６０は、主として、気体透過部材７２を備えた装置本体６１と、副生ガスの発生を伴う液液反応を行う液体Ｌ１、Ｌ２を液体供給管１０４、１０６を介して装置本体６１に供給する液体供給手段１６、１６（図５では省略しており図１参照）と、気体透過部材７２の気体透過性能を向上させる圧力制御手段１１８とで構成される。尚、第２の実施の形態の場合も、２種類の液体Ｌ１、Ｌ２で液液反応を行う例で説明する。   As shown in FIG. 5, a laminar flow type microreactor 60 mainly supplies an apparatus main body 61 having a gas permeable member 72 and liquids L1 and L2 for performing a liquid-liquid reaction accompanied by by-product gas generation. Liquid supply means 16 and 16 (not shown in FIG. 5; see FIG. 1) for supplying to the apparatus main body 61 via the pipes 104 and 106, and pressure control means 118 for improving the gas permeation performance of the gas permeation member 72 Composed. In the second embodiment, an example in which a liquid-liquid reaction is performed with two types of liquids L1 and L2 will be described.

図５に示されるように、円環状型のマイクロリアクター６０は、全体として略円柱状に形成されており、装置の外殻部を構成する円筒状の円管部材６２を備えている。ここで、図中における直線Ｓは装置の軸心を示しており、この軸心Ｓに沿った方向を装置の軸方向として以下の説明を行う。この円管部材６２の先端面には液体Ｌ１、Ｌ２が反応した後の反応生成液ＬＭの吐出口６４が開口し、また円管部材６２の先端部には吐出口６４の外周側に延出するようにリング状のフランジ部６６が設けられる。このフランジ部６６は反応生成液ＬＭに対して次の処理を行う配管等に接続される。   As shown in FIG. 5, the annular microreactor 60 is formed in a substantially cylindrical shape as a whole, and includes a cylindrical circular tube member 62 that constitutes an outer shell portion of the apparatus. Here, the straight line S in the figure indicates the axial center of the apparatus, and the following description will be made with the direction along the axial center S as the axial direction of the apparatus. A discharge port 64 for the reaction product liquid LM after the reaction of the liquids L1 and L2 is opened at the front end surface of the circular tube member 62, and the front end portion of the circular tube member 62 extends to the outer peripheral side of the discharge port 64. Thus, a ring-shaped flange portion 66 is provided. The flange portion 66 is connected to a pipe or the like that performs the next process on the reaction product liquid LM.

円管部材６２は、その基端部側に胴体部６３よりも大径な大径部６８を有すると共に、胴体部６３の基端位置には、中心部が丸穴状に開口した第１仕切板７０が円管部材６２の内側に張り出すように設けられる。胴体部６３内には、該胴体部６３内の空間を軸方向に沿って仕切る円筒状の気体透過部材７２が設けられ、気体透過部材７２の両端が第１仕切板７０の開口周縁とフランジ部６６の開口周縁とに固着支持される。これにより、胴体部６３内が気体透過部材７２によって内側空間と外側空間の２つの空間に仕切られる。ここで、内側空間は液体Ｌ１、Ｌ２が流れる断面円環状の円環状液体流路７４を形成すると共に、外側空間は円環状液体流路７４で発生した副生ガスが気体透過部材７２を介して透過する断面円環状の円環状空洞部７６を形成する。即ち、円環状液体流路７４を形成する流路壁全体が気体透過部材７２で構成され、気体透過部材７２の外側に円環状空洞部７６が形成されている。胴体部６３と気体透過部材７２との間には、複数個のスペーサ７８（本実施の形態では４個）が介装され、円環状空洞部７６の幅Ｗ１（図５（Ａ）参照）が設定される。円環状型のマイクロリアクター６０のように、円環状液体流路７４の流路壁全体を気体透過部材７２で構成する場合には、マイクロマシンニング技術により、金属材料やプラスチック樹脂材料等の硬質材料に、液体は通さないが気体は通す極めて微細な穴を開けることにより気体透過部材７２を製作するとよい。   The circular pipe member 62 has a large-diameter portion 68 having a diameter larger than that of the body portion 63 on the base end side, and a first partition having a central portion opened in a round hole shape at the base end position of the body portion 63. The plate 70 is provided so as to protrude inside the circular tube member 62. A cylindrical gas permeable member 72 for partitioning the space in the body portion 63 along the axial direction is provided in the body portion 63, and both ends of the gas permeable member 72 are connected to the opening peripheral edge of the first partition plate 70 and the flange portion. 66 is firmly fixed to the peripheral edge of the opening. As a result, the body portion 63 is partitioned into two spaces, an inner space and an outer space, by the gas permeable member 72. Here, the inner space forms an annular liquid channel 74 having an annular cross section through which the liquids L1 and L2 flow, and the outer space is formed by the by-product gas generated in the annular liquid channel 74 via the gas permeable member 72. An annular cavity 76 having an annular cross section is formed. That is, the entire flow path wall forming the annular liquid flow path 74 is constituted by the gas permeable member 72, and the annular cavity 76 is formed outside the gas permeable member 72. A plurality of spacers 78 (four in the present embodiment) are interposed between the body 63 and the gas permeable member 72, and the width W1 of the annular cavity 76 (see FIG. 5A). Is set. When the entire flow path wall of the annular liquid flow path 74 is configured by the gas permeable member 72 as in the annular microreactor 60, it is made of a hard material such as a metal material or a plastic resin material by a micromachining technique. The gas permeable member 72 may be manufactured by making a very fine hole that does not allow liquid to pass but allows gas to pass.

円管部材６２の基端面は円板状の蓋板８０により閉塞されており、この蓋板８０の中心部には円形の嵌挿穴８２が穿設されている。円管部材６２内には、その基端部側から円管部材６２内へ挿入されるように円柱状の整流部材８４が同軸的に設けられており、整流部材８４の基端部は蓋板８０の嵌挿穴８２に嵌挿支持される。   The base end surface of the circular tube member 62 is closed by a disc-shaped lid plate 80, and a circular fitting hole 82 is formed in the center of the lid plate 80. In the circular pipe member 62, a columnar rectifying member 84 is provided coaxially so as to be inserted into the circular pipe member 62 from the base end side thereof, and the base end of the rectifying member 84 is a lid plate. It is inserted into and supported by the 80 insertion holes 82.

