JP2004358453A - Microchannel structure and method for chemical operation of liquid using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a microchannel structure wherein fluids adjacent to each other each forms stable fluid interfaces between them in the microchannels and are discharged each severally through given outlet ports without mixing laminar flows with adjacent ones, and to provide a method for more effective chemical operation with the microchannel structure making the fluids contact each other at their interfaces along the flow direction in the microchannels only by introducing the fluids into the microchannels. <P>SOLUTION: The microchannel structure comprises two or more inlet ports 11 and introducing channels for introducing the fluids, the microchannels 19 communicating to a junction where the introducing channels join each other for running the introduced fluids, and two or more outlet ports 12 and discharging channels communicating to the microchannels and having a fork 4 where prescribed fluids are separated. The microchannels are provided with a plurality of partition walls 22 along the fluid interfaces 3 formed between two or more kinds of introduced fluids for preventing the introduced fluids from mixing with each other. The method comprises a chemical operation of liquids using the microchannel structure. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

表１は、等速条件下で、各送液速度における混入率を、水相への有機相の混入率（％）、有機相への水相の混入率（％）として示したものであり、流速は３、５、８、１０、２０、５０μＬ／分であり、流体進行方向の仕切り壁と仕切り壁の最短の間隔は５０、１００、２００、４００、８００μｍである。
【００９９】
第１の実施例の結果から、流体進行方向の仕切り壁と仕切り壁の最短の間隔が４００μｍ以下のとき、送液速度の範囲が少なくとも８〜５０μＬ／分の範囲で混入率１０％未満を実現した。流体進行方向の仕切り壁と仕切り壁の最短の間隔が８００μｍの場合は、どの送液速度においても混入率１０％未満にはならなかった。
（実施例２）
第２の実施例として、実施例１で使用した図６に示す微小流路構造体を使用して、シクロヘキサンを８μＬ／分の固定した送液速度で送液し、それに対して水を３μＬ／分〜２０μＬ／分の間で送液速度を変えて送液した。すなわち、シクロヘキサンに対する水の送液速度比が０．３７５〜２．５の間で、導入口Ａ（２８）から水を、導入口Ｂ（２９）からシクロヘキサンを上記条件で送液し、排出口Ｃ（３０）から排出された水の量と混入したシクロヘキサンの量を、排出口Ｄ（３１）から排出されたシクロヘキサンの量と混入した水の量を、それぞれ、メスシリンダーにて秤量して測定し、その結果を表２に示した。
【０１００】
【表２】

表２は、各送液速度比における混入率を、水相への有機相の混入率（％）、有機相への水相の混入率（％）として示したものであり、送液速度比は０．３７５、０．６２５、１．０００、１．２５０、２．５００であり、流体進行方向の仕切り壁と仕切り壁の最短の間隔は５０、１００、２００、４００、８００μｍである。
【０１０１】
第２の実施例の結果から、流体進行方向の仕切り壁と仕切り壁の最短の間隔が２００μｍ以下のとき、送液速度比の範囲が少なくとも０．６２５〜１．２５の範囲で混入率１０％未満を実現した。、流体進行方向の仕切り壁と仕切り壁の最短の間隔が４００μｍ、および８００μｍの場合は、送液速度の比が１：１以外は混入率１０％未満にはならなかった。
（比較例１）
第１の比較例として図５（ｂ）に使用した微小流路構造体の構成を示した。微小流路の形状は流体導入口側と流体排出口側がＹ字状に２本の微小流路に分岐しており、微小流路の内部構造としては、図５（ａ）に示すように微小流路の幅方向に対してほぼ中央に、微小流路の深さ（１７）の約２０％程度の高さの流体進行方向に沿った連続したガイド状（１６）を形成した。製作した微小流路の幅は１００μｍ、深さは２０μｍ、長さ３０ｍｍである。ガイド状の厚さ（３６）は約５μｍである。
【０１０２】
図５（ｂ）に示すように、微小流路は、７０ｍｍ×３８ｍｍ×１ｍｍ（厚さ）のパイレックス（登録商標）基板（３７）に一般的なフォトリソグラフィーとウエットエッチングにより形成し、導入口Ａ（２８）と導入口Ｂ（２９）、排出口Ｃ（３０）と排出口Ｄ（３１）に相当する位置に、直径０．６ｍｍの貫通した小穴（３５）を機械的加工手段により設けた同サイズのパイレックス（登録商標）基板をカバー体（３４）として熱融着により接合することで微小流路を密閉した。
【０１０３】
この微小流路構造体に水とシクロヘキサンをそれぞれ、実施例１と同様にして５μＬ／分〜２０μＬ／分の間で等しい送液速度で送液した。導入口Ａ（２８）から水を、導入口Ｂ（２９）からシクロヘキサンを上記条件で送液し、排出口Ｃ（３０）から排出された水の量と混入したシクロヘキサンの量を、排出口Ｄ（３１）から排出されたシクロヘキサンの量と混入した水の量を、それぞれ、メスシリンダーにて秤量して測定し、測定結果を表１に示した。その結果、水へのシクロヘキサン及び、シクロヘキサンへの水への混入率はどの送液速度においても、３０％以上となり非常に高い混入率となった。
【０１０４】
また、同様の微小流路構造体を用いて、実施例２と同様にして、シクロヘキサンを８μＬ／分の固定した送液速度で送液し、それに対して水を３μＬ／分〜２０μＬ／分の間で送液速度を変えて送液した。すなわち、シクロヘキサンに対する水の送液速度比が０．３７５〜２．５の間で、導入口Ａ（２８）から水を、導入口Ｂ（２９）からシクロヘキサンを上記条件で送液し、排出口Ｃ（３０）から排出された水の量と混入したシクロヘキサンの量を、排出口Ｄ（３１）から排出されたシクロヘキサンの量と混入した水の量を、それぞれ、メスシリンダーにて秤量して測定し、測定結果を表２に示した。その結果、水へのシクロヘキサン及び、シクロヘキサンへの水への混入率はどの送液速度比においても、２０％以上となり非常に高い混入率となった。
（実施例３）
第３の実施例として、図６（ｂ）の微小流路構造体の構成及び図６（ａ）に示す微小流路の内部構造を有する実施例１で使用した微小流路構造体のうち、流体進行方向の仕切り壁と仕切り壁の最短の間隔が２００μｍと４００μｍの微小流路構造体の微小流路の片側内壁を以下の手順で疎水化処理した。
【０１０５】
まず、飽和ＫＯＨ−エタノール溶液を導入口Ａ（２８）および導入口Ｂ（２９）から送液速度５μＬ／分で３０分間程度送液し、次に導入口Ａからはトルエン、導入口Ｂからは１０％オクタデシルトリクロロシランのトルエン溶液を送液速度５μＬ／分で３時間程度送液した。この処理により、トルエンのみを送液した導入口Ａから導入されて排出口Ｃ（３０）から排出される側の微小流路片側内壁はもともとのパイレックス（登録商標）ガラスの親水性の状態であり、１０％オクタデシルトリクロロシランのトルエン溶液を送液した導入口Ｂから導入されて排出口Ｄ（３１）から排出される側の微小流路片側内壁は疎水性に修飾される。
【０１０６】
この微小流路の片側内壁を疎水化処理した、流体進行方向の仕切り壁と仕切り壁の最短の間隔が４００μｍの微小流路構造体に水とシクロヘキサンをそれぞれ、３μＬ／分〜５０μＬ／分の間で等しい送液速度で送液した。導入口Ａ（２８）から水を、導入口Ｂ（２９）からシクロヘキサンを上記条件で送液し、排出口Ｃ（３０）から排出された水の量と混入したシクロヘキサンの量を、排出口Ｄ（３１）から排出されたシクロヘキサンの量と混入した水の量を、それぞれ、メスシリンダーにて秤量して測定し、測定結果を表３に示した。
【０１０７】
【表３】

表３は、等速条件下で、各送液速度における混入率を、水相への有機相の混入率（％）、有機相への水相の混入率（％）として示したものであり、流速は３、５、８、１０、２０、５０μＬ／分である。
【０１０８】
第３の実施例の結果、実施例１での仕切り壁４００μｍにおける混入率１０％未満の送液速度の範囲において、混入率が８％未満となり混入率が低減した。
【０１０９】
また、この微小流路の片側内壁を疎水化処理した、流体進行方向の仕切り壁と仕切り壁の最短の間隔が２００μｍの微小流路構造体にシクロヘキサンを８μＬ／分の固定した送液速度で送液し、それに対して水を３μＬ／分〜２０μＬ／分の間で送液速度を変えて送液した。すなわち、シクロヘキサンに対する水の送液速度比が０．３７５〜２．５の間で、導入口Ａ（２８）から水を、導入口Ｂ（２９）からシクロヘキサンを上記条件で送液し、排出口Ｃ（３０）から排出された水の量と混入したシクロヘキサンの量を、排出口Ｄ（３１）から排出されたシクロヘキサンの量と混入した水の量を、それぞれ、メスシリンダーにて秤量して測定し、測定結果を表４に示した。
【０１１０】
【表４】

表４は、各送液速度比における混入率を、水相への有機相の混入率（％）、有機相への水相の混入率（％）として示したものであり、送液速度比は０．３７５、０．６２５、１．０００、１．２５０、２．５００である。
その結果、実施例２での仕切り壁２００μｍにおける混入率１０％未満の送液速度比の範囲において、混入率が８％未満となり混入率が低減した。
（実施例４）
第４の実施例として使用した微小流路構造体の構成を図６（ｂ）に示した。微小流路の形状は流体導入口側と流体排出口側がＹ字状に２本の微小流路に分岐している。また本実施例に使用した微小流路の内部構造を図２１に示した。図２１（ａ）は、本実施例で用いた微小流路を上面から見たＳＥＭ写真であり、図２１（ｂ）は本実施例で用いた微小流路の内部構造の形状を示した概念図である。形成した微小流路の幅は２４０μｍ、深さは６０μｍ、長さ３０ｍｍであり、導入口Ａと排出口Ｃ側の微小流路の片側の側壁から３０μｍの突起（２０）を多数形成した。また、図６（ａ）に示すように、微小流路の中央付近には、流体進行方向の最大長さ５０μｍの不連続な高さ６０μｍの仕切り壁（２２）を流体進行方向に５０μｍ間隔で形成した。
【０１１１】
実施例１と同様の手法により、流路は、７０ｍｍ×３８ｍｍ×１ｍｍ（厚さ）のパイレックス（登録商標）基板に一般的なフォトリソグラフィーとウエットエッチングにより形成し、流体の導入口Ａ（２８）と導入口Ｂ（２９）、流体の排出口Ｃ（３０）と排出口Ｄ（３１）に相当する位置に、直径０．６ｍｍの貫通した小穴（３５）を機械的加工手段により設けた同サイズのパイレックス（登録商標）基板をカバー体（３４）として熱融着により接合することで微小流路を密閉した。
【０１１２】
この微小流路構造体を用いて、エチレンジアミンのヨードメタンによるメチル化反応を行なった。導入口Ａから、すなわち微小流路の側壁に突起を有した側にエチレンジアミンの水溶液の水相を１０μＬ／分で送液し、導入口Ｂからヨードメタンのブタノール溶液の有機相を３μＬ／分で送液した。この反応系は、エチレンジアミンがヨードメタンと反応し、Ｎ−メチルエチレンジアミンが合成され水相に抽出される反応系である。流体導入口から各溶液を送液した状態で微小流路を顕微鏡で観察したところ、水相と有機相の流体境界が観察され、流体排出口側の分岐部において流体を分離し、排出口Ｃから水相を、排出口Ｄから有機相を実質的にほぼお互いの混入なしに分離して排出することができた。また、流体排出口から排出された水相を試験管で回収し、高速液体クロマトグラフィーを用いて分析したところ、エチレンジアミンとＮ−メチルエチレンジアミンの量比が約９０：１０で確認され、この反応におけるＮ−メチルエチレンジアミンの転換率は約１０％程度であった。
（実施例５）
第５の実施例として使用した微小流路構造体の構成を図６（ｂ）に示した。微小流路の形状は流体導入口側と流体排出口側がＹ字状に２本の微小流路に分岐している。形成した微小流路（１９）の幅は２４０μｍ、深さは６０μｍ、長さ３０ｍｍである。また、微小流路の内部構造としては、図６（ａ）に示すように微小流路の中央付近に流体進行方向の最大長さ５０μｍの不連続な高さ６０μｍの仕切り壁（２２）を流体進行方向に５０μｍ間隔で形成した。
【０１１３】
実施例１と同様の手法により、微小流路は、７０ｍｍ×３８ｍｍ×１ｍｍ（厚さ）のパイレックス（登録商標）基板に一般的なフォトリソグラフィーとウエットエッチングにより形成し、導入口Ａ（２８）と導入口Ｃ（２９）、排出口Ｃ（３０）と排出口Ｄ（３１）に相当する位置に、直径０．６ｍｍの貫通した小穴（３５）を機械的加工手段により設けた同サイズのパイレックス（登録商標）基板をカバー体（３４）として熱融着により接合することで微小流路を密閉した。この微小流路を用いて、エチレンジアミンのヨードメタンによるメチル化反応を行なった。導入口Ａからエチレンジアミンの水溶液の水相に平均粒径５μｍのシリカの微粒子を混入して１０μＬ／分で送液し、導入口Ｂからヨードメタンのブタノール溶液の有機相を図２０に示す流体進行方向（２７）に３μＬ／分で送液した。この反応系は、エチレンジアミンがヨードメタンと反応し、Ｎ−メチルエチレンジアミンが合成され水相に抽出される反応系である。流体導入口から各溶液を送液した状態で微小流路を顕微鏡で観察したところ、水相と有機相の流体境界が観察され、流体排出口側の分岐部において流体を分離し、排出口Ｃから水相を、排出口Ｄから有機相を実質的にほぼお互いの混入なしに分離して排出することができた。また、排出口Ｃから排出された水相を試験管で回収し、高速液体クロマトグラフィーを用いて分析したところ、エチレンジアミンとＮ−メチルエチレンジアミンの量比が約９０：１０で確認され、この反応におけるＮ−メチルエチレンジアミンの転換率は約１０％程度であった。
（実施例６）
第６の実施例として使用した微小流路構造体の構成を図６（ｂ）に示した。微小流路の形状は流体導入口側と流体排出口側がＹ字状に２本の微小流路に分岐している。。形成した微小流路の幅は２４０μｍ、深さは６０μｍ、長さ３０ｍｍである。また、微小流路の内部構造としては、図６（ａ）に示すように流路の中央付近には高さ６０μｍの仕切り壁を形成した。
【０１１４】
実施例１と同様の手法により、流路は、７０ｍｍ×３８ｍｍ×１ｍｍ（厚さ）のパイレックス（登録商標）基板に一般的なフォトリソグラフィーとウエットエッチングにより形成し、導入口Ａ（２８）と導入口Ｂ（２９）、排出口Ｃ（３０）と排出口Ｄ（３１）に相当する位置に、直径０．６ｍｍの貫通した小穴を機械的加工手段により設けた、同サイズのパイレックス（登録商標）基板をカバー体として熱融着により接合することで微小流路を密閉した。
【０１１５】
この微小流路構造体を用いて、エチレンジアミンのヨードメタンによるメチル化反応を行なった。導入口Ａからエチレンジアミンの水溶液の水相を１０μＬ／分で送液し、導入口Ｂからヨードメタンのブタノール溶液の有機相を３μＬ／分で送液した。流体導入口から各溶液を送液した状態で微小流路を顕微鏡で観察したところ、水相と有機相の流体境界が観察され、流体排出口側の分岐部において流体を分離し、排出口Ｃから水相を、排出口Ｄから有機相を実質的にほぼお互いの混入なしに分離して排出することができた。また、排出口Ｃから排出された水相を試験管で回収し、高速液体クロマトグラフィーを用いて分析したところ、エチレンジアミンとＮ−メチルエチレンジアミンの量比が約９３：７で確認され、この反応におけるＮ−メチルエチレンジアミンの転換率は約７％程度であった。
【０１１６】
以上の実施例４、実施例５、実施例６から、本発明により２種以上の流体が層流を形成して流体境界で接触し、不連続な仕切り壁によりその流体境界を安定に保ちながら、流体排出口側の微小流路の分岐部において実質的にほぼお互いの混入なしに分離し、かつ、反応に必要な原料や反応生成物を含んだ流体をその流体内で攪拌するような微細構造を微小流路内に形成することや、微粒子を混入させた流体内で攪拌することで、化学反応や溶媒抽出、分離がすみやかに実施可能な微小流路を有する微小流路構造体および化学操作方法を提供することことが可能となったことがわかる。
（実施例７）
第７の実施例として、図２２（ｂ）に示す微小流路構造体を用いて、触媒反応の一つである環境汚染物質分解作用を持つラッカーゼによるｐ−クロロフェノールの分解反応を行なった。微小流路（１９）の形状は、導入口Ａ（２８）と導入口Ｂ（２９）に連通する２本の導入流路と、排出口Ｃ（３０）と排出口Ｄ（３１）に連通する２本の排出流路がそれぞれＹ字状に分岐している微小流路を用いた。形成した微小流路の幅は１００μｍ、深さは２５μｍ、長さは４００ｍｍである。微小流路の内部構造は、実施例４と同様に図２１に示すように、導入口Ａと排出口Ｃ側の微小流路の片側の側壁から３０μｍの突起（２０）を多数形成した。また、図２２（ａ）に示すように、微小流路の中央付近には、流体進行方向の最大長さ５０μｍの不連続な高さ２５μｍの仕切り壁（２２）を流体進行方向に５０μｍ間隔で形成した。
【０１１７】
この微小流路構造体を用いて、触媒反応の一つである環境汚染物質分解作用を持つラッカーゼによるｐ−クロロフェノールの分解反応を行なった。導入口Ａから、すなわち微小流路の側壁に突起を有した側に有機相として、ｐ−クロロフェノール１００μＭを含有するイソオクタン溶液を５μＬ／分で送液し、導入口Ｂから水相としてラッカーゼ３０μＭを含有するコハク酸緩衝溶液（ｐＨ５．０）を５μＬ／分で送液し、反応前後の両相のｐ−クロロフェノール量を液体クロマトグラフィーにより定量した。
【０１１８】
結果として、流体排出口側の分岐部において流体を分離し、排出口Ｃから水相を、排出口Ｄから有機相を実質的にほぼお互いの混入なしに分離して排出することができた。また、約８秒でｐ−クロロフェノールの分解率が８２％まで到達した。
（実施例８）
第８の実施例として、図２２（ｂ）に示す微小流路構造体を用いて、触媒反応の一つである環境汚染物質分解作用を持つラッカーゼによるｐ−クロロフェノールの分解反応を行なった。微小流路（１９）の形状は、導入口Ａ（２８）と導入口Ｂ（２９）に連通する２本の導入流路と、排出口Ｃ（３０）と排出口Ｄ（３１）に連通する２本の排出流路がそれぞれＹ字状に分岐している微小流路を用いた。形成した微小流路の幅は１００μｍ、深さは２５μｍ、長さは４００ｍｍである。微小流路の内部構造としては、図２２（ａ）に示すように微小流路の中央付近には、流体進行方向の最大長さ５０μｍの不連続な高さ２５μｍの仕切り壁（２２）を流体進行方向に５０μｍ間隔で形成した。
【０１１９】
この微小流路構造体を用いて、導入口Ａから、有機相として、ｐ−クロロフェノール１００μＭを含有するイソオクタン溶液に平均粒径５μｍのシリカの微粒子を混入して５μＬ／分で送液し、導入口Ｂから水相としてラッカーゼ３０μＭを含有するコハク酸緩衝溶液（ｐＨ５．０）を５μＬ／分で送液し、反応前後、２つの流体排出口から出てくるの両相のｐ−クロロフェノール量を液体クロマトグラフィーにより定量した。
【０１２０】
結果として、流体排出口側の分岐部において流体を分離し、排出口Ｃから水相を、排出口Ｄから有機相を実質的にほぼお互いの混入なしに分離して排出することができた。また、約８秒でｐ−クロロフェノールの分解率が８５％まで到達した。
（実施例９）
実施例９として、図２２（ｂ）に示す微小流路構造体を用いて、触媒反応の一つである環境汚染物質分解作用を持つラッカーゼによるｐ−クロロフェノールの分解反応を行なった。微小流路（１９）の形状は、導入口Ａ（２８）と導入口Ｂ（２９）に連通する導入流路と、排出口Ｃ（３０）と排出口Ｄ（３１）に連通する排出流路がそれぞれＹ字状に２本に分岐している微小流路を用いた。形成した微小流路の幅は１００μｍ、深さは２５μｍ、長さは４００ｍｍである。微小流路の内部構造として図２２（ａ）に示すように微小流路の中央付近には、流体進行方向の最大長さ５０μｍの不連続な高さ２５μｍの仕切り壁（２２）を流体進行方向に５０μｍ間隔で形成した。