円管部材６２の大径部６８部分は、中心部が丸穴状に開口した第２仕切板８６によって大径部６８内の空間が２等分されるように区画されており、液体Ｌ１が導入される第１ヘッダー部８８、液体Ｌ２が導入される第２ヘッダー部９０とされる。第２仕切板８６の開口周縁から円管部材６２の軸方向に突出するように円筒状の隔壁部材９２が第２仕切板８６に一体的に設けられる。この隔壁部材９２により、円環状液体流路７４の途中までが２分割され、気体透過部材７２と隔壁部材９２との間に第１ヘッダー部８８に導入された液体Ｌ１の供給路である第１の液体供給路９４が形成され、隔壁部材９２と整流部材８４との間に第２ヘッダー部９０に導入された液体Ｌ２の供給路である第２の液体供給路９６が形成される。そして、気体透過部材７２の内周面と隔壁部材９２の外周面との間に複数個（本実施の形態では４個）のスペーサ９８が介装されると共に、隔壁部材９２と整流部材８４との間に複数個（本実施の形態では４個）のスペーサ１００が介装される。これら複数個のスペーサ９８、１００はそれぞれ矩形プレート状に形成され、その表裏面部が円環状液体流路７４における流通方向（矢印Ｆ方向）と平行になるように支持される。これにより、第１の液体供給路９４の流路幅Ｗ２及び第２の液体供給路９６の流路幅Ｗ３が設定される。   The large-diameter portion 68 of the circular tube member 62 is partitioned so that the space in the large-diameter portion 68 is divided into two equal parts by a second partition plate 86 whose center is opened in a round hole shape. The first header part 88 to be introduced and the second header part 90 to which the liquid L2 is introduced are used. A cylindrical partition member 92 is provided integrally with the second partition plate 86 so as to protrude from the opening periphery of the second partition plate 86 in the axial direction of the circular tube member 62. The partition member 92 divides the annular liquid channel 74 halfway into two parts, and is a first supply path for the liquid L1 introduced into the first header portion 88 between the gas permeable member 72 and the partition member 92. The liquid supply path 94 is formed, and a second liquid supply path 96 that is a supply path of the liquid L2 introduced into the second header portion 90 is formed between the partition wall member 92 and the rectifying member 84. A plurality (four in this embodiment) of spacers 98 are interposed between the inner peripheral surface of the gas permeable member 72 and the outer peripheral surface of the partition member 92, and the partition member 92, the rectifying member 84, A plurality (four in this embodiment) of spacers 100 are interposed between the two. The plurality of spacers 98 and 100 are each formed in a rectangular plate shape, and are supported so that the front and back surface portions thereof are parallel to the flow direction (arrow F direction) in the annular liquid channel 74. Thereby, the flow path width W2 of the first liquid supply path 94 and the flow path width W3 of the second liquid supply path 96 are set.

また、円管部材６２内には、隔壁部材９２よりも先端側であって整流部材８４の円錐部８４Ａよりも基端部側に第１及び第２の液体供給路９４、９６に連通する断面円環状の空間が形成され、この断面円環状の空間は、液体Ｌ１、Ｌ２とが合流して副生ガスの発生を伴う液液反応を行う円環状マイクロ流路１０２とされる。この場合、円環状マイクロ流路１０２内の出口部で液体Ｌ１、Ｌ２の液液反応が完了している必要があるので、円環状マイクロ流路１０２の流通方向に沿った路長ＰＬ（図５（Ａ）参照）は、液体Ｌ１、Ｌ２の液液反応が完了する長さに設定する必要がある。尚、上記したように円環状液体流路７４の流路壁全体を気体透過部材７２で構成するようにしたが、液体Ｌ１、Ｌ２が反応して副生ガスを発生する円環状マイクロ流路１０２の流路壁部分のみを気体透過部材７２で構成してもよい。   In the circular tube member 62, a cross section that communicates with the first and second liquid supply paths 94 and 96 on the distal end side of the partition wall member 92 and on the proximal end side of the conical portion 84 </ b> A of the rectifying member 84. An annular space is formed, and the annular space with the cross-section is formed into an annular microchannel 102 in which the liquids L1 and L2 merge to perform a liquid-liquid reaction accompanied by the generation of by-product gas. In this case, since the liquid-liquid reaction of the liquids L1 and L2 needs to be completed at the outlet in the annular microchannel 102, the path length PL along the circulation direction of the annular microchannel 102 (FIG. 5). (Refer to (A)) needs to be set to a length at which the liquid-liquid reaction of the liquids L1 and L2 is completed. As described above, the entire flow path wall of the annular liquid flow path 74 is configured by the gas permeable member 72. However, the annular micro flow path 102 in which the liquids L1 and L2 react to generate a by-product gas. Only the flow path wall portion may be configured by the gas permeable member 72.

また、円管部材６２の基端面に設けられた蓋板８０には、第１及び第２の液体供給路９４、９６に連通する嵌挿穴が穿設されており、これらの嵌挿穴に、それぞれ第１及び第２の液体供給管１０４、１０６が接続される。そして、２本の液体供給管１０４、１０６に、図１に示した液体Ｌ１、Ｌ２を供給するシリンジポンプ１６、１６がそれぞれ接続され、液体供給管１０４、１０６を通して第１及び第２のヘッダー部８８、９０には液液反応を行う液体Ｌ１、Ｌ２が加圧状態で供給される。図５（Ｂ）に示されるように、第１及び第２の液体供給路９４、９６の先端部には、それぞれ円環状マイクロ流路１０２内へ開口する第１及び第２の液体供給口１０８、１１０が形成される。これらの供給口１０８、１１０は、それぞれ軸心Ｓを中心とする円軌跡に沿って断面円環状に開口し、互いに同心円状となるように配設されている。ここで、前記した開口幅Ｗ２、Ｗ３は、それぞれの供給口１０８、１１０の開口面積を規定し、この供給口１０８、１１０の開口面積と液体Ｌ１、Ｌ２の供給量に応じて、供給口１０８、１１０を通して円環状マイクロ流路１０２へ導入される液体Ｌ１、Ｌ２の初期流速が定まる。   The lid plate 80 provided on the base end surface of the circular pipe member 62 is provided with fitting insertion holes communicating with the first and second liquid supply paths 94 and 96. The first and second liquid supply pipes 104 and 106 are connected, respectively. The syringe pumps 16 and 16 for supplying the liquids L1 and L2 shown in FIG. 1 are connected to the two liquid supply pipes 104 and 106, respectively, and the first and second header sections are connected through the liquid supply pipes 104 and 106, respectively. The liquids L1 and L2 that perform liquid-liquid reaction are supplied to 88 and 90 in a pressurized state. As shown in FIG. 5B, the first and second liquid supply ports 108 that open into the annular microchannel 102 are respectively provided at the distal ends of the first and second liquid supply paths 94 and 96. 110 are formed. These supply ports 108 and 110 each have an annular cross section along a circular locus centered on the axis S, and are arranged so as to be concentric with each other. Here, the opening widths W2 and W3 described above define the opening areas of the supply ports 108 and 110, respectively, and the supply ports 108 according to the opening areas of the supply ports 108 and 110 and the supply amounts of the liquids L1 and L2. , 110, the initial flow rates of the liquids L1 and L2 introduced into the annular microchannel 102 are determined.

円管部材６２内における円環状マイクロ流路１０２よりも先端側の空間は、円環状マイクロ流路１０２内で液体Ｌ１、Ｌ２の反応が行われた反応生成液ＬＭが吐出口６４に向かって流れる出液路１１２とされる。また、円管部材６２周面の基端面側（蓋板側）には短管１１４が連結されると共に、円管部材６２周面の先端面側（フランジ側）には短管１１６が連結される。   The reaction product liquid LM in which the reactions of the liquids L1 and L2 are performed in the annular microchannel 102 flows toward the discharge port 64 in the space on the tip side of the annular microchannel 102 in the circular tube member 62. A liquid discharge path 112 is provided. Further, the short tube 114 is connected to the base end surface side (the cover plate side) of the circumferential surface of the circular tube member 62, and the short tube 116 is connected to the distal surface side (flange side) of the circumferential surface of the circular tube member 62. The

円環状空洞部７６の圧力を制御する圧力制御手段１１８は、主として、円環状空洞部７６を減圧する真空ポンプやアスピレータ等の吸引手段１２０と、円環状空洞部７６の圧力を測定する圧力計１２２と、圧力計１２２の測定値に基づいて吸引手段１２０の吸引力を調整するバルブ１２４の開度をコントロールするコントローラ１２６とで構成される。即ち、装置本体６１の短管１１４、１１６のうち、短管１１４は大気に開放された状態にされると共に、短管１１６には吸引管１２８を介して吸引手段１２０が連結される。そして、圧力計１２２で測定された円環状空洞部７６の圧力がコントローラ１２６に入力される。このように構成された圧力制御手段１１８によれば、吸引手段１２０を駆動すると、短管１１４から円環状空洞部７６に吸い込まれたエアは短管１１６を通って排気されるので、円環状空洞部７６には図５の矢印１３０で示す高速の気流が発生し、ピトー管現象により気体透過部材７２の微細な穴に円環状液体流路７４側から円環状空洞部７６側への気体透過力を発生させることができる。気流の速度はバルブ１２４の開度によって調整する。気体透過部材７２の気体透過性能にもよるが、気流の速度は気体透過部材７２による副生ガスのスムーズな透過を補助する程度でよく、円環状空洞部７６の穏やかな減圧が好ましい。従って、圧力制御手段１１８としてアスピレータを使用することも好ましい。圧力制御手段１１８で使用するバルブ１２４としては、１０ミリ秒以下、より好ましくは５ミリ秒以下のレベルの応答速度で開閉動作を行ってバルブ開度を調整することのできるサーボバルブを使用することが好ましい。これにより、吸引手段１２０の吸引力を一定に維持することができるので、円環状空洞部７６に発生する気流速度を一定に維持することができる。   The pressure control means 118 for controlling the pressure of the annular cavity 76 mainly includes a suction means 120 such as a vacuum pump or an aspirator for reducing the pressure of the annular cavity 76, and a pressure gauge 122 for measuring the pressure of the annular cavity 76. And a controller 126 that controls the opening degree of the valve 124 that adjusts the suction force of the suction means 120 based on the measured value of the pressure gauge 122. That is, of the short tubes 114 and 116 of the apparatus main body 61, the short tube 114 is opened to the atmosphere, and the suction unit 120 is connected to the short tube 116 via the suction tube 128. Then, the pressure of the annular cavity 76 measured by the pressure gauge 122 is input to the controller 126. According to the pressure control means 118 configured in this way, when the suction means 120 is driven, the air sucked into the annular cavity 76 from the short pipe 114 is exhausted through the short pipe 116, so that the annular cavity A high-speed air flow indicated by an arrow 130 in FIG. 5 is generated in the portion 76, and the gas permeation force from the annular liquid channel 74 side to the annular cavity 76 side in the minute hole of the gas permeable member 72 due to the Pitot tube phenomenon. Can be generated. The speed of the airflow is adjusted by the opening degree of the valve 124. Although depending on the gas permeation performance of the gas permeable member 72, the velocity of the air flow may be sufficient to assist the smooth permeation of the by-product gas by the gas permeable member 72, and gentle pressure reduction of the annular cavity 76 is preferable. Therefore, it is also preferable to use an aspirator as the pressure control means 118. As the valve 124 used in the pressure control means 118, a servo valve capable of adjusting the valve opening by performing an opening / closing operation at a response speed of 10 milliseconds or less, more preferably 5 milliseconds or less is used. Is preferred. As a result, the suction force of the suction means 120 can be kept constant, so that the air velocity generated in the annular cavity 76 can be kept constant.