【０１２１】
この微小流路構造体を用いて、導入口Ａから有機相として、ｐ−クロロフェノール１００μＭを含有するイソオクタン溶液を５μＬ／分で送液し、導入口Ｂからは水相としてラッカーゼ３０μＭを含有するコハク酸緩衝溶液（ｐＨ５．０）を５μＬ／分で送液し、反応前後の両相のｐ−クロロフェノール量を液体クロマトグラフィーにより定量した。
【０１２２】
結果として、流体排出口側の分岐部において流体を分離し、排出口Ｃから水相を、排出口Ｄから有機相を実質的にほぼお互いの混入なしに分離して排出することができた。また、約８秒でｐ−クロロフェノールの分解率が８０％まで到達した。
【０１２３】
以上の実施例７、実施例８、実施例９から、本発明により２種以上の流体が層流を形成して流体境界で接触し、不連続な仕切り壁によりその流体境界を安定に保ちながら、微小流路の分岐部で流体をほぼお互いの混入なしに分離することができ、かつ、反応に必要な原料や反応生成物を含んだ流体をその流体内で攪拌するような微細構造を微小流路内に形成することや、また微粒子を混入した流体のみを攪拌することで、化学反応や溶媒抽出、分離をすみやかに実施可能な微小流路を有する微小流路構造体と化学操作方法を提供することことが可能となったことがわかる。
（実施例１０）
第１０の実施例として、図２２（ｂ）に示すような微小流路構造体を製作した。微小流路（１９）の形状は、導入口Ａ（２８）と導入口Ｂ（２９）に連通する導入流路と排出口Ｃ（３０）と排出口Ｄ（に連通する、排出流路がそれぞれＹ字状に２本に分岐している微小流路（１９）を用いた。形成した微小流路の幅は１００μｍ、深さは２５μｍ、長さは４００ｍｍである。また、微小流路内部の構造として、微小流路の中央付近には、図２２（ａ）に示したような流体進行方向の最大長さが５０μｍの不連続な高さ２５μｍの仕切り壁（２２）を流体進行方向に５０μｍ間隔で形成した。微小流路は、７０ｍｍ×３８ｍｍ×１ｍｍ（厚さ）のパイレックス（登録商標）基板に一般的なフォトリソグラフィーとウエットエッチングにより形成した。導入口Ａ（２８）と導入口Ｂ（２９）、排出口Ｃ（３０）と排出口Ｄ（３１）に相当する位置に、直径０．６ｍｍの貫通した小穴（３５）を機械的加工手段により設けた同サイズのパイレックス（登録商標）基板をカバー体（３４）として熱融着により接合することで微小流路を密閉し、微小流路構造体を形成した。
【０１２４】
この微小流路構造体を用いて、触媒反応の一つである環境汚染物質分解作用を持つラッカーゼによるｐ−クロロフェノールの分解反応を行なった。微小流路には、導入口Ａから水相としてラッカーゼ３０μＭを含有するコハク酸緩衝溶液（ｐＨ５．０）を５μＬ／分で送液し、導入口Ｂから有機相として、ｐ−クロロフェノール１００μＭを含有するイソオクタン溶液を５μＬ／分で送液し、反応前後の両相のｐ−クロロフェノール量を液体クロマトグラフィーにより定量した。
【０１２５】
結果として、流体排出口側の分岐部において流体を分離し、排出口Ｃから水相を、排出口Ｄから有機相を実質的にほぼお互いの混入なしに分離して排出することができた。また、ｐ−クロロフェノールの分解率が８０％まで到達するのに約８秒であった。さらに、酵素の活性の度合いをフェノールアミノアンチピリン法（Ｐ−４ＡＡ法）により測定したところ、上記反応を１０回繰り返しても、酵素の活性は９０％以上を維持した。
（比較例２）
第２の比較例として、５０ｍｌのサンプルビンに、水相としてラッカーゼ３０μＭを含有するコハク酸緩衝溶液（ｐＨ５．０）を１５ｍｌ、有機相として、ｐ−クロロフェノール１００μＭを含有するイソオクタン溶液を１５ｍｌ入れ、マグネチックスターラーを用いて激しく攪拌し、反応前後の両相のｐ−クロロフェノール量を液体クロマトグラフィーにより定量した。その結果、ｐ−クロロフェノールの分解率が８０％まで到達するのに約３０分を要した。また、酵素の活性の度合いをフェノールアミノアンチピリン法（Ｐ−４ＡＡ法）により測定したところ、約３０分後には酵素の活性は約８０％程度に低下し、約９０分後には酵素の活性は約５％程度に低下した。
【０１２６】
以上の実施例１０と比較例２から、本発明により２種以上の流体が層流を形成して流体境界で接触し、不連続な仕切り壁により流体境界を安定に保ちながらその流体境界で反応し、微小空間の特徴である大きな比界面積と短い分子拡散距離により、機械的攪拌を必要とせずに速やかに酵素反応が進行し、機械的攪拌による物理的な作用や有機相中で酵素が懸濁状になることに起因する酵素の活性が失われること無しに、酵素を回収し再利用することが可能であり酵素反応が効率よく進行したことがわかる。
【０１２７】
【発明の効果】
本発明によれば、以下の効果を奏することができる。
【０１２８】
本発明の微小流路構造体は、流体を導入するための２以上の導入口及びそれらに連通する導入流路と、前記導入流路が合流する合流部と連通しかつ導入された流体を流すための微小流路と、前記微小流路に連通しかつ所定の流体を分離する分岐部を有した２以上の排出流路及びそれらに連通する排出口と、を有した微小流路構造体であって、前記微小流路には、導入された２種以上の流体により形成される境界に沿って、導入された流体が互いに混入しないための複数の仕切り壁が設けられている微小流路構造体である。このような構造にすることで、流体を送液するポンプなどに起因する送液速度の時間的変動等による流体境界の位置の変動を抑制し、かつ、微小流路内壁と送液する流体との親和性の違いによる流体の回り込みを防止することができ、微小流路の流体排出口から、各々の流体を他の流体が混入することなく排出することができる。
【０１２９】
また、微小流路に導入するすべての流体の送液速度が等しい場合、流体進行方向に対する仕切り壁と仕切り壁の間隔を一定間隔以下（仕切り壁と仕切り壁の間隔を８００μｍ程度以下、好ましくは４００μｍ程度以下）とすることで、粘性の等しい隣接した流体が所定の送液速度範囲において、各々の流体に他の流体が混入せずに排出流路を通って排出口から排出することができる。
【０１３０】
また、微小流路に導入する流体のうち隣接する流体の、相対的に流路壁面と親媒性の低い流体に対する流路壁面と親媒性の高い流体の送液速度と粘性係数の積が異なる場合、仕切り壁と仕切り壁の流体進行方向に対する最短の間隔を一定間隔以下（仕切り壁と仕切り壁の間隔を４００μｍ程度以下、好ましくは２００μｍ程度以下）とすることで、微小流路に導入する流体のうち隣接する流体の、相対的に流路壁面と親媒性の低い流体に対する流路壁面と親媒性の高い流体の送液速度と粘性係数の積がある程度変動しても、各々の流体に他の流体が混入せずに排出流路を通って排出口から排出することができる。
【０１３１】
また、流路修飾による方法のような多数の工程を経ずにエッチングや機械加工、成型などの方法を用いて、微小流路の形状作製と同時に行なうことができるので、流路修飾による方法に比べ流路作製の時間とコストが大幅に削減できる。特に、樹脂やセラミック、ガラスなどの成型により本発明の微小流路構造体を作製する場合に最大限の流路作製の時間とコストの削減効果を得られる。
【０１３２】
さらに、基本的に、上述した効果は本発明の微小流路構造体の微小流路の形状によって実現しているため、流路修飾による方法に比べて、前述した効果の実現の持続、すなわち効果の耐久性が半永久的な微小流路を本発明の微小流路構造体により初めて実現することができる。また、前記微小流路の分岐部に最も近い仕切り壁が、前記微小流路の分岐部と連通していることで、隣接する流体をゆるやかに分離し、各々の流体の混入を抑制することができる。
【０１３３】
また、本発明における微小流路の直線以外の形状の部分において、前記仕切り壁が前記微小流路の直線以外の形状の部分の直前の近傍付近から前記微小流路の直線以外の形状の部分の直後の近傍付近まで連続して形成することで、微小流路の曲線状の部分において曲線状の微小流路の内側の流体が遠心力により外側の流体に向かって出て行くような現象を防止することができ、混入することが無くなる。
【０１３４】
また、微小流路に導入するすべての流体の送液速度が等しい場合、流体進行方向に対する仕切り壁と仕切り壁の間隔を一定間隔より小さくすることで、粘性の等しい隣接した流体が所定の送液速度範囲において、各々の流体に他の流体が混入せずに排出流路を通って排出口から排出することができる。
【０１３５】
また、微小流路に導入する流体のうち隣接する流体の、相対的に流路壁面と親媒性の低い流体に対する流路壁面と親媒性の高い流体の送液速度と粘性係数の積が異なる場合、仕切り壁と仕切り壁の流体進行方向に対する最短の間隔を一定間隔より小さくすることで、微小流路に導入する流体のうち隣接する流体の、相対的に流路壁面と親媒性の低い流体に対する流路壁面と親媒性の高い流体の送液速度と粘性係数の積が約３０〜４０％程度変動しても、各々の流体に他の流体が混入せずに排出流路を通って排出口から排出することができ、化学反応の進行によって各々の流体の粘性が変動しても、粘性の変動が上記の範囲内であれば、各流体が形成する層流の安定な流体境界を維持することができ、各々の流体に他の流体が混入せずに排出流路を通って排出口から排出することができる。
【０１３６】
また、本発明の微小流路構造体は、仕切り壁で仕切られた微小流路の内壁の親和性が、仕切り壁を介在して隣接する微小流路の内壁の親和性と異なっており、このようにすることで、微小流路内壁と親和性のある流体が、微小流路内壁と親和性のない流体を覆うことによる回り込みをさらに効果的に抑えることができ、排出口において、各々の流体を他の流体が混入することなしに分離して排出することがさらに確実になる。
【０１３７】
本発明の微小流路構造体を用いて初めて実現可能となる上記効果により、微小流路内に導入した２種以上の流体を各々の流体境界を安定に維持し、なおかつ、各々の流体を隣接する流体が混入すること無く微小流路から排出することが非常に容易になり、この効果を利用して、さらに以下のような従属効果を得ることができる。
【０１３８】
まず第１の従属効果として、２種以上の流体が微小流路を通過後に、隣接し合う流体が混入せずに各々の流体を十分に分離できるので、混合時間及び／又は化学反応の時間を微小流路の流路長および／又は流体の送液速度によって決まる微小流路の中で隣接する流体の接触時間が微小流路の中だけで決定でき、従って、微小流路内だけで混合及び／又は化学反応を止めることができ、微小流路が有する逐次反応の制御や副反応の抑制などの本来の特徴を生かす化学反応を実現することができる。また、触媒反応などで仕様する触媒の活性を維持したまま回収し、再利用することが可能となる。
【０１３９】
第２の従属効果として、隣接し合う流体が混入せずに各々の流体を十分に分離して排出できるので、溶媒抽出の時間を微小流路の流路長および／又は流体の送液速度によって正確に制御でき、従って、微小流路内で微小流路内だけで溶媒抽出を止めることができる上に、微小流路の中で溶媒抽出した抽出溶媒を微小流路の外に出た後に被抽出溶媒から十分に分離することが可能となる。
【０１４０】
第３の従属効果として、微小流路に２種以上の流体を流した時にできる隣接する流体境界に膜を形成し、微小流路内の隣接する２流体間で前記膜を介して流体内の物質の選択的透過や前記膜への触媒や酵素の担持による触媒反応や酵素反応などを行なう際に、実用的な数ｃｍ〜数十ｃｍの流路長の中に前述した膜を形成したり膜に触媒や酵素を固定化することができる。
【０１４１】
第４の従属効果として、微小流路の中で層流となった隣接する流体を互いに反対の流体進行方向にして送液することが可能となり、化学反応や溶媒抽出の平衡をずらすことなどができる否かを検証するための実験を行なうことが初めて可能となる。また、流路修飾による方法のような多数の工程を経ずにエッチングや機械加工、成型などの方法を用いて、微小流路の形状作製と同時に行なうことができるので、流路修飾による方法に比べ流路作製の時間とコストが大幅に削減できる。特に、樹脂やセラミック、ガラスなどの成型により本発明の微小流路構造体を作製する場合に最大限の流路作製の時間とコストの削減効果を得られる。さらに、基本的に、上述した効果は本発明の微小流路構造体の微小流路の形状によって実現しているため、流路修飾による方法に比べて、前述した効果の実現の持続、すなわち効果の耐久性が半永久的な微小流路を本発明の微小流路構造体により初めて実現することができる。
【０１４２】
第５の従属効果として、微小流路内に流体の流れを維持できる程度に張り出した突起を形成したり、微粒子を混入したりすることで、各流体の形成する層流の流体境界を安定に保ったまま、各流体ごとに攪拌することが可能となり、各流体に含有する物質を各流体内で均一に分散させることができる。
【図面の簡単な説明】
【図１】Ｙ字状微小流路内における層流を示す概念図である。
【図２】ダブルＹ字状微小流路内における層流を示す概念図である。また、比較例２と比較例３に使用した微小流路の概念図である。
【図３】（ａ），（ｂ），（ｃ）はいずれも流体境界の位置が変動する様子を示す概念図である。
【図４】（ａ），（ｂ）はいずれもハーゲン・ポアズイユの式を説明するための概念図である。
【図５】（ａ）は比較例１に使用した微小流路の内部構造の概念図であり、（ｂ）は比較例１に使用した微小流路構造体の構成を示す。
【図６】（ａ）は実施例１、実施例２、実施例３、実施例５、実施例６に使用した微小流路の内部構造の概念図であり、（ｂ）は実施例１、実施例２、実施例３、実施例４、実施例５、実施例６に使用した微小流路構造体の構成を示す。
【図７】本発明における微小流路の曲線状部分における仕切り壁の形状の概略平面図である。
【図８】本発明における微小流路の合流部近傍及び、分岐部近傍における仕切り壁のいくつかの態様の概略平面図であり、（ａ）は仕切り壁が微小流路の合流部及び分岐部から離れている場合、（ｂ）は微小流路の分岐部に最も近い仕切り壁が、微小流路の分岐部と連通している場合、（ｃ）及び（ｄ）は微小流路の合流部近傍において仕切り壁が合流部と連続し、かつ、微小流路の分岐部近傍にて仕切り壁が分岐部と連続している場合を示す。
【図９】本発明における微小流路の中で隣接する流体を互いに反対方向から流した場合の概念図である。
【図１０】本発明の微小流路構造体の流体進行方向の仕切り壁と仕切り壁の間に、無機材料の薄膜を形成する概略フロー図である。
【図１１】（ａ），（ｂ），（ｃ）はいずれも本発明の微小流路構造体の微小流路内に金属膜を配置したときの微小流路の断面図の概略図であり、図１１の上図は上方から見た図である。
【図１２】（ａ）〜（ｄ）はいずれも本発明における微小流路内に形成した流体境界を保持しながら流体を攪拌するための突起のいくつかの態様を示す概略図である。
【図１３】本発明における微小流路を用いて、流体を導入、排出、回収する手段を示した概念図であり、（ａ）は流体を微小流路構造体の外部に設置した送液ポンプにより送液する手段を示す概念図であり、（ｂ）は流体を微小流路構造体の内部に埋め込んだマイクロポンプにより送液する手段を示す概念図である。
【図１４】相間移動触媒を使用した反応系の一例を示す図である。
【図１５】温度依存性相間移動触媒を使用した反応系の概念を示す図である。
【図１６】温度依存性相間移動触媒を使用した反応の例である。
【図１７】温度依存性相間移動触媒に用いる微小流路構造体の概念を示す図である。
【図１８】微小流路構造体内部の微小流路の一部に光照射しエネルギーを供給する微小流路構造体の概略図である。
【図１９】（ａ）〜（ｄ）はいずれも本発明における微小流路構造体に触媒を含有する流体と基質を含有する流体を微小流路の中で層流を形成させて化学操作をおこなういくつかの態様を示す図である。
【図２０】本発明における微小流路の片側の流体に微粒子を混入した例を示す概念図である。
【図２１】（ａ）は実施例４と実施例７に使用した微小流路の内部構造の平面図のＳＥＭ写真を示し、（ｂ）は実施例４と実施例７に使用した微小流路の内部構造の概念図である。
【図２２】（ａ）は実施例８、実施例９、実施例１０に使用した微小流路の内部構造を示す概念図であり、（ｂ）は実施例７、実施例８、実施例９、実施例１０に使用した微小流路構造体の構成を示す。
【符号の説明】
１：水相
２：有機相
３：流体境界
４：分岐部
５：線速度
６：直径
７：水平円管
８：円管端面
９：微小流路の幅
１０：流路長
１１：流体導入口
１２：流体排出口
１３：流体Ａ
１４：流体Ｂ
１５：流体の回り込み
１６：ガイド状
１７：流路深さ
１８：微小流路の底面
１９：微小流路
２０：突起
２１：流路幅
２２：仕切り壁
２３：仕切り壁の厚さ
２４：仕切り壁の高さ
２５：流体進行方向の仕切り壁と仕切り壁の最短間隔
２６：流体進行方向の仕切り壁の最長の長さ
２７：流体進行方向
２８：導入口Ａ
２９：導入口Ｂ
３０：排出口Ｃ
３１：排出口Ｄ
３２：基板
３３：流体幅
３４：カバー体
３５：小穴
３６：ガイド状の厚さ
３７：合流部
３８：導入流路近傍
３９：排出流路近傍
４０：微小流路の中央近傍
４１：微小流路が直線以外の形状の部分の直前及び／又は直後の近傍付近
４２：合流部近傍
４３：分岐部近傍
４４：熱硬化性樹脂
４５：ヒーター
４６：無機材料を含んだ懸濁液
４７：酸あるいはアルカリ
４８：無機材料のポーラスな薄膜
４９：金属膜
５０：微小流路の上面
５１：微小流路の側面
５２：微小流路基板
５３：壁
５４：流体境界の幅
５５：微小流路構造体
５６：送液ポンプ
５７：容器
５８：キャピラリーチューブ
５９：マイクロポンプ
６０：回収流路
６１：リザーバータンク
６２：求核アニオン
６３：アルキルハライド
６４：ニトリル
６５：四級アンモニウム塩
６６：ハロゲンアニオン
６７：触媒Ｄ
６８：触媒相
６９：反応相
７０：反応物質Ａ
７１：反応物質Ｂ
７２：生成物Ｃ
７３：ヒーター
７４：断熱材
７５：光照射
７６：マスク
７７：光照射スポット
７８：触媒を含有する流体
７９：基質を含有する流体
８０：微粒子
８１：微粒子の動き[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a microchannel structure having a microchannel for performing a chemical reaction, droplet generation, analysis, etc., in which a fluid introduced into the microchannel is mixed, and a chemical reaction and a solvent extraction, separation, and catalyst recovery of a product are performed. The present invention relates to a microchannel structure suitable for performing the above-described processes and a method of chemically operating a fluid using the microchannel structure.
[0002]
[Prior art]
In recent years, a fluid has been introduced into a microchannel by using a microchannel structure having a microchannel with a length of about several cm, a width and a depth of sub-micrometer to several hundred μm on a glass substrate of several cm square in recent years. Attention has been paid to research on performing a chemical reaction by doing. In such a microchannel, a short molecular diffusion distance in a minute space and rapid molecular diffusion due to the effect of a large specific interface area enable efficient chemical reaction without a special stirring operation. In addition, it has been suggested that a target compound generated by a chemical reaction is rapidly extracted and separated from a reaction phase to an extraction phase by a solvent, thereby suppressing a subsequent side reaction (for example, see Non-Patent Document 1). Here, the micro channel generally means a channel having a width of 50 to 300 μm and a depth of 10 to 100 μm.
[0003]
In the above example, as shown in FIG. 1, an aqueous phase (1) in which raw materials are dissolved and an organic phase (2) are introduced into a Y-shaped microchannel, and an organic phase formed at a Y-shaped junction is formed. A chemical reaction occurs at the fluid boundary (3) between the and the aqueous phase. In general, in most cases, the Reynolds number is smaller than 1 in a micro-scale flow path, and unless the flow velocity is set to be very high, a laminar flow state as shown in FIG. 1 is obtained. In addition, since the diffusion time of a molecule is proportional to the square of the width (9) of the microchannel, the smaller the width (9) of the microchannel, the more the reaction solution is not actively mixed, and the more the mixture is mixed by diffusion of the molecule. And chemical reaction and solvent extraction are likely to occur. The fluid boundary is sometimes called a laminar interface.
[0004]
In addition, as shown in FIG. 2, it is generally said that the water phase and the organic phase can be separated by setting the fluid discharge port (12) of the microchannel in a Y-shape. The complete separation and discharge of the fluid introduced at the fluid outlet in this manner requires complete removal of the chemical reaction and solvent extraction caused by the contact of the fluid in the microchannel at the branch (4) of the microchannel. This is a very important function in stopping the operation at once or reusing the fluid once introduced into the microchannel.
[0005]
However, in practice, the position of the fluid boundary is unstable and fluctuates. The first factor is that, as shown in FIGS. 3A and 3B, the position of the fluid boundary fluctuates due to a temporal fluctuation of a liquid sending speed caused by a pump for sending a fluid or the like. This phenomenon will be described using a Hagen-Poiseuille equation, which is a theoretical equation representing a pressure loss based on internal friction of a fluid in a laminar flow in a circular pipe. As shown in FIG. 4 (a), when a fluid forms a laminar flow at a linear velocity u [m / s] (5) in a horizontal pipe (7) having a diameter d [m] (6). , The pressure loss ΔP [Pa], which is the difference between the pressures P1 and P2 acting on both the pipe end faces (8),
ΔP = P2-P1 = 32 μLu / d²      (Equation 1)
Becomes This is called the Hagen-Poiseuille equation. Here, μ [Pa · s] is a viscosity coefficient, and L [m] is a flow path length (10). Now, as shown in FIG. 4 (b), when two fluids A (13) and B (14) are flowing in a micro channel in a laminar flow to form a fluid boundary, ( Equation 1) holds, and the pressure loss ΔP between the fluid A and the fluid B_AAnd ΔP_BAre represented by (Equation 2) and (Equation 3), respectively.
[0006]
ΔP_A= 32μ_ALu_A/ D_A ²      (Equation 2)
ΔP_B= 32μ_BLu_B/ D_B ²      (Equation 3)
Where μ_A, U_A, D_AAre the viscosity coefficient of fluid A, the linear velocity (5), and the fluid width (33), respectively._B, U_B, D_BAre the viscosity coefficient, the linear velocity, and the fluid width of the fluid B, respectively. Here, since the fluid A and the fluid B flow in the same microchannel having a channel width D [m] (22), ΔP_AAnd ΔP_BAre balanced and (Equation 4) holds.
[0007]
μ_Au_A/ D_A ²= Μ_Bu_B/ D_B ²      (Equation 4)
Further, the relationship between the liquid sending speed v [μL / min] and the linear velocity u [m / s] is expressed by a cross section perpendicular to the direction of the fluid flow, S [m²]
u = 1.67 × 10^-11・ V / S (Equation 5)
Substituting this relationship into (Equation 4) gives
μ_Av_A/ S_Ad_A ²= Μ_Bv_B/ S_Bd_B ²      (Equation 6)
And. Where v_A, V_BAre the feed rates of fluid A and fluid B, respectively._A, S_BIs the cross-sectional area perpendicular to the direction of flow of fluid A and fluid B, respectively. Further, the sectional area S [m²] Is proportional to the square of the fluid width d [m].
μ_Av_A/ D_A ⁴= Μ_Bv_B/ D_B ⁴      (Equation 7)
Holds, and the fluid A and the fluid B flow in the same microchannel having a channel width D [m].
D = d_A+ D_B      (Equation 8)
Holds.
[0008]
Here, it is assumed that the viscosities of the fluid A and the fluid B do not change. Now, when the liquid sending speed of the fluid A changes and becomes large, v_ABecomes large and d_ABecomes large, and an attempt is made to maintain the balance of (Equation 7). d_ABecomes larger, the flow path width D is constant, so d_BBecomes smaller and v_BAnd the balance of (Equation 7) is maintained. Therefore, the position of the fluid boundary fluctuates due to a temporal variation of the liquid sending speed caused by a pump for sending the fluid or the like. In the above example, it is assumed that the viscosity of the fluid A and the fluid B does not change. However, when the viscosity of the fluid A and the fluid B changes according to the progress of the chemical reaction or the solvent extraction, the equation (7) In order to keep the balance, d_A, D_BChanges, and the position of the fluid boundary fluctuates.
[0009]
The second factor in which the position of the fluid boundary is unstable and fluctuates is that, as shown in FIG. 3C, the fluid wraps around (15) due to the difference in affinity between the inner wall of the microchannel and the fluid to be sent. It is in. For example, when an aqueous phase (1) and an organic phase (2) are fed into a glass microchannel as shown in FIG. 3B, the aqueous phase has a higher affinity for glass than the organic phase. Due to the high height, as shown in FIG. 3B, the aqueous phase gradually flows around from the inner wall of the flow channel so as to surround the outside of the organic phase. When branching at the branch of the microchannel in this state, the aqueous phase is mixed with the organic phase and the organic phase is mixed with the aqueous phase.
[0010]
Due to the above factors, it is not easy to stably form the fluid boundary (3) as shown in FIG. In particular, if the liquid is sent at a low flow rate in order to lengthen the residence time of the fluid in the microchannel for the purpose of lengthening the time for the chemical reaction and the time for extracting the solvent in the microchannel, the fluctuation of the liquid sending speed And spillage of fluid is likely to occur.
[0011]
In order to stabilize the fluid boundary between the fluids introduced into the microchannel, for example, as shown in FIG. 5A, about 20% of the channel depth (17) is formed on the bottom surface (18) of the microchannel. A microchannel structure having a guide shape (16) of a degree or less has been proposed (for example, see Patent Documents 1 and 2). By forming such a guide shape on the bottom surface of the microchannel, the fluctuation of the position of the fluid boundary (3) shown in FIG. 3A can be suppressed to some extent, but the microchannel shown in FIG. Fluid wrap (15) due to the difference in affinity between the inner wall and the fluid to be fed cannot be sufficiently suppressed. For this reason, it is very difficult to discharge each fluid from the fluid discharge port of the microchannel without mixing other fluids even if a microchannel formed with a guide shape on the bottom surface of the microchannel is used. there were.
[0012]
That is, the laminar flow cannot be maintained by changing the position of the fluid boundary due to the temporal fluctuation of the liquid sending speed caused by a pump for sending the fluid or the like, and the fluid to be sent to the inner wall of the micro flow path Owing to the difference in affinity between the fluid and the other fluids mixed into each fluid discharged from the fluid discharge port of the microchannel, It is impossible to completely stop the resulting chemical reaction or solvent extraction at the branch of the microchannel, and in order to reuse the fluid once introduced into the microchannel, each fluid discharged from the outlet is used. It is necessary to separate the fluid mixed into the fluid, and it is not easy to reuse the fluid.
[0013]
Also, as described above, after two or more types of fluids have passed through the microchannel, adjacent fluids could not be sufficiently separated without mixing of adjacent fluids, so that the mixing time and / or the time of the chemical reaction were reduced. The contact time between adjacent fluids in the microchannel determined by the channel length of the microchannel and / or the liquid sending speed cannot be determined only in the microchannel. Therefore, the mixing and / or chemical reaction cannot be stopped only in the microchannel, and the mixing and / or chemical reaction proceeds even after the fluid exits the microchannel, for example, the generation of by-products due to the sequential reaction Proceeds after exiting the microchannel, resulting in a reduction in the reaction yield and the original nature of the microchannel, such as control of sequential reactions and suppression of side reactions (for example, see Non-Patent Document 1). I couldn't take advantage of the features.