圧力制御手段１１８は、上記した円環状空洞部７６の一端側から他端側への気体流を発生させる気体流方式に限定されるものではなく、短管１１４を閉塞させた状態で吸引手段１２０を駆動して円環状空洞部７６の圧力を減圧する吸引方式、あるいは副生ガスが気体透過部材７２を透過する際の圧力損失以上の圧力を円環状液体流路７４側に加える加圧方式も採用することができる。円環状液体流路７４の加圧は後記する液体供給手段１６によって制御することができる。この加圧方式の場合、短管１１４、１１６を大気に開放して円環状空洞部７６を大気圧状態にしてもよく、あるいは気流方式や吸引方式を併用して円環状空洞部７６を減圧してもよい。   The pressure control means 118 is not limited to a gas flow system that generates a gas flow from one end side to the other end side of the annular cavity 76 described above, and the suction means 120 is in a state where the short pipe 114 is closed. A suction method for reducing the pressure of the annular cavity 76 by driving the pressure, or a pressurization method for applying a pressure higher than the pressure loss when the by-product gas permeates the gas permeable member 72 to the annular liquid channel 74 side. Can be adopted. The pressurization of the annular liquid channel 74 can be controlled by the liquid supply means 16 described later. In the case of this pressurization method, the short tubes 114 and 116 may be opened to the atmosphere so that the annular cavity 76 is brought into an atmospheric pressure state, or the annular cavity 76 is decompressed by using an airflow method or a suction method. May be.

次に、上記の如く構成された円環状流型のマイクロリアクター６０を用いて副生ガスを伴う液液反応を行う本発明の反応方法を説明する。   Next, the reaction method of the present invention in which a liquid-liquid reaction with by-product gas is performed using the annular flow type microreactor 60 configured as described above will be described.

シリンジポンプ１６，１６から第１及び第２の液体供給路９４、９６に供給された液体Ｌ１、Ｌ２は、円環状マイクロ流路１０２で合流して同心円状に積層された断面円環状の層流となって流通する。そして、円環状マイクロ流路１０２内を流通する２つの液体Ｌ１、Ｌ２は、互いに隣接する層流間の接触界面の法線方向へ拡散して液液反応を行う。かかる液液反応によって発生した副生ガスの気泡は円環状マイクロ流路９６に溜まって塊となるために、円環状マイクロ流路１０２にはスラグ流が発生する。これにより、反応させるべき液体Ｌ１、Ｌ２の連続処理の流れを妨げたり、乱したりすることで連続処理の流れが不安定になって反応場が不均一になると共に、反応の平衡が反応促進側に進みにくくなる。また、反応のための液温制御を行う場合、副生ガスを連続処理の流れの中で効率的に除去できないと、気体は熱伝導率が小さいので、反応温度を精度良く制御できなくなる。   The liquids L1 and L2 supplied from the syringe pumps 16 and 16 to the first and second liquid supply passages 94 and 96 merge in the annular microchannel 102 and are stacked concentrically in a circular cross section. It becomes and circulates. Then, the two liquids L1 and L2 flowing through the annular microchannel 102 are diffused in the normal direction of the contact interface between the adjacent laminar flows to perform a liquid-liquid reaction. By-product gas bubbles generated by the liquid-liquid reaction accumulate in the annular micro-channel 96 and become a lump, so that a slag flow is generated in the annular micro-channel 102. This obstructs or disturbs the continuous processing flow of the liquids L1 and L2 to be reacted, thereby making the continuous processing flow unstable and making the reaction field non-uniform, and the reaction equilibrium promotes the reaction. It becomes difficult to go to the side. In addition, when controlling the liquid temperature for the reaction, if the by-product gas cannot be efficiently removed in the flow of continuous processing, the gas has a low thermal conductivity, so the reaction temperature cannot be controlled with high accuracy.

そこで、本発明の円環状流型のマイクロリアクター６０によれば、円環状液体流路７４を形成する円筒状の流路壁の全体を、液体は通さないが気体は通す気体透過部材７２で構成し、液液反応に伴って円環状マイクロ流路１０２に発生する副生ガスだけを気体透過部材７２を介して円環状空洞部７６に透過させながら液液反応を行わせるようにした。これにより、図６に示すように、液体Ｌ１、Ｌ２による液液反応で発生した副生ガスの気泡４８は気体透過部材７２を透過し、円環状空洞部７６に排出される。円環状空洞部７６に排出された副生ガスは円環状空洞部７６を流れる気流に伴われて短管１１６から装置本体６１外に排出される。   Therefore, according to the annular flow type microreactor 60 of the present invention, the entire cylindrical flow path wall forming the circular liquid flow path 74 is constituted by the gas permeable member 72 that does not allow liquid to pass but allows gas to pass. Then, the liquid-liquid reaction is performed while only the by-product gas generated in the annular micro-channel 102 due to the liquid-liquid reaction is transmitted through the gas-permeable member 72 to the annular cavity 76. As a result, as shown in FIG. 6, the by-product gas bubbles 48 generated by the liquid-liquid reaction with the liquids L <b> 1 and L <b> 2 pass through the gas permeable member 72 and are discharged to the annular cavity 76. The by-product gas discharged to the annular cavity 76 is discharged from the short tube 116 to the outside of the apparatus main body 61 along with the airflow flowing through the annular cavity 76.

これにより、本発明の第２の実施の形態の場合にも、円環状液体流路７４を流れる液体Ｌ１、Ｌ２の液液反応により、等価直径が例えば１ｍｍ以下の微細な円環状マイクロ流路１０２で副生ガスが発生しても、発生する副生ガスを円環状マイクロ流路１０２から効率的に脱ガスすることができる。従って、液液反応に伴って副生ガスが発生する化学反応をマイクロリアクターで行っても、円環状マイクロ流路１０２における液体Ｌ１、Ｌ２の流れを不安定化させることなく液液反応を行うことができる。従って、反応の平衡が反応促進側に進み易くなると共に、反応温度を精度良く制御し易くなる。   Thereby, also in the case of the second embodiment of the present invention, due to the liquid-liquid reaction of the liquids L1 and L2 flowing through the annular liquid channel 74, a fine annular microchannel 102 having an equivalent diameter of 1 mm or less, for example. Even if the by-product gas is generated, the generated by-product gas can be efficiently degassed from the annular microchannel 102. Therefore, even if a chemical reaction in which a by-product gas is generated with the liquid-liquid reaction is performed in the microreactor, the liquid-liquid reaction is performed without destabilizing the flow of the liquids L1 and L2 in the annular microchannel 102. Can do. Accordingly, the equilibrium of the reaction can easily proceed to the reaction promoting side, and the reaction temperature can be easily controlled with high accuracy.

本発明の薄片状流型のマイクロリアクター１０を用いて２つの液体Ｌ１、Ｌ２で副生ガスの発生を伴う液液反応を実施した実施例を以下に説明する。装置本体１２は図２のように蓋部材２０にＹ字型空洞部３６を形成し、本体部材２１にＹ字型液体流路３０を形成するタイプのもので実施した。   An embodiment in which a liquid-liquid reaction involving generation of by-product gas is performed in two liquids L1 and L2 using the flaky flow type microreactor 10 of the present invention will be described below. As shown in FIG. 2, the apparatus main body 12 is a type in which a Y-shaped cavity 36 is formed in the lid member 20 and a Y-shaped liquid flow path 30 is formed in the main body member 21.

［マイクロリアクターの製作］
マイクロリアクター１０の装置本体１２は、透明ガラス板を機械加工により切削加工することで製作した。先ず、本体部材２２を製作するためのガラスプレートを準備し、ＰＭＴ社製のマシニングセンター（ＭＣ機）にダイヤモンド焼結型のマイクロドリルを用いて２本の液体供給路２８と１本のマイクロ流路２６とでなるＹ字型液体流路３０を切削加工した。液体供給路２８は幅２５０μｍ、深さ２００μｍとし、マイクロ流路２６は幅５００μｍ、深さ２００μｍとした。また、マイクロ流路２６の流路長を３０ｃｍとした。 [Production of microreactors]
The device body 12 of the microreactor 10 was manufactured by cutting a transparent glass plate by machining. First, a glass plate for preparing the main body member 22 is prepared, and two liquid supply paths 28 and one micro flow path are used in a machining center (MC machine) manufactured by PMT using a diamond sintered micro drill. The Y-shaped liquid flow path 30 consisting of 26 was cut. The liquid supply path 28 has a width of 250 μm and a depth of 200 μm, and the microchannel 26 has a width of 500 μm and a depth of 200 μm. The channel length of the microchannel 26 was 30 cm.

一方、蓋部材２４を製作するためのガラスプレートには、本体部材２２と同じ機械加工によって、上記したＹ字型液体流路３０に対向するようにＹ字型空洞部３６を切削加工した。このＹ字型空洞部３６の流路幅はＹ字型液体流路３０の流路幅よりも大きめに形成した。そして、本体部材２２と蓋部材２４とでゴアテックス膜（気体透過部材１８）をサンドイッチ状にした状態で、Ｙ字型空洞部３６やＹ字型液体流路３０を塞がないように、接着剤で互いに接合した。更に、その外側を上板２０と下板２１とで挟み込み、上板２０と下板２１の４角に形成されたボルト穴に通したボルト２３とナット２５とを締め付け、装置本体１２を組み立てた。   On the other hand, the Y-shaped cavity 36 was cut into the glass plate for manufacturing the lid member 24 so as to face the Y-shaped liquid flow path 30 by the same machining as the main body member 22. The channel width of the Y-shaped cavity 36 was formed larger than the channel width of the Y-shaped liquid channel 30. Then, in a state where the Gore-Tex membrane (gas permeable member 18) is sandwiched between the main body member 22 and the lid member 24, bonding is performed so as not to block the Y-shaped cavity 36 and the Y-shaped liquid flow path 30. Bonded to each other with an agent. Further, the outer body is sandwiched between the upper plate 20 and the lower plate 21, and bolts 23 and nuts 25 passed through bolt holes formed at four corners of the upper plate 20 and the lower plate 21 are tightened to assemble the apparatus main body 12. .

また、本体部材２２及び下板２１には、液体供給路２８に連通する１０００μｍの液体導入口３４、３４を予め穿孔しておき、このそれぞれの液体導入口３４、３４に外径９５０μｍ、内径２５０μｍのテフロンチューブ（液体供給管１４）をそれぞれ差し込み接着剤で固定した。液体導入口３４に接続されていないテフロンチューブの一端は、液体用のシリンジポンプ１６に接続した。また、マイクロ流路２６の終端部にガラスプレートを貫通するかたちで１０００μｍの液体排出口３２を開け、この液体排出口３２に外径９５０μｍ、内径２５０μｍのテフロンチューブをそれぞれ差し込み接着剤で固定した。   The main body member 22 and the lower plate 21 are previously perforated with 1000 μm liquid inlets 34, 34 communicating with the liquid supply path 28, and the liquid inlets 34, 34 have an outer diameter of 950 μm and an inner diameter of 250 μm. Each Teflon tube (liquid supply tube 14) was inserted and fixed with an adhesive. One end of the Teflon tube not connected to the liquid inlet 34 was connected to the liquid syringe pump 16. In addition, a 1000 μm liquid discharge port 32 was opened at the end of the microchannel 26 so as to penetrate the glass plate, and a Teflon tube having an outer diameter of 950 μm and an inner diameter of 250 μm was inserted into the liquid discharge port 32 and fixed with an adhesive.

一方、蓋部材２４及び上板２０には、Ｙ字型空洞部３６の３つの端部位置にそれぞれ開口３８、３９、４１を予め穿孔しておき、それぞれの開口３８、３９、４１にそれぞれ短管３８Ａ、３９Ａ、４１Ａを連結した。そして、この短管３８Ａ、３９Ａを大気に開放し、短管４１Ａには吸引管４２を介してアスピレータ（吸引手段４４）を連結した。アスピレータでＹ字型空洞部３６を３００Torrに減圧した。これにより、本発明の実施例を行う薄片状流型のマイクロリアクター１０を作製した。   On the other hand, the lid member 24 and the upper plate 20 are previously drilled with openings 38, 39, and 41 at three end positions of the Y-shaped cavity 36, respectively, and the openings 38, 39, and 41 are respectively short. Tubes 38A, 39A, 41A were connected. The short pipes 38A and 39A were opened to the atmosphere, and an aspirator (suction means 44) was connected to the short pipe 41A via a suction pipe 42. The Y-shaped cavity 36 was decompressed to 300 Torr with an aspirator. Thus, a flaky flow type microreactor 10 according to an embodiment of the present invention was produced.