[0014]
Also, as described above, after two or more types of fluids have passed through the microchannel, the respective fluids could not be sufficiently separated without admixture of adjacent fluids. The contact time of adjacent fluids in the microchannel determined by the channel length of the microchannel and / or the liquid sending speed can be determined only in the microchannel. Did not. Therefore, the solvent extraction cannot be stopped only in the microchannel in the microchannel, and the solvent extraction proceeds even after the fluid has exited the microchannel. Thus, the solvent extraction could not be performed while maintaining the volume ratio between the extraction solvent and the solvent to be extracted. In addition, the extraction solvent extracted by the solvent in the microchannel cannot be sufficiently separated from the solvent to be extracted after leaving the extraction channel. Here, the solvent extraction means to extract the substance to be extracted from the solvent to be extracted into the extraction solvent as described above. In the present specification, the solvent extraction is performed by evaporating a liquid phase composed of a liquid and forming an adjacent gas. Including in the gas phase.
[0015]
Further, recently, a film is formed on an adjacent fluid boundary formed when two or more kinds of fluids are flown in the microchannel, and a substance in the fluid is selected between the two adjacent fluids in the microchannel via the membrane. There have been attempts to perform permeation (for example, see Non-Patent Document 2), catalytic reaction or enzymatic reaction by carrying a catalyst or enzyme on the membrane (for example, see Non-Patent Document 3). However, it is difficult to form a membrane along the direction of fluid flow unless the length of the microchannel is a short channel length of about 1 mm or less, and the membrane is continuous with the long microchannel along the direction of fluid flow. It was difficult to form a film.
[0016]
Also, recently, attempts have been made to send adjacent fluids that have become laminar flows in the microchannel in opposite fluid traveling directions, or to contact adjacent fluids by crossing them at an arbitrary angle. (For example, see Non-Patent Document 4). These are expected to be able to shift the equilibrium of the chemical reaction and the solvent extraction by keeping the traveling directions of the adjacent fluids in the same direction. In Non-Patent Document 4, one side half of the inner wall of a glass microchannel which is originally hydrophilic is modified to be hydrophobic with trichlorooctadecylsilane, which is a generally known hydrophobic modifier, so that 1 mm An example of an experiment with a length of about the following is shown. As described above, it is difficult to send the adjacent fluids that have become laminar flows in the microchannel in opposite fluid traveling directions or to make the adjacent fluids cross and contact at an arbitrary angle, and it is particularly difficult. It is very difficult to realize a microchannel over a long distance, and it has not even been possible to carry out an experiment to verify whether the above-mentioned operation can shift the equilibrium of a chemical reaction or solvent extraction.
[0017]
Also, performing the channel modification as in Non-Patent Document 4 requires a plurality of steps such as a pre-cleaning step, a modifier supplying step, a modifier stabilizing step, and a post-cleaning step. In addition to the cost, the durability of the modifier is only about 1 to 4 weeks, and there is no microchannel for semipermanently realizing the above-described liquid sending.
[0018]
In general, in the case of FIG. 1, the progress of the chemical reaction mainly proceeds at the fluid boundary (3) (for example, see Non-Patent Document 5). However, sufficient effects such as efficient chemical reaction, quick solvent extraction, separation, and suppression of side reactions, which are characteristics of the above-described chemical reaction in a small space, could not be obtained sufficiently. As described above, if the width (9) of the microchannel is narrowed, the diffusion time of the molecule can be further shortened, and the accumulation of products at the fluid boundary can be suppressed. Is large, and it becomes difficult to feed the solution itself, which is not practical. Also, if the fluid boundary is actively broken and mixed, the product can be distributed uniformly in the flow path, which may improve the efficiency of the chemical reaction. The product could not be easily separated from the reaction phase, and the effects of solvent extraction and separation and the effect of suppressing side reactions could not be sufficiently obtained.
[0019]
On the other hand, for example, as a conventional chemical reaction using a catalyst, a heterogeneous catalytic reaction in which a reactant and a catalyst are in different phases, and a catalytic reaction proceeds when both the reactant and the catalyst are present in the same phase. There is a homogeneous catalytic reaction. In the heterogeneous catalytic reaction, a solid catalyst is often used as a catalyst. For example, a liquid or a gas containing a reactant is continuously passed through the solid catalyst to advance a chemical reaction.
[0020]
Therefore, there is no need for the operation of separating the catalyst and the product, and there is an advantage that mass production is possible.However, since the catalytic action occurs only on the surface of the solid catalyst, the reaction efficiency is compared with the homogeneous catalytic reaction. There are drawbacks such as poor quality and poor selectivity to the product.
[0021]
On the other hand, in a homogeneous catalytic reaction, the catalyst and the raw materials are generally mixed and suspended in a reaction vessel to cause a chemical reaction, so that the specific interface area of the catalyst with respect to the reactant becomes large, resulting in a heterogeneous catalytic reaction. Compared to the reaction, the reaction efficiency and the selectivity to the product are good, but it is necessary to separate and recover the solvent, the catalyst and the product by means of distillation or filtration after the reaction. However, since the catalyst is generally dissolved in a solvent, it is very difficult to separate and reuse an expensive catalyst.
[0022]
Conventionally, as a means of complementing the advantages and disadvantages of the above heterogeneous catalytic reaction and homogeneous catalytic reaction, the catalyst is supported on a carrier such as a polymer or oxide to make it heterogeneous. After the completion, a method of separating the supported carrier together has been performed. However, by supporting the catalyst on a carrier such as a polymer or an oxide, the expensive catalyst becomes more expensive, becomes thermally or chemically unstable, or has the advantage of the catalyst, rapid heat removal. And the reaction efficiency is deteriorated.
[0023]
Furthermore, a chemical reaction is generally performed in which an enzyme (biocatalyst), which is a type of catalyst contained in the aqueous phase, and a substrate contained in the organic phase are mixed, and the enzyme hydrolyzes or esterifies the substrate. ing. In this case, if the aqueous phase and the organic phase are mixed by mechanical stirring or the like in order to increase the reaction efficiency, the structure of the enzyme is mechanically broken and the activity is lost. There is a problem that the properties change and the activity is lost due to the contact with the metal.
[0024]
[Patent Document 1]
JP-A-2002-1102
[Patent Document 2]
WO 96/12541
[Non-patent document 1]
H. Hisamoto et. al. (H. Hisamoto et al.) "Fast and high conversion phase-transfer synthesis explosing the liquid-liquid interface formed in a microchannel chip.", Chem. Commun. , 2001, pp.2662-2663.
[Non-patent document 2]
Yuki Shimizu et al., “Creation of Polymer Diaphragm in Microchannel”, Proceedings of the 3rd Technical Meeting on Chemistry and Microsystems, 2001, p.11
[Non-Patent Document 3]
Yuki Shimizu et al., "Creation and Application of Polymeric Film Structure in Microchannel", Proceedings of the 5th Chemistry and Microsystems Workshop, 2002, p.37
[Non-patent document 4]
Akihide Hihara et al., "Development of Multi-Layer Flow Forming at Three-Dimensional Intersection", Proc.
[Non-Patent Document 5]
Fujii, "Integrated Microreactor Chip", Nagare, Volume 20, 2001, pp. 99-105,
[0025]
[Problems to be solved by the invention]
The object of the present invention has been proposed in view of such a conventional situation. Two or more types of fluids are introduced into a microchannel, and each adjacent fluid forms a stable fluid boundary in the microchannel. Then, to provide a micro-channel structure that can be separately discharged from a predetermined outlet without mixing of adjacent laminar flows, and by using the micro-channel structure, only by sending a fluid Providing a method for performing a chemical operation of a fluid that performs more efficient mixing, chemical reaction, solvent extraction, separation, catalyst recovery, etc. by being brought into contact with each other in the flow direction of the fluid in the microchannel, An object of the present invention is to provide a microchannel structure capable of being recovered and reused without losing the activity of the catalyst in the course of a chemical reaction in a multi-layered catalytic reaction, and a chemical operation method using the same.
[0026]
[Means for Solving the Problems]
Means for Solving the Problems The present invention solves the above-mentioned problem by flowing two or more introduction ports for introducing a fluid, an introduction flow path communicating with the two or more introduction ports, and a junction where the introduction flow paths merge, and flowing the introduced fluid. Channel structure, and two or more discharge channels having a branch portion communicating with the micro channel and separating a predetermined fluid, and a discharge port communicating with them. In addition, a microchannel structure is proposed in which a plurality of partition walls are provided in a microchannel along a boundary formed by two or more types of introduced fluids so that the introduced fluids do not mix with each other. Further, by using such a microchannel structure and performing chemical operations such as mixing, chemical reaction, solvent, separation, and catalyst recovery, the above-described problems of the prior art can be solved. The invention has been completed. Note that the expression “boundary formed by two or more types of fluids” is used synonymously with the expression “fluid boundary” in the present invention.
[0027]
Hereinafter, the present invention will be described in detail.
[0028]
As described above, in general, when the liquid is sent at a low flow rate in order to lengthen the residence time of the fluid in the microchannel for the purpose of lengthening the time of the chemical reaction or the time of solvent extraction in the microchannel. Fluctuation of the liquid sending speed and spillage of the fluid are likely to occur. Conversely, this means that the shorter the length of the microchannel, the less the flow of the fluid due to the fluctuation of the position of the fluid boundary and the difference in the affinity between the inner wall of the microchannel and the fluid to be fed. This is presumably because the contact distance and the contact time of the fluid are short, the fluctuation of the position of the fluid boundary is small, and the wraparound of the fluid due to the difference in affinity between the inner wall of the microchannel and the fluid to be supplied is small. .
[0029]
Therefore, the fluids are brought into contact in the microchannel, and the position of the fluid boundary of each fluid is small, and the wraparound of the fluid due to the difference in affinity between the inner wall of the microchannel and the fluid to be sent is small. The fluid is kept stable over the entire microchannel by repeating the operation of contact and separation multiple times, such as contacting each fluid again afterwards, and the fluid to be sent to the inner wall of the channel. It is conceivable that the fluid can be prevented from flowing around due to a difference in affinity with the fluid, and can be separated without mixing other fluids into each fluid at the branch portion of the microchannel.
[0030]
Therefore, the microchannel structure of the present invention, the two or more inlets for introducing a fluid and an introduction channel that communicates with them, and a fluid that communicates and is introduced with a junction where the introduction channels merge. A microchannel structure having a microchannel for flowing, two or more discharge channels having a branch portion communicating with the microchannel and separating a predetermined fluid, and a discharge port communicating with them. In the microchannel, the introduced fluids are not mixed with each other at a position apart from the junction and the branch along the fluid boundary formed by the introduced two or more kinds of fluids. Characterized in that a plurality of partition walls having a height substantially equal to the depth of the microchannel are provided.
[0031]
Here, the fluid means a liquid or a gas. Further, that the introduced fluids do not mix with each other means that there is substantially no mixing of other fluids with each fluid, and more specifically, that the mixing ratio is less than 10%. .
[0032]
In addition, the above-mentioned minute flow path is a flow path generally having a width of 500 μm or less and a depth of 300 μm or less. Further, the width and depth of the introduction flow channel and the discharge flow channel are not particularly limited, but may be the same width and depth as the minute flow channel. The size of the inlet and the outlet is not particularly limited, but may be generally about 0.1 mm to several mm in diameter.
[0033]
Further, the vicinity of the junction of the introduction flow path means 10 μm or more and 500 μm or less from the junction, and the vicinity of the branch of the discharge flow path means 10 μm or more and 500 μm or less from the branch.
The microchannel structure of the present invention is a microchannel structure in which two or more fluids in which a target reactant or a substance to be extracted is dissolved in a medium such as water or an organic solvent are formed in the microchannel structure. Introduced into the flow channel, the introduced fluid is sent while maintaining a laminar flow in the micro flow channel space, so that the fluids come into contact with each other, mixing by molecular diffusion, chemical reaction, solvent extraction, and Even when the liquid is sent from the minute flow path to the discharge flow path, each of the introduced fluids is configured to be sent to a predetermined discharge flow path.
[0034]
For this reason, the microchannel structure of the present invention is introduced and communicated with two or more inlets for introducing a fluid and an inlet channel communicating therewith, and a junction where the inlet channels merge. Micro flow path for flowing the fluid, and two or more discharge flow paths having a branch portion communicating with the micro flow path and separating a predetermined fluid, and a discharge port communicating with them. A channel structure, wherein the microchannel is provided with a plurality of partition walls along a boundary formed by two or more types of introduced fluids so that the introduced fluids do not mix with each other. It is preferable that the partition wall is discontinuous with respect to the traveling direction of the fluid. If a wall for partitioning adjacent fluids is provided in this manner, the introduced fluids do not mix with each other, and further, by making the partition walls discontinuous, the adjacent fluids come into contact with each other to form molecules. Mixing by diffusion, chemical reaction, solvent extraction, separation, etc. can be performed efficiently.
[0035]
The partition wall is provided so that the introduced fluids do not mix with each other in the microchannel. The height of the partition wall is substantially equal to the depth of the microchannel, or the fluid is separated from the partition wall. It is sufficient if the height is such that it cannot move to the phase of another fluid beyond the flow path, and preferably the height is equal to the depth of the microchannel.
[0036]
With such a structure, the fluctuation of the position of the fluid boundary due to the temporal fluctuation of the liquid sending speed caused by a pump for sending the fluid or the like is suppressed, and the fluid to be sent to the inner wall of the microchannel is Can be prevented from flowing around due to a difference in affinity between the fluids, and each fluid can be discharged from the fluid discharge port of the microchannel without mixing other fluids.
[0037]
Hereinafter, the microchannel structure of the present invention will be described in more detail with reference to the drawings.
[0038]
In the present invention, the position of the junction between the partition wall and the introduction flow path, and the positional relationship between the partition wall and the branching part of the discharge flow path are as shown in FIG. In a basic mode, the partition 22) is formed at a position away from the junction (37) and the branch (4). However, as shown in FIG. Preferably, the wall is in communication with the branch of the microchannel. This makes it possible to gently separate adjacent fluids and suppress the mixing of each fluid. In addition, the partition wall has one or more non-existent portions except for the vicinity of the junction of the introduction flow channel (42) and the vicinity of the branch portion of the discharge flow channel (43), that is, as shown in FIG. In addition, the distance between the partition wall and the partition wall in the direction of fluid flow is shorter than the distance between the partition wall and the partition wall in the direction of flow of the fluid between portions other than the vicinity of the introduction flow path and / or the vicinity of the discharge flow path in the micro flow path. As shown in FIG. 8D, a partition wall continuous from the junction and a partition wall continuous from the branch are formed in the vicinity of the junction and the branch. It is further preferable that a partition wall and a partition wall continuous from the branch portion and the branch portion are continuously formed in the vicinity of the junction in the direction of fluid flow. Thus, by providing the partition wall near the junction, it is possible to suppress the mixing of each fluid due to the collision of the adjacent fluid, and by providing the partition wall near the branch portion, the adjacent fluid can be rapidly reduced. Mixing of each fluid due to the division can be suppressed. In addition, the fact that there is one or more places where the partition wall does not exist in the fluid traveling direction except for the vicinity of the branch part of the discharge channel means that the partition wall is formed at least one or more in the fluid traveling direction. Means
[0039]
In addition, it can be performed simultaneously with the formation of the shape of the micro flow channel by using a method such as etching, machining, molding, etc. without going through a number of steps such as a method by flow channel modification. Compared with this, the time and cost for manufacturing the flow channel can be significantly reduced. In particular, when the microchannel structure of the present invention is manufactured by molding a resin, ceramic, glass, or the like, the maximum time and cost reduction effect of manufacturing the channel can be obtained. Furthermore, basically, since the above-mentioned effects are realized by the shape of the microchannel of the microchannel structure of the present invention, the continuation of the above-mentioned effects can be realized, that is, the effect, Can be realized for the first time by the microchannel structure of the present invention.
[0040]
A plurality of partition walls may be provided so that the longest lengths of the partition walls in the fluid traveling direction are all the same, but partition walls having different lengths may be used. Also, the spacing between the partition walls in the fluid traveling direction may be the same or different.