比較する従来のマイクロリアクターとしては、Ｙ字型液体流路３０を切削加工した本体部材２２の開放された上面を、平板状の蓋部材２４（Ｙ字型空洞部３６のない板状のもの）で蓋をして装置本体を組み立てた以外は本発明のマイクロリアクターと同様に製作した。   As a conventional microreactor to be compared, the open upper surface of the main body member 22 obtained by cutting the Y-shaped liquid flow path 30 is formed as a flat lid member 24 (a plate-shaped member without the Y-shaped cavity 36). The microreactor was manufactured in the same manner as the microreactor of the present invention except that the device body was assembled with the lid.

上記の如く製作した本発明のマイクロリアクター１０と従来のマイクロリアクターとを使用して、液液反応によって副生ガスを発生させる２つの液体Ｌ１、Ｌ２を液体供給路２８からマイクロ流路２６に合流させて液液反応を行わせ、液液反応により発生する酸素ガスによってマイクロ流路２６の流れがどのようになるかを観察した。   Using the microreactor 10 of the present invention manufactured as described above and a conventional microreactor, two liquids L1 and L2 that generate by-product gas by liquid-liquid reaction are joined from the liquid supply path 28 to the microflow path 26. The liquid-liquid reaction was performed, and the flow of the microchannel 26 was observed by the oxygen gas generated by the liquid-liquid reaction.

副生ガスの発生を伴う液液反応としては、二酸化マンガンの粉末１ｇを水１００ｍｌに分散した二酸化マンガン水溶液Ｌ１と過酸化水素水Ｌ２を反応させて、副生ガスとして酸素ガスを発生させる反応実験を行った。液体Ｌ１、Ｌ２の流量としては、二酸化マンガン水溶液Ｌ１及び過酸化水素水Ｌ２ともに１００μｌ／分に設定した。   A liquid-liquid reaction involving the generation of by-product gas is a reaction experiment in which an aqueous solution of manganese dioxide L1 in which 1 g of manganese dioxide powder is dispersed in 100 ml of water and hydrogen peroxide solution L2 are reacted to generate oxygen gas as a by-product gas. Went. The flow rates of the liquids L1 and L2 were set to 100 μl / min for both the manganese dioxide aqueous solution L1 and the hydrogen peroxide solution L2.

その結果、従来のマイクロリアクターは、液液反応により発生した酸素ガスの気泡４８はマイクロ流路２６内に溜まって大きな塊となり、その影響でマイクロ流路２６の流れは非常に不安定なスラグ流状態となった。   As a result, in the conventional microreactor, the oxygen gas bubbles 48 generated by the liquid-liquid reaction accumulate in the microchannel 26 to form a large lump, and the flow of the microchannel 26 is very unstable due to the influence. It became a state.

これに対し、本発明のマイクロリアクターは、液液反応により発生した酸素ガスの気泡４８は液体内を上昇してゴアテックス膜１８からスムーズにＹ字型空洞部３６に透過し、マイクロ流路２６から脱ガスされた。これにより、マイクロ流路２６の流れを安定させることができ、安定した液液反応を行うことができた。   On the other hand, in the microreactor of the present invention, the oxygen gas bubbles 48 generated by the liquid-liquid reaction ascend in the liquid and smoothly permeate from the Gore-Tex film 18 to the Y-shaped cavity 36, and the microchannel 26. Was degassed from. Thereby, the flow of the microchannel 26 could be stabilized, and a stable liquid-liquid reaction could be performed.

本発明の第１の実施の形態である薄片状流型のマイクロリアクターを概念的に説明する斜視図1 is a perspective view conceptually explaining a flaky flow type microreactor according to a first embodiment of the present invention. マイクロリアクターの装置本体の上面図、断面図及び下面図Top view, sectional view and bottom view of the microreactor main unit 本発明の薄片状流型のマイクロリアクターを用いて副生ガスの発生を伴う液液反応を行った場合の円環状マイクロ流路の流れを説明する説明図Explanatory drawing explaining the flow of the annular | circular shaped microchannel at the time of performing liquid-liquid reaction with generation | occurrence | production of by-product gas using the flaky flow type microreactor of this invention 本発明に係る薄片状流型のマイクロリアクターの装置本体の変形例を説明する上面図、断面図及び下面図The top view, sectional drawing, and bottom view explaining the modification of the apparatus main body of the flaky flow type microreactor concerning the present invention 本発明の第２の実施の形態である円環状流型のマイクロリアクターを説明する断面図Sectional drawing explaining the annular flow type microreactor which is the 2nd Embodiment of this invention 本発明の円環状流型のマイクロリアクターを用いて副生ガスの発生を伴う液液反応を行った場合の円環状マイクロ流路の流れを説明する説明図Explanatory drawing explaining the flow of the annular | circular shaped microchannel at the time of performing the liquid-liquid reaction accompanying generation | occurrence | production of by-product gas using the annular flow type microreactor of this invention. 従来のマイクロリアクターで副生ガスを伴う反応を行ったときの円環状マイクロ流路の流れを説明する説明図Explanatory drawing explaining the flow of an annular micro channel when reaction with byproduct gas was performed in the conventional micro reactor