[0041]
In addition, as shown in FIG. 7, in the portion of the minute flow path (19) of the present invention other than the straight line, the partition wall (22) is in the vicinity of immediately before the portion of the minute flow path other than the straight line ( It is desirable to continue from 41) to the vicinity (41) immediately after the portion of the minute flow path other than the straight line. The vicinity in this case is not particularly limited, but preferably means within 5000 μm. For example, when a fluid is caused to flow in a curved microchannel, a centrifugal force acts on the curved portion of the microchannel, whereby the fluid inside the curved microchannel is pushed out toward the outer fluid. As a result, the fluid inside and outside of the curved microchannel may be mixed. However, in a portion of the minute flow path having a shape other than the straight line, the partition wall is located near a portion immediately before the portion having a shape other than the straight line of the minute flow channel to a portion immediately after the portion having a shape other than the straight line of the minute flow channel. By forming a partition wall continuously to the vicinity, such a phenomenon can be prevented, and the fluid inside and outside the curved minute flow path is mixed in the curved part of the minute flow path. Disappears.
[0042]
Based on the above idea, the present invention, as shown in FIG. 6 (a), places a fluid flow direction (27) at or near two or more types of fluid boundaries (3) inside a microchannel (19). ), A plurality of partition walls (22) that are discontinuous with respect to the direction of fluid flow having a height equal to or less than the microchannel depth (17) are formed, so that the fluid is brought into contact with a place where there is no partition wall, Further, the fluid can be separated at the place where the partition wall exists, and if a plurality of discontinuous partition walls are formed in the direction of the fluid flow of the microchannel, the contact and separation of the fluid are repeated. In this way, fluctuations in the position of the fluid boundary due to temporal fluctuations in the liquid sending speed caused by a pump or the like that sends the fluid are suppressed, and the affinity between the inner wall of the microchannel and the fluid to be sent is reduced. It is possible to prevent the fluid wraparound (15) (shown at 15 in FIG. 3 (c)) due to the difference in gender, and to prevent each fluid from being mixed with another fluid from the fluid outlet of the microchannel. Can be discharged. Therefore, mixing, chemical reaction, and solvent extraction due to molecular diffusion caused by contact of the fluid in the microchannel can be completely stopped at the fluid outlet, or the fluid once introduced into the microchannel can be reused. It becomes.
[0043]
Here, the position of the partition wall in the width direction of the microchannel is not particularly limited, and can be changed according to the properties of the solution such as the flow rate, flow rate, and viscosity of the solution. Naturally, even if the viscosity of the adjacent fluid changes due to mixing, chemical reaction, or solvent extraction, and the position of the fluid boundary gradually changes according to the fluid traveling direction, it is necessary to calculate and predict the change in viscosity in advance by simulation or the like. The partition wall may be provided along the predicted fluid boundary. Conversely, when the partition wall is formed near the center with respect to the width direction of the flow path and a fluid having a different viscosity flows, the fluid is supplied at a liquid supply speed inversely proportional to the viscosity of the fluid from (Equation 7). If liquid is applied, a fluid boundary can be formed near the partition wall. Further, the thickness (23) of the partition wall is not particularly limited, but is preferably about 3 to 10% of the flow path width so as not to hinder the liquid sending itself. The height (24) of the partition wall is not particularly limited as long as it is equal to or less than the flow channel depth, but it is most preferable that the height of the partition wall is equal to the flow channel depth (17). The minimum value of the shortest distance (25) between the partition walls in the fluid traveling direction is not particularly limited if the partition wall (22) is discontinuous, but if the partition wall (22) is too short, the contact time of the fluid is short. Therefore, it is not possible to perform a chemical reaction or solvent extraction, so that the thickness is preferably about 50 μm or more.
[0044]
Further, in the microchannel structure of the present invention, when the liquid feeding speeds of all the fluids introduced into the microchannel are equal, the shortest distance between the partition wall and the partition wall with respect to the fluid traveling direction is preferably less than 800 μm, more preferably. Is desirably 400 μm or less. As will be described in an embodiment described later, when the shortest distance between the partition walls in the fluid traveling direction is 800 μm, each fluid discharged from the discharge port is discharged through the discharge flow path without mixing other fluids. It may not be possible to discharge from the outlet. This is because, when the shortest distance between the partition walls in the fluid traveling direction exceeds 800 μm, there is a temporal variation in the liquid supply speed caused by a pump for supplying the fluid or the like, and the difference between the fluid to be transmitted and the inner wall of the micro channel. This is because the position of the fluid boundary becomes unstable due to the flow of the fluid due to a difference in affinity. From the embodiment shown in the present invention, the partition wall and the partition wall in the fluid traveling direction can be discharged from the discharge port through the discharge flow path without mixing other fluids into each fluid discharged from the discharge port. Is preferably 400 μm or less.
[0045]
This condition is based on the assumption that the partition wall in the width direction of the flow path has the same viscosity coefficient of the fluid at the center, but when the viscosity coefficients of the adjacent fluids are different, (Equation 7) and (Equation 7) From equation 8), d for the case where the liquid sending speed is equal_AOr d_BIs calculated and a partition wall is formed at that position, the same relational expression holds.
[0046]
Further, the microchannel structure of the present invention, when the product of the liquid feeding speed and the viscosity coefficient of the adjacent fluid among the fluids introduced into the microchannel is different, the shortest distance between the partition wall and the partition wall with respect to the fluid traveling direction. Is preferably less than 400 μm, more preferably 200 μm or less, so that even if the product of the liquid sending speed and the viscosity coefficient of the fluid introduced into the microchannel fluctuates in the range of 0.625 or more and 1.25 or less, The fluid can be discharged from a predetermined discharge port through the discharge flow path without being mixed with another fluid.
[0047]
In other words, when the viscosity coefficients of the fluids are the same, the flow rate of the fluid having a relatively high affinity with the flow path wall surface is assumed to be 10 μL / min when the flow velocity of the fluid having a relatively low affinity with the flow path wall face is 10 μL / min. Can vary from 6.25 to 12.5 μL / min, and can be discharged from the discharge port through the discharge flow path without mixing other fluids with each fluid. Alternatively, when the fluid sending speeds are equal, if the viscosity coefficient of the fluid having a relatively low affinity for the flow path wall surface is set to 1 mPa · s, the lower limit of the viscosity of the fluid having a relatively high affinity for the flow path wall surface is obtained. Even if the value fluctuates in the range of 0.625 or more and 1.25 mPa · s or less, each fluid can be discharged from the discharge port through the discharge channel without mixing other fluids. This condition is based on the assumption that the partition wall in the width direction of the flow path has the same viscosity coefficient of the fluid at the center, but when the viscosity coefficients of the adjacent fluids are different, (Equation 7) and (Equation 7) From equation 8), d for the case where the liquid sending speed is equal_AOr d_BIs calculated and a partition wall is formed at that position, the same relational expression holds.
[0048]
In the linear portion of the microchannel according to the present invention, the longest length (26) of the partition wall in the fluid traveling direction shown in FIG. 6A is the shortest distance between the partition wall and the partition wall in the fluid traveling direction. (25) More preferably, That is, since the longest length of the partition wall in the fluid traveling direction is shorter than the shortest interval of the partition wall in the fluid traveling direction, the contact time of the fluid in the length of the microchannel, that is, the time of the chemical reaction And a longer time for solvent extraction. In addition, the longest length of the partition wall in the fluid traveling direction is 50 μm or more, which stably forms a fluid boundary, and separates each fluid at the discharge port without mixing other fluids. More preferred to discharge.
[0049]
Further, as shown in FIGS. 8A to 8D, the partition wall (22) and the partition wall (39) in the vicinity of the introduction channel (38) and / or the vicinity of the discharge channel (39) in the minute channel (19). It is preferable that the shortest interval (25) in the fluid traveling direction is shorter than the shortest interval in the fluid traveling direction between the partition wall near the center (40) of the microchannel. Here, the vicinity of the introduction channel means within 5000 μm from the junction (37), and the vicinity of the discharge channel means within 5000 μm from the branch portion (4). By doing so, the fluid boundary can be more stabilized in the vicinity of the introduction flow path and / or in the vicinity of the discharge flow path, so that each fluid is mixed with another fluid in the junction and the branch. It is more reliable to separate and discharge the waste.
[0050]
Further, in the microchannel structure of the present invention, the affinity of the inner wall of the microchannel divided by the partition wall is different from the affinity of the inner wall of the adjacent microchannel via the partition wall. This is a characteristic microchannel structure. By doing so, it is possible to further effectively prevent the fluid having an affinity for the inner wall of the microchannel from wrapping around by covering the fluid having no affinity for the inner wall of the microchannel. It is further assured that the fluids are separated and discharged without contamination of other fluids.
[0051]
Further, the microchannel structure according to the present invention is characterized in that a plurality of protrusions protruding to the extent that a fluid flow can be maintained are formed on the inner wall of the microchannel divided by the discontinuous partition wall. It is a microchannel structure. By forming such projections, the fluid can contact the projections to change the direction of the flow of the fluid, so that a stirring effect can be obtained. By forming such a structure in a micro channel, a power supply or the like is not required as compared with a stirring means or the like utilizing mechanical vibration by a known piezoelectric element or the like, and each fluid is separated by a discontinuous partition wall. Since the fluid boundary is agitated in the fluid while being kept stable, the substances contained in the fluid are more rapidly and uniformly dispersed in each fluid, and sufficient chemical reaction and extraction of the solvent can be rapidly performed. .
[0052]
Further, since each fluid stably holds the fluid boundary by the discontinuous partition wall, each fluid can be easily separated at the branch portion of the microchannel. FIGS. 12A to 12D show conceptual diagrams of some forms of the protrusions formed in the microchannel. FIG. 12 shows an example in which two fluids are introduced. In addition, the present invention is not limited to only these examples, and it goes without saying that the present invention can be arbitrarily changed without departing from the gist of the invention.
[0053]
FIG. 12A shows an example in which a plurality of protrusions (20) are formed on the bottom surface (18) of the microchannel on one half. The protrusions agitate one or more fluids within each fluid while maintaining fluid boundaries, projecting to the extent that fluid flow can be maintained, and having a height and width that do not substantially block microchannels. There are no particular restrictions if you do. The number of the projections is not limited as long as the number of the projections can be maintained without substantially blocking the microchannel. There is no particular limitation on the arrangement of the protrusions, and they may be arranged regularly or randomly. In FIG. 12A, the protrusions are formed only on the bottom surface of the microchannel on one half, but may be formed on the entire bottom surface of the microchannel, or the microchannel may be formed from the upper surface of the microchannel (19). A protrusion may be formed toward the inside of the road, and both may be provided together. With the bottom of the microchannel. When a projection is formed on the upper surface (50) of the microchannel, the position of the projection is the same on the bottom surface of the microchannel and the upper surface of the microchannel unless the projection substantially blocks the microchannel. May be different.
[0054]
FIG. 12B shows an example in which a plurality of protrusions (20) are formed from the side surface (51) of the microchannel on one side. The projections agitate one or more fluids within each fluid while maintaining fluid boundaries, projecting to the extent that fluid flow can be maintained, and having a height and width that do not substantially block the microchannel (19). There is no particular limitation as long as it has. The number of the projections is not limited as long as the number of the projections can be maintained without substantially blocking the microchannel. There is no particular limitation on the arrangement of the protrusions, and they may be arranged regularly or randomly. In FIG. 12B, the protrusions are formed only on the side surfaces of the microchannels on one side. However, the protrusions may be formed on the side surfaces of the microchannels on both sides. When the protrusions are formed on the side surfaces of the microchannels on both sides, the positions of the protrusions may be the same or different on the side surfaces on both sides, unless the microchannels are practically closed by the protrusions. .
[0055]
FIGS. 12C and 12D show an example in which a wall (53) having an angle θ with respect to the traveling direction (27) of the fluid is formed on the bottom surface (18) of the microchannel perpendicular to the bottom surface of the microchannel. It is. The width of the wall is set to be equal to the width (54) of each fluid boundary. The height of the wall is not particularly limited as long as it has a height that does not substantially block the microchannel (19). Also, the number of walls is not limited as long as the shape of each wall can be maintained without substantially blocking the microchannel. The way of arranging the walls is not particularly limited, and the walls may be arranged regularly at regular intervals or at random intervals. The angle θ of the wall with respect to the traveling direction of the fluid is not particularly limited. The wall may be formed so as to have symmetrical angles θ with respect to the traveling directions of the two fluids as shown in FIG. As shown in FIG. 12D, the two fluids may be formed at the same angle θ with respect to the traveling direction. Of course, the angles θ of all the walls may be formed differently. In FIGS. 12C and 12D, a wall is formed on the bottom surface (18) of the microchannel on both sides. However, a wall may be formed on the bottom surface of the microchannel on one side, A wall may be formed on the upper surface (51) of the channel, the side surface (50) of one of the micro channels, or the side surface of both micro channels, or both may be formed.
[0056]
When walls are formed on the bottom, top, and side surfaces of the microchannel, the wall positions are different even if the bottom, top, and side surfaces are the same unless the microchannel is effectively closed by the wall. May be.
[0057]
In addition, the microchannel structure of the present invention has two or more inlets for two or more fluids introduced into the microchannel so that the traveling directions of adjacent fluids via the partition wall are opposite to each other. By arranging the introduction flow path communicating with them and two or more discharge ports and the discharge flow path communicating with them, as shown in FIG. Adjacent fluids that have become laminar flows can be sent in opposite fluid traveling directions, and as described above, the affinity of the inner wall of the microchannel divided by the partition wall in the microchannel, If modified so that the affinity of the inner wall of the adjacent microchannel is different from that of the adjacent microchannel via a partition wall, the adjacent fluids that have become laminar in the microchannel with a length of about several centimeters are opposite to each other. The liquid can be sent in the traveling direction. This verifies whether it is possible to shift the equilibrium of the chemical reaction and solvent extraction by sending the adjacent fluids that have become laminar flows in the microchannels in opposite flow directions. Experiments can be performed.
[0058]
Further, the microchannel structure of the present invention can easily form a film having a fine hole between the partition walls in the traveling direction of the fluid and no more than the distance between the partition walls. it can. The material of this film may be a polymer material such as nylon, acrylic, or cellulose, or may be an inorganic material such as silicon oxide, titanium oxide, alumina, or zirconia. it can.
[0059]
As for the formation of a membrane in such a microchannel, an example in which nylon is used to form a fluid boundary in the microchannel as described in Non-Patent Document 2 described above has been reported. Is at most about 1 mm, which is not a practically sufficient flow path length. However, as in the case of the micro flow path structure of the present invention, the distance between the partition walls in the fluid traveling direction is set to 1 mm or less. If a large number of partition walls are formed at intervals of 1 mm or less in a micro channel of several cm to several tens cm, polymers such as nylon, acrylic, cellulose, etc. can be surely provided between all the partition walls. A film of the material can be formed. This is only possible with the microchannel structure of the present invention.
[0060]
Therefore, a membrane of a polymer material such as nylon, acrylic, or cellulose is formed by a known method described in Non-Patent Document 2, and a functional polymer membrane that can be selectively separated in a microchannel is of a practical length. Can be formed in the minute flow path. Also, as described in Non-Patent Document 3 already known, an experiment was conducted in which a biochemical reaction was formed in a microchannel having a practical length by immobilizing an enzyme or the like on a polymer film formed on a fluid boundary in the microchannel. And the like are only possible with the microchannel structure of the present invention.
[0061]
As described above, the material of this film may be an inorganic material such as silicon oxide, titanium oxide, alumina, and zirconia. In order to form such an inorganic material film, for example, as shown in FIG. 10, a two-input two-output microchannel structure of the present invention having two inlets and two outlets in step 1) is used. While being heated to an appropriate temperature, a thermosetting resin (44) is introduced from one inlet and an aqueous phase is introduced from the other inlet, and liquid is formed to form a laminar flow. After gradually heating to cure the thermosetting resin, silicon oxide, titanium oxide, alumina, etc. are added to the aqueous ammonia solution or aqueous sodium hydroxide solution by the so-called sol-gel method from the inlet into which water was previously introduced in step 2). And a suspension (46) in which an inorganic material such as zirconia is suspended is flowed while being heated to an appropriate temperature, and the inorganic material is coated on the inner wall on one side of the microchannel in step 3). Step of suspension of inorganic material ahead An acid or an alkali (47) is flowed from the introduced inlet to remove the thermosetting resin hardened in the other microchannel, thereby oxidizing between the partition walls in step 5). A porous film (48) having a thickness of 1 μm to 5 μm made of an inorganic material such as silicon, titanium oxide, alumina, and zirconia can be formed. By utilizing such a porous thin film of an inorganic material for a catalyst or the like, a catalytic reaction between adjacent fluids can be realized. This is also possible only with the microchannel structure of the present invention.
[0062]
In addition, the microchannel structure of the present invention can be configured as shown in FIG. 11 (a), as shown in FIG. 11 (a), for all the inner walls and / or partition walls, or as shown in FIGS. 11 (b) and 11 (c). A metal film (49) may be partially disposed. As shown in FIG. 11A, the affinity of the inner wall of the flow path is changed, an electric current is supplied to the metal by an existing power supply, or an eddy current is generated in the metal by electromagnetic induction or the like, thereby converting the metal. By heating and heating, the fluid in the microchannel is brought into direct contact with the heated metal, and an efficient heating reaction can be performed. If the metal is a metal of tungsten, platinum, palladium, or ruthenium, it can be used as a catalyst for synthesis or decomposition of ammonia or the like.
When metals are arranged as shown in FIGS. 11B and 11C, an electric field can be generated between the metals arranged in the microchannel by supplying a voltage that gives a potential difference between the metals. . The electric field intensity at this time is, for example, 1 × 10 by applying a potential difference of 10 V between the electrodes when the flow channel depth in FIG. 11C is 10 μm.⁶An electric field of V / m can be generated. This corresponds to the electric field strength when a high voltage of 10 kV is applied between the electrodes of 10 mm. In other words, a strong electric field can be easily generated by using a power supply for several dry cells in the microchannel, and the strong electric field controls the orientation of molecules having polarity, thereby increasing the selectivity of the chemical reaction. It is also possible to increase the control.
[0063]
The formation of the metal film in the minute channel can be performed by a known method such as sputtering, electrolytic plating, electroless plating, vapor deposition, and CVD. The thickness of the metal film is not particularly limited, but is preferably about several nanometers to several tens of micrometers in consideration of the size of the microchannel.
[0064]
Further, the microchannel structure of the present invention is a microchannel structure having a structure including a re-introduction channel for guiding a fluid discharged from an outlet from the outlet to the inlet. Here, the re-introduction channel includes a channel for collecting a reaction product and, if necessary, a channel for discarding a fluid. In this specification, the reintroduction channel, the channel for collecting the reaction product, and the channel for discarding the fluid may be collectively referred to as a discharge channel.
[0065]
As described above, the re-introduction channel is for guiding a fluid containing a raw material of a chemical reaction in the separated fluid, and the re-introduction channel is any one of the above-described inlets or an outlet. It is in communication with both. By using a structure having such a flow path, it is possible to separate a reaction product generated by a chemical reaction and the like, collect a fluid containing a raw material, and use the fluid again for the chemical reaction, thereby achieving an efficient chemical reaction. The reaction can be performed.
[0066]
Further, the re-introduction channel is connected to the pump for sending the fluid, and the at least one introduction channel and the at least one discharge channel are temporarily connected to the fluid to temporarily store the fluid. A reservoir tank for storing the fluid may be further provided.With such a structure, the fluid can be collected and reused in the microchannel substrate, and a very compact chemical reaction device can be provided. can do.
[0067]
With the above-described structure, the fluid that has left the chemical reaction raw material in the fluid that has undergone the chemical reaction can be efficiently introduced into the inlet. In addition, it is possible to easily recover very expensive catalysts, particularly asymmetric catalysts, phase transfer catalysts, biocatalysts (enzymes), etc. without discarding them, and to use the same again.
FIG. 13 shows a means for specifically introducing and recovering a fluid.
[0068]
As one example of the form, as shown in FIG. 13A, a fluid is sent using a liquid sending pump (56) installed outside the micro channel structure (55), and a fluid outlet (12) is provided. May be returned through the capillary tube (58) or the like to the container (57) in which the fluid to be sent by the liquid sending pump is previously stored.
[0069]
As another embodiment, as shown in FIG. 13B, a micropump (59) for sending a liquid to a reservoir tank (61) for storing a fluid in a microchannel structure (55). , And the fluid by the micro pump is sent from the reservoir tank to the fluid inlet (11), and the fluid discharged from the fluid outlet (12) through the micro channel (19) is passed through the micro channel structure. May be returned to the reservoir tank through the recovery flow path (60) provided in the above, and the fluid may be sent again by the micro pump. Here, in FIG. 13B, the micro pump is indicated as MP. The size of the reservoir tank is not particularly limited as long as the reservoir tank has a capacity that does not cause the fluid in the reservoir tank to be depleted even when the fluid is supplied to the entire microchannel. Further, the width and depth of the recovery channel are not particularly limited, but may be the same width and depth as the minute channel.
[0070]
Further, the microchannel structure of the present invention may include means for supplying energy to the fluid flowing through the microchannel, and the means for supplying the energy is a heating device and / or a light irradiation device. This is a characteristic microchannel structure. With such a structure, light can be applied to the microchannel portion by irradiating light with a light irradiation device or heating with a heating device, so that a chemical reaction can be efficiently performed.
[0071]
Further, in the microchannel structure of the present invention, a plurality of microchannels having the characteristics described so far may be integrated on one substrate, or the substrates may be laminated and integrated. Is also good. In this way, chemical operations such as mixing of a large amount of fluid, chemical reaction, solvent extraction, and separation can be performed while utilizing the features of the minute space.
[0072]
The microchannel substrate having the microchannels constituting the microchannel structure as described above is, for example, a substrate material such as glass, quartz, ceramic, silicon, or metal or resin, by machining or laser processing. It can be manufactured by direct processing by etching or the like. When the substrate material is ceramic or resin, it can be manufactured by molding using a mold made of metal or the like having a channel shape. In general, the microchannel substrate is laminated and integrated with a fluid inlet, a fluid outlet, and a cover body having a small hole having a diameter of about several mm at a position corresponding to the outlet of each microchannel. Used as a microchannel structure. As a method of joining the cover body and the microchannel substrate, when the substrate material is ceramic or metal, soldering or an adhesive is used, or when the substrate material is glass, quartz, or resin, the temperature is in the range of hundred to several hundred degrees. Bonding methods suitable for each substrate material are used, such as applying a load at a high temperature under a high temperature and bonding the substrate material at room temperature by activating the surface by washing when the substrate material is silicon.
[0073]
The chemical operation method of the fluid of the present invention means chemical operations such as mixing, chemical reaction, solvent extraction, separation, and recovery using the microchannel structure of the present invention described above. It means a chemical operation combining two or more.
[0074]
One of the mixing methods may be a chemical operation method in which fine particles are mixed into at least one or more fluids, and the fluids are stirred while maintaining a fluid boundary to promote mixing. By doing so, the fine particles mixed in the fluid move in the fluid and the direction of the flow of the fluid changes, so that only the fluid mixed with the fine particles is stirred. In this way, the fluid is stirred in the fluid while maintaining the fluid boundary of the fluid, so that the substances contained in the fluid are promptly and uniformly dispersed in each fluid, and sufficient chemical reaction and solvent Extraction becomes possible.
[0075]
In addition, since each fluid holds a fluid boundary, adjacent fluids forming a laminar flow can be easily separated. Further, the width of the microchannel is about several μm to several hundred μm, and the depth is about several tens μm. Since the microparticles need to flow through the microchannel without clogging, the particle diameter of the microparticles is small. The thickness is preferably from submicron to several tens μm so as to be about one digit smaller than the width and depth of the flow path.
[0076]
The number of the fine particles is not particularly limited as long as a certain stirring effect can be obtained in the fluid mixed with the fine particles and the fine particles flow in the fine flow path without clogging.
[0077]
The material of the fine particles is not particularly limited as long as they do not dissolve in the fluid to be mixed, such as an inorganic material such as silica or a resin material such as styrene or acrylic. Further, the surface of the fine particles may be modified to be hydrophilic or hydrophobic with respect to the material of the main body of the fine particles. For example, when the fluid containing the fine particles is a hydrophilic medium such as water or ethanol, the surface of the fine particles uses hydrophilic modified particles having a functional group such as a hydroxyl group or a carboxyl group, and the fluid containing the fine particles is hexane. In the case of a hydrophobic medium such as ethyl acetate, it is preferable to use fine particles whose surface has been modified to have a hydrophobic property having a functional group such as an octadecyl group or a butyl group.
[0078]
As a result, it is possible to prevent the fine particles mixed in one fluid from moving beyond the fluid boundary with the fluid in contact with the fluid at the fluid boundary, and the fluid boundary is stably maintained by the discontinuous partition wall. The fluid mixed with the fine particles can be stirred as it is.
[0079]
FIG. 20 is a conceptual diagram of a method of stirring a fluid in a microchannel using such fine particles. FIG. 20 shows an example in which two kinds of fluids are introduced and fine particles are mixed in only one of the fluids. As shown in FIG. 20, when the fine particles (80) collide with the inner wall of the fine flow path (19) or the fine particles collide with each other, the direction of the flow of the fluid changes and the stirring effect can be obtained. Although FIG. 20 shows an example in which fine particles are mixed into one of the fluids flowing through the minute flow path and stirring is performed, fine particles may be mixed into both fluids and both the fluids may be stirred.
[0080]
Using the microchannel structure of the present invention, by performing chemical operations such as mixing, chemical reaction, solvent extraction, separation, and recovery, conventionally, using a test tube, a beaker, a flask, or the like, The use of the present microchannel structure makes it possible, for the first time, to perform the chemical operations such as reaction, solvent extraction, separation, and catalyst recovery separately in the microchannel. In particular, there is a multiphase catalytic reaction as a target of an effective chemical operation method using the microchannel structure of the present invention.
[0081]
Typical catalysts include acid / base catalysts such as oxonium ions and hydroxide ions, and transition metal complexes containing nickel, palladium, copper, titanium or the like as a central metal. As a kind of catalyst, there is an enzyme which is a protein synthesized in a body called a biocatalyst. Examples of the enzyme include lipase, trypsin, chymotrypsin, cathepsin, fumarate hydratase, and laccase.
[0082]
In the chemical operation method of the present invention, the fluid discharged from the outlet and introduced again through the inlet may be the fluid containing the catalyst described above. In this way, a very expensive catalyst can be recovered and reused as long as its catalytic activity is not lost. Particularly in a chemical reaction using an enzyme that is a biocatalyst, in order to efficiently react the enzyme contained in the aqueous phase with the substrate contained in the organic phase, the aqueous phase and the organic phase are mechanically stirred by a stirrer or other stirrer. In general, the enzyme loses its activity due to the physical action of mechanical stirring, or loses its activity when the enzyme is suspended in the organic phase. . However, by using the microchannel structure according to the present invention, the aqueous phase containing the enzyme and the organic phase containing the substrate can be made into a laminar flow to form a stable fluid boundary in the microchannel and contact them. Even without mechanical stirring, the chemical reaction between the enzyme and the substrate can be performed efficiently because the specific interface area is large and the molecular diffusion distance is short. Furthermore, since the enzyme does not lose its activity due to the physical action of mechanical stirring and the suspension of the enzyme in the organic phase, the aqueous phase containing the enzyme and the organic phase containing the substrate are separated. 1. An organic phase is passed through one discharge channel to take out the substrate chemically reacted with the enzyme. An aqueous phase is passed through one discharge channel, and the aqueous phase discharged from the outlet is taken out. The enzyme can be easily separated, recovered and reused without losing its activity by re-introducing it into the inlet into which is introduced. Such a chemical operation method becomes possible only by using the microchannel structure of the present invention.
[0083]
As shown in FIG. 19 (a), the chemical operation method of the present invention comprises the steps of forming a fluid (78) containing a catalyst and a fluid (79) containing a substrate in a two-phase layer in a microchannel (19). A chemical operation (mixing by diffusion, chemical reaction, solvent extraction, separation, recovery) may be performed by forming a stream, or as shown in FIG. The liquid may be sent between the fluids (79) containing two kinds of substrates in the fluid traveling direction (27) to form a three-phase laminar flow, and the chemical operation may be performed, or as shown in FIG. 19 (c). As described above, the fluid containing the substrate (79) is sandwiched between the fluids (78) containing the catalyst in the fluid traveling direction (27) on both sides, and the fluid is sent to form a three-phase laminar flow, and the chemical operation is performed. Alternatively, as shown in FIG. 19D, a fluid (78) containing a catalyst and a fluid (7) containing a substrate may be used. ) May be carried out chemical operations to form a multi-phase laminar flow in contact alternately with the fluid traveling direction (27) a. Here, the plurality of substrates may be the same or different. The plurality of catalysts may be the same or different.
[0084]
Generally, a so-called phase transfer catalyst is one of expensive catalysts. Here, a two-phase reaction system using a quaternary ammonium salt will be described as an example of the phase transfer catalyst with reference to FIG. In FIG. 14, CN is used as the nucleophilic anion (62).⁻In the reaction of replacing (R-X) which is an alkyl halide (63) with (R-CN) which is a nitrile (64), a quaternary ammonium salt (65) is used (Q⁺X⁻3) shows the concept of a reaction mechanism when ()) is used as a phase transfer catalyst.
[0085]
Na consisting of nucleophilic anion⁺CN⁻And a non-polar organic phase containing (R-X) which is an alkyl halide which is an organic substrate reacting therewith, and is a quaternary ammonium salt of a phase transfer catalyst (Q⁺X⁻) Is the nucleophilic anion of the aqueous phase (CN⁻) And a halogen anion (66) which is an ion pair with itself (X⁻), The nucleophilic anion (CN) is added to the organic phase where the reaction takes place.⁻) To promote the reaction. After the reaction, it is the eliminated halogen anion (X⁻) To form an ion pair, which is again a quaternary ammonium salt (Q⁺X⁻) And return to the aqueous phase and repeat this cycle.
[0086]
As the phase transfer catalyst, phosphonium salts, cinchonium salts, crown ethers, cryptands, dialkyl polyoxyethylene oxides, etc. are generally known in addition to quaternary ammonium salts.
[0087]
The efficiency of the reaction of a reaction system using such a phase transfer catalyst depends on how efficiently the phase transfer catalyst can move between phases.The efficiency of phase transfer of the phase transfer catalyst depends on the catalyst phase and the reaction phase. The larger the relative boundary area of, and the shorter the diffusion distance of the phase movement contact, the better. Here, in the minute space in the minute channel structure of the present invention, the phase transfer from the catalytic phase to the reaction phase of the phase transfer catalyst is large because the specific surface area is large and the molecular diffusion distance is short without performing a special stirring operation. And the phase transfer from the reaction phase to the catalyst phase is performed efficiently.
[0088]
In addition, by using the microchannel structure according to the present invention, the catalyst phase and the reaction phase become laminar in the microchannel, flow while maintaining the respective fluid boundaries, and branch from the microchannel to the discharge channel. In, the reaction phase and the catalyst phase that were in contact with each other were separated, the reaction phase was passed through one discharge channel to take out the product, and the catalyst phase was passed through the other discharge channel and discharged from the outlet. By re-introducing the catalyst phase into the inlet where the catalyst phase has been introduced, the phase transfer catalyst recovered in the catalyst phase can be easily separated, recovered and reused.
[0089]
Further, the phase transfer catalyst may be an energy-dependent phase transfer catalyst. The energy-dependent energy means light or heat, and a catalyst which causes phase transfer of the catalyst by adding this energy is herein referred to as an energy-dependent phase transfer catalyst. The energy-dependent phase transfer catalyst when the energy is heat is particularly called a temperature-dependent phase transfer catalyst.
[0090]
Here, the concept of a reaction system using a temperature-dependent phase transfer catalyst will be described with reference to FIG. As shown in FIG. 15, the catalyst D (67) is dissolved in the reaction phase (69) from the catalyst phase (68) by increasing the temperature, and promotes the reaction between the reactant A (70) and the reactant B (71). , Product C (72). When the temperature decreases, the solubility of the catalyst D in the reaction phase decreases and returns to the catalyst phase, so that the contribution to the synthesis reaction is lost. Generally, such a catalyst D is referred to as a temperature-dependent phase transfer catalyst. Gladysz reaction and Yamamoto reaction shown in FIG. 16 are generally well known as examples of the reaction using such a temperature-dependent catalyst.