符号の説明Explanation of symbols

１０…薄片状流型のマイクロリアクター、１２…装置本体、１４…液体供給管、１６…液体供給手段、１８…気体透過部材、２０…上板、２１…下板、２２…本体部材、２３…ボルト、２４…蓋部材、２５…ナット、２６…マイクロ流路、２８…液体供給路、３０…Ｙ字型液体流路、３２…液体排出口、３４…液体導入口、３６…Ｙ字型空洞部、３８、３９、４１…開口、３８Ａ、３９Ａ、４１Ａ…短管、４２…吸引管、４３…バルブ、４４…吸引手段、４５…圧力計、４６…圧力制御手段、４７…コントローラ、４８…気泡、６０…円環状流型のマイクロリアクター、６１…装置本体、６２…円管部材、６３…胴体部、６４…吐出口、６６…フランジ部、６８…大径部、７０…第１仕切板、７２…気体透過部材、７４…円環状液体流路、７６…円環状空洞部、７８、９８、１００…スペーサ、８０…蓋板、８２…嵌挿穴、８４…整流部材、８６…第２仕切板、８８…第１ヘッダー部、９０…第２ヘッダー部、９２…隔壁部材、９４…第１の液体供給路、９６…第２の液体供給路、１０２…円環状マイクロ流路、１０４…第１の液体供給管、１０６…第２の液体供給管、１０８…第１の液体供給口、１１０…第２の液体供給口、１１２…出液路、１１４、１１６…短管、１１８…圧力制御手段、１２０…吸引手段、１２２…圧力計、１２４…バルブ、１２６…コントローラ、１２８…吸引管   DESCRIPTION OF SYMBOLS 10 ... Flaky flow type micro reactor, 12 ... Apparatus main body, 14 ... Liquid supply pipe | tube, 16 ... Liquid supply means, 18 ... Gas permeation | transmission member, 20 ... Upper plate, 21 ... Lower plate, 22 ... Main body member, 23 ... Bolt, 24 ... lid member, 25 ... nut, 26 ... micro flow path, 28 ... liquid supply path, 30 ... Y-shaped liquid flow path, 32 ... liquid outlet, 34 ... liquid inlet, 36 ... Y-shaped cavity 38, 39, 41 ... opening, 38A, 39A, 41A ... short pipe, 42 ... suction pipe, 43 ... valve, 44 ... suction means, 45 ... pressure gauge, 46 ... pressure control means, 47 ... controller, 48 ... Air bubbles, 60 ... annular flow type microreactor, 61 ... device main body, 62 ... circular pipe member, 63 ... body part, 64 ... discharge port, 66 ... flange part, 68 ... large diameter part, 70 ... first partition plate 72 ... gas permeable member, 74 ... annular liquid flow path, 7 ... annular cavity, 78, 98, 100 ... spacer, 80 ... lid plate, 82 ... insertion hole, 84 ... rectifying member, 86 ... second partition plate, 88 ... first header part, 90 ... second header part , 92 ... partition member, 94 ... first liquid supply path, 96 ... second liquid supply path, 102 ... annular microchannel, 104 ... first liquid supply pipe, 106 ... second liquid supply pipe, DESCRIPTION OF SYMBOLS 108 ... 1st liquid supply port, 110 ... 2nd liquid supply port, 112 ... Outflow path, 114, 116 ... Short tube, 118 ... Pressure control means, 120 ... Suction means, 122 ... Pressure gauge, 124 ... Valve 126 ... Controller, 128 ... Suction tube

Claims (14)