[0091]
The efficiency of a reaction in a reaction system using such a temperature-dependent phase transfer catalyst depends on whether the temperature-dependent phase transfer catalyst can efficiently move between phases. In other words, the phase transfer efficiency of the temperature-dependent phase transfer contact is better as the heating / cooling efficiency is higher, the relative interface area between the catalyst phase and the reaction phase is larger, and the diffusion distance of the temperature-dependent phase transfer contact is shorter. Become. Here, in the minute space in the minute channel structure of the present invention, since the heat capacity is small and rapid heating and cooling are possible, the phase transfer of the temperature-dependent phase transfer catalyst from the catalyst phase to the reaction phase and from the reaction phase. The phase transfer to the catalyst phase is performed efficiently. In addition, as described above, in a small space, the specific interfacial area is large and the molecular diffusion distance is short without any special stirring operation, so that the phase transfer from the catalyst phase to the reaction phase of the temperature-dependent phase transfer catalyst and the reaction phase occur. Transfer from the catalyst to the catalyst phase is performed more efficiently.
[0092]
In addition, by using the microchannel structure according to the present invention, in the microchannel, the catalyst phase and the reaction phase become laminar and flow while maintaining respective fluid boundaries, and branch from the microchannel to two discharge channels. In the section, the catalyst phase and the reaction phase that were in contact with each other were separated, the reaction phase was passed through one discharge channel to take out the product, the catalyst phase was passed through the other discharge channel, and the product was discharged from the discharge port. The temperature-dependent phase-transfer catalyst recovered in the catalyst phase can be easily separated, recovered, and reused by re-introducing the recovered catalyst phase into the inlet into which the catalyst phase has been introduced.
[0093]
For example, in the microchannel structure of the present invention, as shown in FIG. 17, a heater (73) serving as a heating device is installed and heated in the first half of the microchannel located on the inlet (11) side. After efficiently transferring the temperature-dependent phase transfer catalyst from the catalyst phase to the reaction phase in the first half of the microchannel (19), the reaction is carried out, and the second half of the microchannel located on the outlet (12) side is performed. The fluid is cooled from a heated state to a normal temperature by thermally insulating the first half of the microchannel by a known heat insulation method such as embedding a heat insulator (74) in the microchannel structure (55). The temperature-dependent phase-transfer catalyst can be efficiently phase-transferred to the catalyst phase, separated, recovered, and reused.
[0094]
FIG. 18 shows an example of a microchannel structure having a light irradiation device for irradiating a part of the microchannel inside the microchannel structure when the energy of the energy-dependent phase transfer catalyst is light. showed that. FIG. 18 shows a structure in which the light irradiation (75) irradiated through the mask (76) is applied to a part of the microchannel (19) as a light irradiation spot (77), and the other symbols are shown in FIG. It is the same as that shown in FIG.
[0095]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, embodiments of the present invention will be described in detail. It is needless to say that the present invention is not limited to only these embodiments, and can be arbitrarily changed without departing from the gist of the invention.
(Example 1)
FIG. 6B shows the configuration of the microchannel structure used in the first embodiment. The shape of the microchannel is such that the fluid inlet side and the fluid outlet side are branched into two Y-shaped microchannels, and the internal structure of the microchannel of the microchannel structure is shown in FIG. As shown in (2), a discontinuous partition wall (22) was formed substantially at the center of the width direction of the microchannel in the direction of fluid flow at a height equal to the depth of the microchannel. The width (9) of the manufactured microchannel is 100 μm, the depth (17) is 20 μm, and the length is 30 mm. Five types of microchannels in which the shortest distance (25) between the partition walls in the fluid traveling direction and the longest length (26) of the partition walls in the fluid traveling direction are 50 μm, 100 μm, 200 μm, 400 μm, and 800 μm, respectively. Was produced. The thickness (23) of the partition wall in the channel width direction is about 5 μm.
[0096]
As shown in FIG. 6B, the microchannel is formed on a Pyrex (registered trademark) substrate (32) of 70 mm × 38 mm × 1 mm (thickness) by general photolithography and wet etching. Pyrex of the same size provided with a small through hole having a diameter of 0.6 mm by mechanical processing means at positions corresponding to (28) and inlet B (29), outlet C (30) and outlet D (31). The microchannel was sealed by bonding a (registered trademark) substrate as a cover body (34) by heat fusion.
[0097]
Water and cyclohexane were supplied to the microchannel structure at an equal liquid supply speed of 3 μL / min to 50 μL / min. The viscosity of water at 20 ° C. is 1.002 [mPa · s], and the viscosity of cyclohexane is 0.979 [mPa · s], which are almost equal. Water is fed from the inlet A (28) and cyclohexane is fed from the inlet B (29) under the above conditions, and the amount of water discharged from the outlet C (30) and the amount of mixed cyclohexane are measured at the outlet D. The amount of cyclohexane discharged from (31) and the amount of mixed water were each weighed and measured with a measuring cylinder, and the results are shown in Table 1.
[0098]
[Table 1]

Table 1 shows the mixing ratio at each liquid sending speed under the constant velocity condition as a mixing ratio (%) of the organic phase in the aqueous phase and a mixing ratio (%) of the aqueous phase in the organic phase. The flow rates are 3, 5, 8, 10, 20, and 50 μL / min, and the shortest intervals between the partition walls in the fluid traveling direction are 50, 100, 200, 400, and 800 μm.
[0099]
According to the results of the first embodiment, when the shortest distance between the partition walls in the fluid traveling direction is 400 μm or less, the mixing rate is less than 10% when the range of the liquid sending speed is at least 8 to 50 μL / min. did. When the shortest distance between the partition walls in the fluid traveling direction was 800 μm, the mixing ratio did not become less than 10% at any liquid feeding speed.
(Example 2)
As a second example, cyclohexane was supplied at a fixed liquid supply rate of 8 μL / min using the microchannel structure shown in FIG. 6 used in Example 1, and 3 μL / water was supplied thereto. The solution was sent at a different solution sending speed between 20 and 20 μL / min. That is, when the liquid sending rate ratio of cyclohexane to water is 0.375 to 2.5, water is supplied from the inlet A (28) and cyclohexane is supplied from the inlet B (29) under the above conditions, and the outlet is supplied. The amount of water discharged from C (30) and the amount of mixed cyclohexane are measured by measuring the amount of cyclohexane discharged from outlet D (31) and the amount of mixed water with a measuring cylinder, respectively. The results are shown in Table 2.
[0100]
[Table 2]

Table 2 shows the mixing ratio at each liquid sending speed ratio as the mixing ratio (%) of the organic phase in the aqueous phase and the mixing ratio (%) of the aqueous phase in the organic phase. Is 0.375, 0.625, 1.000, 1.250, 2.500, and the shortest distance between the partition walls in the fluid traveling direction is 50, 100, 200, 400, 800 μm.
[0101]
According to the results of the second embodiment, when the shortest distance between the partition walls in the fluid traveling direction is 200 μm or less, the mixing rate is 10% when the range of the liquid sending speed ratio is at least 0.625 to 1.25. Less than realized. In the case where the shortest distance between the partition walls in the fluid traveling direction was 400 μm and 800 μm, the mixing ratio did not become less than 10% except for the liquid feeding speed ratio of 1: 1.
(Comparative Example 1)
As a first comparative example, the configuration of the microchannel structure used is shown in FIG. The shape of the microchannel is such that the fluid inlet side and the fluid outlet side are branched into two Y-shaped microchannels, and the internal structure of the microchannel is as shown in FIG. A continuous guide (16) having a height of about 20% of the depth (17) of the microchannel along the direction of fluid flow was formed substantially at the center with respect to the width direction of the channel. The manufactured microchannel has a width of 100 μm, a depth of 20 μm, and a length of 30 mm. The guide-like thickness (36) is about 5 μm.
[0102]
As shown in FIG. 5B, the microchannel is formed on a Pyrex (registered trademark) substrate (37) having a size of 70 mm × 38 mm × 1 mm (thickness) by general photolithography and wet etching. At the positions corresponding to (28) and the inlet B (29), the outlet C (30) and the outlet D (31), a small through hole (35) having a diameter of 0.6 mm was provided by mechanical processing means. The microchannel was sealed by bonding a Pyrex (registered trademark) substrate of a size as a cover body (34) by heat fusion.
[0103]
Water and cyclohexane were sent to the microchannel structure at the same liquid sending speed between 5 μL / min and 20 μL / min as in Example 1. Water is fed from the inlet A (28) and cyclohexane is fed from the inlet B (29) under the above conditions, and the amount of water discharged from the outlet C (30) and the amount of mixed cyclohexane are measured at the outlet D. The amount of cyclohexane discharged from (31) and the amount of contaminated water were each weighed and measured with a measuring cylinder, and the measurement results are shown in Table 1. As a result, the mixing ratio of cyclohexane to water and the mixing ratio of cyclohexane to water was 30% or more at any liquid feeding speed, which was a very high mixing ratio.
[0104]
Further, using the same microchannel structure, cyclohexane was sent at a fixed liquid sending rate of 8 μL / min in the same manner as in Example 2, while water was supplied at 3 μL / min to 20 μL / min. The liquid was sent at different liquid feeding speeds. That is, when the liquid sending rate ratio of cyclohexane to water is 0.375 to 2.5, water is supplied from the inlet A (28) and cyclohexane is supplied from the inlet B (29) under the above conditions, and the outlet is supplied. The amount of water discharged from C (30) and the amount of mixed cyclohexane are measured by measuring the amount of cyclohexane discharged from outlet D (31) and the amount of mixed water with a measuring cylinder, respectively. Table 2 shows the measurement results. As a result, the mixing ratio of cyclohexane to water and the mixing ratio of water to cyclohexane was 20% or more at any liquid feeding speed ratio, which was a very high mixing ratio.
(Example 3)
As a third embodiment, of the microchannel structure used in the first embodiment having the configuration of the microchannel structure shown in FIG. 6B and the internal structure of the microchannel shown in FIG. The inner wall on one side of the microchannel of the microchannel structure in which the shortest distance between the partition walls in the fluid traveling direction is 200 μm and 400 μm was subjected to a hydrophobic treatment according to the following procedure.
[0105]
First, a saturated KOH-ethanol solution is sent from the inlet A (28) and the inlet B (29) at a feed rate of 5 μL / min for about 30 minutes, and then toluene is introduced from the inlet A and from the inlet B. A toluene solution of 10% octadecyltrichlorosilane was fed at a feed rate of 5 μL / min for about 3 hours. As a result of this treatment, the inner wall on one side of the microchannel on the side that is introduced from the inlet A to which only toluene was sent and is discharged from the outlet C (30) is in the hydrophilic state of the original Pyrex (registered trademark) glass. The inner wall of one side of the microchannel on the side that is introduced from the inlet B to which the toluene solution of 10% octadecyltrichlorosilane was sent and is discharged from the outlet D (31) is modified to be hydrophobic.
[0106]
Water and cyclohexane are applied to a microchannel structure in which the inner wall on one side of the microchannel has been hydrophobized and the shortest distance between the partition walls in the direction of fluid flow is 400 μm, and water and cyclohexane are between 3 μL / min to 50 μL / min. At the same liquid sending speed. Water is fed from the inlet A (28) and cyclohexane is fed from the inlet B (29) under the above conditions, and the amount of water discharged from the outlet C (30) and the amount of mixed cyclohexane are measured at the outlet D. The amount of cyclohexane discharged from (31) and the amount of mixed water were each weighed and measured with a measuring cylinder, and the measurement results are shown in Table 3.
[0107]
[Table 3]

Table 3 shows the mixing ratio of the organic phase in the aqueous phase (%) and the mixing ratio of the aqueous phase in the organic phase (%) under the constant-velocity conditions at each liquid sending speed. , Flow rates are 3, 5, 8, 10, 20, 50 μL / min.
[0108]
As a result of the third example, the mixing rate was less than 8% and the mixing rate was reduced in the range of the liquid feeding speed of the mixing rate of less than 10% at the partition wall of 400 μm in the first example.
[0109]
In addition, cyclohexane is sent at a fixed liquid sending speed of 8 μL / min to a microchannel structure in which the shortest distance between the partition walls in the fluid traveling direction is 200 μm, in which the inner wall on one side of the microchannel is hydrophobized. The solution was fed, and water was sent at a rate of 3 μL / min to 20 μL / min. That is, when the liquid sending rate ratio of cyclohexane to water is 0.375 to 2.5, water is supplied from the inlet A (28) and cyclohexane is supplied from the inlet B (29) under the above conditions, and the outlet is supplied. The amount of water discharged from C (30) and the amount of mixed cyclohexane are measured by measuring the amount of cyclohexane discharged from outlet D (31) and the amount of mixed water with a measuring cylinder, respectively. Table 4 shows the measurement results.
[0110]
[Table 4]

Table 4 shows the mixing ratio at each liquid sending speed ratio as the mixing ratio (%) of the organic phase in the aqueous phase and the mixing ratio (%) of the aqueous phase in the organic phase. Are 0.375, 0.625, 1.000, 1.250, 2.500.
As a result, in the range of the liquid feeding speed ratio of less than 10% in the partition wall 200 μm in Example 2, the mixing rate was less than 8%, and the mixing rate was reduced.
(Example 4)
FIG. 6B shows the configuration of the microchannel structure used as the fourth embodiment. The shape of the microchannel is such that the fluid inlet side and the fluid outlet side are branched into two Y-shaped microchannels. FIG. 21 shows the internal structure of the microchannel used in this example. FIG. 21A is an SEM photograph of the microchannel used in the present embodiment viewed from above, and FIG. 21B is a concept showing the shape of the internal structure of the microchannel used in the embodiment. FIG. The formed microchannel had a width of 240 μm, a depth of 60 μm, and a length of 30 mm, and a number of 30 μm projections (20) were formed from one side wall of the microchannel on the inlet A and outlet C side. In addition, as shown in FIG. 6A, near the center of the micro channel, a partition wall (22) having a maximum length of 50 μm in the fluid traveling direction and a discontinuous height of 60 μm is provided at intervals of 50 μm in the fluid traveling direction. Formed.
[0111]
In the same manner as in Example 1, a flow path is formed on a Pyrex (registered trademark) substrate of 70 mm × 38 mm × 1 mm (thickness) by general photolithography and wet etching, and a fluid inlet A (28) And a through hole (35) having a diameter of 0.6 mm provided by mechanical processing means at positions corresponding to the inlet port B (29), the fluid outlet port C (30) and the outlet port D (31). The Pyrex (registered trademark) substrate as a cover body (34) was joined by heat fusion to seal the microchannel.
[0112]
Using this microchannel structure, methylation reaction of ethylenediamine with iodomethane was performed. An aqueous phase of an aqueous solution of ethylenediamine is sent at 10 μL / min from the inlet A, that is, to the side having the protrusion on the side wall of the microchannel, and an organic phase of a butanol solution of iodomethane is sent at 3 μL / min from the inlet B. Liquid. This reaction system is a reaction system in which ethylenediamine reacts with iodomethane, and N-methylethylenediamine is synthesized and extracted into an aqueous phase. When the microchannels were observed with a microscope while each solution was sent from the fluid inlet, the fluid boundary between the aqueous phase and the organic phase was observed, and the fluid was separated at the fluid outlet side branch, and the outlet C , And the organic phase could be separated and discharged from the outlet D substantially without mixing with each other. The aqueous phase discharged from the fluid discharge port was collected in a test tube and analyzed by high performance liquid chromatography. As a result, the amount ratio of ethylenediamine and N-methylethylenediamine was confirmed to be about 90:10. The conversion of N-methylethylenediamine was about 10%.
(Example 5)
FIG. 6B shows the configuration of the microchannel structure used as the fifth embodiment. The shape of the microchannel is such that the fluid inlet side and the fluid outlet side are branched into two Y-shaped microchannels. The width of the formed microchannel (19) is 240 μm, the depth is 60 μm, and the length is 30 mm. As the internal structure of the microchannel, as shown in FIG. 6A, a discontinuous partition wall (22) having a maximum length of 50 μm in the direction of fluid flow and a discontinuous height of 60 μm is provided near the center of the microchannel. They were formed at 50 μm intervals in the traveling direction.