複数の液体をそれぞれの液体供給路を通してマイクロ流路に合流させて、これらの液体を薄片状の層流として流通させつつ、液体同士をその接触界面の法線方向へ拡散して液液反応を行わせる薄片状流型のマイクロリアクターを用いて、副生ガスの発生を伴う液液反応を行うマイクロリアクターの反応方法において、
前記液液反応の進行に伴って発生する副生ガスを、液体を通さずに気体を通す気体透過部材を介して前記マイクロ流路外に随時透過しながら前記液液反応を行わせることを特徴とするマイクロリアクターを用いた反応方法。 A plurality of liquids are joined to the micro flow path through each liquid supply path, and these liquids are circulated as a laminar laminar flow, while the liquids are diffused in the normal direction of the contact interface to perform a liquid-liquid reaction. In a reaction method of a microreactor that performs a liquid-liquid reaction with generation of by-product gas using a flaky flow type microreactor to be performed,
The by-product gas generated with the progress of the liquid-liquid reaction is allowed to perform the liquid-liquid reaction while passing through the gas flow member through the gas without passing through the liquid as needed. A reaction method using a microreactor. 円環状なマイクロ流路に連通する複数の液体供給路を同心軸の多重筒構造にして、複数の液体を前記液体供給路を通して前記マイクロ流路に合流させることにより、これらの液体を同心軸状に積層させて該同心軸に直交する断面が円環状の層流として流通させつつ、液体同士をその接触界面の法線方向へ拡散して液液反応を行わせる円環状流型のマイクロリアクターを用いて、副生ガスの発生を伴う液液反応を行うマイクロリアクターの反応方法において、
前記液液反応の進行に伴って発生する副生ガスを、液体を通さずに気体を通す気体透過部材を介して前記マイクロ流路外に随時透過しながら前記液液反応を行わせることを特徴とするマイクロリアクターを用いた反応方法。 A plurality of liquid supply passages communicating with the annular microchannel are formed into a concentric multiple tube structure, and a plurality of liquids are merged into the microchannel through the liquid supply passage, thereby concentrating the liquids in a concentric shape. An annular flow type microreactor that allows liquid-liquid reaction to be performed by diffusing liquids in the normal direction of the contact interface while allowing the cross section perpendicular to the concentric axis to circulate as an annular laminar flow. In a reaction method of a microreactor that uses a liquid-liquid reaction accompanied by generation of by-product gas,
The by-product gas generated with the progress of the liquid-liquid reaction is allowed to perform the liquid-liquid reaction while passing through the gas flow member through the gas without passing through the liquid as needed. A reaction method using a microreactor. 前記マイクロ流路の等価直径は１ｍｍ以下であることを特徴とする請求項１又は２のマイクロリアクターを用いた反応方法。   The reaction method using a microreactor according to claim 1 or 2, wherein the equivalent diameter of the microchannel is 1 mm or less. 前記マイクロ流路側の第１の圧力が該マイクロ流路の外側の第２の圧力よりも大きくなるように、前記第１及び第２の圧力を相対的に制御することを特徴とする請求項１〜３の何れか１のマイクロリアクターを用いた反応方法。   2. The first and second pressures are controlled relative to each other so that the first pressure on the micro-channel side is larger than the second pressure outside the micro-channel. A reaction method using the microreactor of any one of -3. 複数の液体をそれぞれの液体供給路を通してマイクロ流路に合流させてこれらの液体を薄片状の層流として流通させつつ、液体同士をその接触界面の法線方向へ拡散して液液反応を行わせるマイクロリアクターにおいて、
前記液体供給路及び前記マイクロ流路のうちの少なくともマイクロ流路の流路壁の一部又は全部が、液体は通さずに気体を通す気体透過部材で形成されていることを特徴とするマイクロリアクター。 A plurality of liquids are joined to the micro flow path through the respective liquid supply paths, and these liquids are circulated as a laminar laminar flow, while the liquids are diffused in the normal direction of the contact interface to perform a liquid-liquid reaction. In a microreactor
A microreactor characterized in that at least a part or all of a channel wall of the microchannel among the liquid supply channel and the microchannel is formed of a gas permeable member that allows a gas to pass through without passing a liquid. . 円環状のマイクロ流路に連通する複数の液体供給路を同心軸の多重円筒構造にして、複数の液体を前記液体供給路を通して前記マイクロ流路に合流させることにより、これらの液体を同心軸状に積層させて該同心軸に直交する断面が円環状の層流として流通させつつ、液体同士をその接触界面の法線方向へ拡散して副生ガスを伴う液液反応を行わせる円環状流型のマイクロリアクターにおいて、
前記液体供給路及び前記マイクロ流路のうちの少なくとも円環状のマイクロ流路の流路壁の一部又は全部が、液体は通さずに気体を通す気体透過部材で形成されていることを特徴とするマイクロリアクター。 A plurality of liquid supply passages communicating with the annular micro-channel are formed into a concentric multi-cylindrical structure, and a plurality of liquids are merged into the micro-channel through the liquid supply channels, so that these liquids are concentric. An annular flow in which a cross-section perpendicular to the concentric axis is circulated as an annular laminar flow and a liquid-liquid reaction involving a by-product gas is performed by diffusing liquids in the normal direction of the contact interface. In type microreactor,
A part or all of the channel wall of at least the annular microchannel of the liquid supply channel and the microchannel is formed of a gas permeable member that allows gas to pass without passing liquid. Microreactor to do. 前記マイクロ流路の等価直径は１ｍｍ以下であることを特徴とする請求項５又は６のマイクロリアクター。   The microreactor according to claim 5 or 6, wherein an equivalent diameter of the microchannel is 1 mm or less. 前記気体透過部材を挟んで前記マイクロ流路反対側に形成され、前記液体供給路及び前記マイクロ流路のうちの少なくともマイクロ流路の流れ方向に沿った空洞部と、
前記マイクロ流路側の第１の圧力が前記空洞部側の第２の圧力よりも大きくなるように、前記第１及び第２の圧力を相対的に制御する圧力制御手段と、を備えたことを特徴とする請求項５〜７の何れか１のマイクロリアクター。 A cavity formed along the flow direction of at least the microchannel among the liquid supply channel and the microchannel, and formed on the opposite side of the microchannel with the gas permeable member interposed therebetween;
Pressure control means for relatively controlling the first and second pressures so that the first pressure on the microchannel side is larger than the second pressure on the cavity side. The microreactor according to any one of claims 5 to 7, characterized in that 前記圧力制御手段は、前記空洞部を吸引して該空洞部を減圧する吸引方式であることを特徴とする請求項８のマイクロリアクター。   9. The microreactor according to claim 8, wherein the pressure control means is a suction system that sucks the cavity and depressurizes the cavity. 前記圧力制御手段は、前記空洞部に高速気流を発生させてピトー管現象を生じさせる気体流方式であることを特徴とする請求項８のマイクロリアクター。   9. The microreactor according to claim 8, wherein the pressure control means is a gas flow system that generates a pitot tube phenomenon by generating a high-speed air flow in the cavity. 前記圧力制御手段は、前記副生ガスが前記気体透過部材を透過する際の圧力損失以上の圧力を前記マイクロ流路側に加える加圧方式であることを特徴とする請求項８のマイクロリアクター。   9. The microreactor according to claim 8, wherein the pressure control means is a pressurizing system that applies a pressure higher than a pressure loss when the by-product gas permeates the gas permeable member to the micro flow path side. 前記マイクロリアクターの装置本体を本体部材と蓋部材とで構成し、前記液体供給路から前記マイクロ流路の終端に至る液体流路及び前記空洞部の両方を前記本体部材に形成し、前記液体流路と前記空洞部との間に前記気体透過部材を設けたことを特徴とする請求項５のマイクロリアクター。   The main body of the microreactor is composed of a main body member and a lid member, and both the liquid flow path from the liquid supply path to the end of the micro flow path and the cavity are formed in the main body member, and the liquid flow 6. The microreactor according to claim 5, wherein the gas permeable member is provided between a path and the cavity. 前記マイクロリアクターの装置本体を本体部材と蓋部材とで構成し、前記液体供給路から前記マイクロ流路の終端に至る液体流路を前記本体部材に形成し、前記空洞部を前記蓋部材に形成し、本体部材と蓋部材とで前記気体透過部材を挟むことを特徴とする請求項５のマイクロリアクター。   The main body of the microreactor is composed of a main body member and a lid member, a liquid flow path from the liquid supply path to the end of the micro flow path is formed in the main body member, and the cavity is formed in the lid member The microreactor according to claim 5, wherein the gas permeable member is sandwiched between the main body member and the lid member. 前記マイクロリアクターの装置本体を形成する材料は、金属、ガラス、セラミックス、プラスチック樹脂、シリコンの何れかであることを特徴とする請求項５〜１３の何れか１のマイクロリアクター。   The microreactor according to any one of claims 5 to 13, wherein a material forming the device body of the microreactor is any one of metal, glass, ceramics, plastic resin, and silicon.
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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005103541A (en) * 2003-09-30 2005-04-21 Boehringer Ingelheim Microparts Gmbh Method and apparatus for separating and leading out air bubbles from liquid
JP2007090135A (en) * 2005-09-27 2007-04-12 Yamaha Corp Microchip
JP2007090160A (en) * 2005-09-27 2007-04-12 Fujifilm Corp Fluid device
JP4646125B2 (en) * 2005-09-27 2011-03-09 ヤマハ株式会社 Microchip and bubble separation method using the same
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