[0113]
By the same method as in Example 1, the microchannel is formed on a Pyrex (registered trademark) substrate of 70 mm × 38 mm × 1 mm (thickness) by general photolithography and wet etching, and the inlet A (28) is formed. Pyrex (of the same size) provided with a small through-hole (35) having a diameter of 0.6 mm by mechanical processing means at positions corresponding to the inlet C (29), the outlet C (30) and the outlet D (31). (Registered trademark) substrate as a cover body (34) and bonded by heat fusion to seal the microchannel. The methylation reaction of ethylenediamine with iodomethane was performed using this microchannel. Fine particles of silica having an average particle size of 5 μm are mixed into the aqueous phase of an aqueous solution of ethylenediamine from the inlet A and the solution is sent at 10 μL / min. The organic phase of the butanol solution of iodomethane is introduced from the inlet B into the fluid traveling direction shown in FIG. The solution was sent to (27) at 3 μL / min. This reaction system is a reaction system in which ethylenediamine reacts with iodomethane, and N-methylethylenediamine is synthesized and extracted into an aqueous phase. When the microchannels were observed with a microscope while each solution was sent from the fluid inlet, the fluid boundary between the aqueous phase and the organic phase was observed, and the fluid was separated at the fluid outlet side branch, and the outlet C , And the organic phase could be separated and discharged from the outlet D substantially without mixing with each other. The aqueous phase discharged from the outlet C was collected in a test tube and analyzed by high performance liquid chromatography. As a result, the amount ratio of ethylenediamine and N-methylethylenediamine was confirmed to be about 90:10. The conversion of N-methylethylenediamine was about 10%.
(Example 6)
FIG. 6B shows the configuration of the microchannel structure used as the sixth embodiment. The shape of the microchannel is such that the fluid inlet side and the fluid outlet side are branched into two Y-shaped microchannels. . The width of the formed microchannel is 240 μm, the depth is 60 μm, and the length is 30 mm. As the internal structure of the microchannel, a partition wall having a height of 60 μm was formed near the center of the channel as shown in FIG.
[0114]
In the same manner as in Example 1, the flow path was formed on a Pyrex (registered trademark) substrate of 70 mm × 38 mm × 1 mm (thickness) by general photolithography and wet etching, and introduced into the inlet A (28). Pyrex (registered trademark) of the same size, in which small holes having a diameter of 0.6 mm are provided by mechanical processing means at positions corresponding to the outlet B (29), the outlet C (30), and the outlet D (31). The microchannel was hermetically sealed by bonding the substrate as a cover by heat fusion.
[0115]
Using this microchannel structure, methylation reaction of ethylenediamine with iodomethane was performed. An aqueous phase of an aqueous solution of ethylenediamine was fed from the inlet A at 10 μL / min, and an organic phase of a butanol solution of iodomethane was sent from the inlet B at 3 μL / min. When the microchannels were observed with a microscope while each solution was sent from the fluid inlet, the fluid boundary between the aqueous phase and the organic phase was observed, and the fluid was separated at the fluid outlet side branch, and the outlet C , And the organic phase could be separated and discharged from the outlet D substantially without mixing with each other. The aqueous phase discharged from the outlet C was collected in a test tube and analyzed by high performance liquid chromatography. As a result, the quantitative ratio of ethylenediamine and N-methylethylenediamine was confirmed to be about 93: 7. The conversion of N-methylethylenediamine was about 7%.
[0116]
According to the fourth, fifth, and sixth embodiments, two or more fluids form a laminar flow and come into contact at a fluid boundary according to the present invention, and the fluid boundary is stably maintained by a discontinuous partition wall. , Which separates the fluid at the branch of the microchannel on the fluid outlet side substantially without mixing, and stirs the fluid containing the raw materials and reaction products required for the reaction in the fluid. By forming a structure in a microchannel or stirring in a fluid mixed with fine particles, a microchannel structure and a chemical that have a microchannel that can perform chemical reaction, solvent extraction and separation quickly It can be seen that it has become possible to provide an operation method.
(Example 7)
As a seventh example, a decomposition reaction of p-chlorophenol was carried out by a laccase having an action of decomposing environmental pollutants, which is one of the catalytic reactions, using the microchannel structure shown in FIG. The shape of the micro channel (19) is such that two inlet channels communicating with the inlet A (28) and the inlet B (29), and the outlet C (30) and the outlet D (31). A minute flow path in which two discharge flow paths were branched in a Y-shape was used. The width of the formed microchannel is 100 μm, the depth is 25 μm, and the length is 400 mm. As shown in FIG. 21, the internal structure of the microchannel has a large number of 30 μm projections (20) formed on one side wall of the microchannel on the inlet A and outlet C side, as shown in FIG. Further, as shown in FIG. 22 (a), near the center of the microchannel, a partition wall (22) having a maximum length of 50 μm in the fluid traveling direction and a discontinuous height of 25 μm is provided at intervals of 50 μm in the fluid traveling direction. Formed.
[0117]
Using this microchannel structure, a decomposition reaction of p-chlorophenol was performed by laccase having an action of decomposing environmental pollutants, which is one of the catalytic reactions. An isooctane solution containing 100 μM of p-chlorophenol was fed at 5 μL / min as an organic phase from the inlet A, that is, on the side having the protrusion on the side wall of the microchannel, and laccase 30 μM as an aqueous phase from the inlet B. Was fed at a rate of 5 μL / min, and the amounts of p-chlorophenol in both phases before and after the reaction were quantified by liquid chromatography.
[0118]
As a result, the fluid was separated at the branch portion on the fluid discharge port side, and the aqueous phase could be separated from the discharge port C and the organic phase could be separated and discharged from the discharge port D substantially without mixing with each other. In about 8 seconds, the decomposition rate of p-chlorophenol reached 82%.
(Example 8)
As an eighth example, a decomposition reaction of p-chlorophenol was performed using a laccase having an action of decomposing environmental pollutants, which is one of the catalytic reactions, using the microchannel structure shown in FIG. 22B. The shape of the micro channel (19) is such that two inlet channels communicating with the inlet A (28) and the inlet B (29), and the outlet C (30) and the outlet D (31). A minute flow path in which two discharge flow paths were branched in a Y-shape was used. The width of the formed microchannel is 100 μm, the depth is 25 μm, and the length is 400 mm. As shown in FIG. 22 (a), a discontinuous partition wall (22) having a maximum length of 50 μm in the fluid traveling direction and a discontinuous height of 25 μm is provided near the center of the micro channel as shown in FIG. They were formed at 50 μm intervals in the traveling direction.
[0119]
Using this microchannel structure, silica fine particles having an average particle size of 5 μm were mixed into an isooctane solution containing 100 μM of p-chlorophenol as an organic phase and fed at 5 μL / min from an inlet A, A succinate buffer solution (pH 5.0) containing 30 μM of laccase was fed as an aqueous phase from the inlet B at 5 μL / min, and p-chlorophenol in both phases coming out of the two fluid outlets before and after the reaction. The amount was determined by liquid chromatography.
[0120]
As a result, the fluid was separated at the branch portion on the fluid discharge port side, and the aqueous phase could be separated from the discharge port C and the organic phase could be separated and discharged from the discharge port D substantially without mixing with each other. Also, the decomposition rate of p-chlorophenol reached 85% in about 8 seconds.
(Example 9)
Example 9 As a ninth example, a decomposition reaction of p-chlorophenol was performed by a laccase having an action of decomposing environmental pollutants, which is one of the catalytic reactions, using the microchannel structure shown in FIG. The shape of the minute flow path (19) is such that the introduction flow path communicating with the introduction port A (28) and the introduction port B (29), and the discharge flow path communicating with the discharge port C (30) and the discharge port D (31). Used microchannels branched into two each in a Y-shape. The width of the formed microchannel is 100 μm, the depth is 25 μm, and the length is 400 mm. As shown in FIG. 22A, a discontinuous partition wall (22) having a maximum length of 50 μm in the direction of fluid flow and a discontinuous height of 25 μm is provided near the center of the micro channel as the internal structure of the micro channel. Was formed at intervals of 50 μm.
[0121]
Using this microchannel structure, an isooctane solution containing 100 μM of p-chlorophenol was sent as an organic phase from the inlet A at a rate of 5 μL / min, and 30 μM of laccase as an aqueous phase was sent from the inlet B. A succinate buffer solution (pH 5.0) was fed at 5 μL / min, and the amount of p-chlorophenol in both phases before and after the reaction was quantified by liquid chromatography.
[0122]
As a result, the fluid was separated at the branch portion on the fluid discharge port side, and the aqueous phase could be separated from the discharge port C and the organic phase could be separated and discharged from the discharge port D substantially without mixing with each other. Also, the decomposition rate of p-chlorophenol reached 80% in about 8 seconds.
[0123]
From the above-described Embodiments 7, 8, and 9, two or more fluids form a laminar flow according to the present invention and come into contact with each other at a fluid boundary, and the fluid boundary is kept stable by a discontinuous partition wall. It is possible to separate the fluid at the branch of the microchannel almost without mixing with each other, and to create a microstructure in which the fluid containing the raw materials and reaction products necessary for the reaction is stirred in the fluid. By forming in the flow channel and stirring only the fluid mixed with fine particles, a micro flow channel structure with a micro flow channel that can quickly perform chemical reaction, solvent extraction and separation, and a chemical operation method It can be seen that it has become possible to provide.
(Example 10)
As a tenth embodiment, a microchannel structure as shown in FIG. The shape of the minute flow path (19) is such that the introduction flow path communicating with the introduction port A (28) and the introduction port B (29) and the discharge flow path communicating with the discharge port C (30) and the discharge port D ( A microchannel (19) branched into two in a Y-shape was used, and the formed microchannel had a width of 100 μm, a depth of 25 μm, and a length of 400 mm. As a structure, in the vicinity of the center of the microchannel, a discontinuous partition wall (22) having a maximum height of 50 μm in the fluid traveling direction and a height of 25 μm as shown in FIG. The microchannels were formed on a Pyrex (registered trademark) substrate of 70 mm × 38 mm × 1 mm (thickness) by general photolithography and wet etching, and the inlet A (28) and the inlet B ( 29), outlet C (30) and outlet D (31) At the corresponding position, a Pyrex (registered trademark) substrate of the same size, in which a penetrating small hole (35) having a diameter of 0.6 mm is provided by a mechanical processing means, is joined as a cover body (34) by heat fusion to form a micro flow. The passage was sealed to form a microchannel structure.
[0124]
Using this microchannel structure, a decomposition reaction of p-chlorophenol was performed by laccase having an action of decomposing environmental pollutants, which is one of the catalytic reactions. To the microchannel, a succinate buffer solution (pH 5.0) containing 30 μM of laccase as an aqueous phase was fed from the inlet A at 5 μL / min, and 100 μM of p-chlorophenol as an organic phase was fed from the inlet B. The contained isooctane solution was fed at 5 μL / min, and the amount of p-chlorophenol in both phases before and after the reaction was quantified by liquid chromatography.
[0125]
As a result, the fluid was separated at the branch portion on the fluid discharge port side, and the aqueous phase could be separated from the discharge port C and the organic phase could be separated and discharged from the discharge port D substantially without mixing with each other. Also, it took about 8 seconds for the decomposition rate of p-chlorophenol to reach 80%. Furthermore, when the degree of the activity of the enzyme was measured by the phenolaminoantipyrine method (P-4AA method), the activity of the enzyme was maintained at 90% or more even when the above reaction was repeated 10 times.
(Comparative Example 2)
As a second comparative example, 15 ml of a succinate buffer solution (pH 5.0) containing 30 μM of laccase as an aqueous phase and 15 ml of an isooctane solution containing 100 μM of p-chlorophenol as an organic phase were placed in a 50 ml sample bottle. The mixture was vigorously stirred using a magnetic stirrer, and the amount of p-chlorophenol in both phases before and after the reaction was determined by liquid chromatography. As a result, it took about 30 minutes for the decomposition rate of p-chlorophenol to reach 80%. When the activity of the enzyme was measured by the phenolaminoantipyrine method (P-4AA method), the activity of the enzyme decreased to about 80% after about 30 minutes, and decreased to about 80% after about 90 minutes. It decreased to about 5%.
[0126]
From the above Example 10 and Comparative Example 2, according to the present invention, two or more kinds of fluids form a laminar flow and come into contact at the fluid boundary, and react at the fluid boundary while maintaining the fluid boundary stably by the discontinuous partition wall. However, due to the large interfacial area and the short molecular diffusion distance, which are the characteristics of the minute space, the enzymatic reaction proceeds rapidly without the need for mechanical stirring, and the enzyme acts in the physical action of the mechanical stirring and in the organic phase. The enzyme can be recovered and reused without losing the activity of the enzyme due to the suspension, which indicates that the enzyme reaction proceeded efficiently.
[0127]
【The invention's effect】
According to the present invention, the following effects can be obtained.
[0128]
The microchannel structure according to the present invention has two or more inlets for introducing a fluid, an introduction channel communicating with the two or more introduction ports, and a fluid that communicates with the junction where the introduction channels merge and flows the introduced fluid. A microchannel structure having two or more discharge channels having a branch portion communicating with the microchannel and separating a predetermined fluid, and a discharge port communicating with them. A microchannel structure in which the microchannel is provided with a plurality of partition walls along a boundary formed by two or more types of introduced fluids so that the introduced fluids do not mix with each other. Body. With such a structure, the fluctuation of the position of the fluid boundary due to the temporal fluctuation of the liquid sending speed caused by a pump for sending the fluid or the like is suppressed, and the fluid to be sent to the inner wall of the microchannel is Can be prevented from flowing around due to a difference in affinity between the fluids, and each fluid can be discharged from the fluid discharge port of the microchannel without mixing other fluids.
[0129]
Further, when the liquid feeding speeds of all the fluids introduced into the microchannels are equal, the interval between the partition walls in the fluid traveling direction is equal to or less than a predetermined interval (the interval between the partition walls is approximately 800 μm or less, preferably 400 μm or less). In this case, adjacent fluids having equal viscosities can be discharged from the discharge port through the discharge flow path without mixing other fluids with each other within a predetermined liquid sending speed range.
[0130]
In addition, the product of the liquid transfer speed and the viscosity coefficient of the fluid having a high affinity for the fluid having a relatively low affinity for the fluid and the fluid having a relatively low affinity for the fluid of the adjacent fluid among the fluids to be introduced into the minute flow channel. If different, the shortest distance between the partition wall and the partition wall with respect to the fluid traveling direction is set to a certain distance or less (the distance between the partition wall and the partition wall is about 400 μm or less, preferably about 200 μm or less), so that the partition wall is introduced into the microchannel. Even if the product of the flow rate and the viscosity coefficient of the fluid having a relatively low affinity for the flow path wall and the fluid having a relatively low affinity for the fluid adjacent to the fluid fluctuates to some extent, The fluid can be discharged from the discharge port through the discharge channel without mixing other fluids.
[0131]
In addition, it can be performed simultaneously with the formation of the shape of the micro flow channel by using a method such as etching, machining, molding, etc. without going through a number of steps such as a method by flow channel modification. Compared with this, the time and cost for manufacturing the flow channel can be significantly reduced. In particular, when the microchannel structure of the present invention is manufactured by molding a resin, ceramic, glass, or the like, the maximum time and cost reduction effect of manufacturing the channel can be obtained.
[0132]
Furthermore, basically, since the above-mentioned effects are realized by the shape of the microchannel of the microchannel structure of the present invention, the continuation of the above-mentioned effects can be realized, that is, the effect, Can be realized for the first time by the microchannel structure of the present invention. Further, since the partition wall closest to the branch portion of the microchannel is in communication with the branch portion of the microchannel, the adjacent fluids are gently separated and the mixing of each fluid can be suppressed. it can.
[0133]
Further, in the portion having a shape other than the straight line of the minute flow channel in the present invention, the partition wall has a portion of a shape other than the straight line of the minute flow passage from near the vicinity immediately before the portion having the shape other than the straight line of the minute flow passage. By continuously forming to the vicinity immediately after, the phenomenon that the fluid inside the curved micro flow path goes out to the outer fluid due to centrifugal force in the curved part of the micro flow path is prevented And can be eliminated.
[0134]
In addition, when the liquid sending speeds of all the fluids introduced into the microchannels are equal, by making the interval between the partition walls in the fluid traveling direction smaller than a certain interval, adjacent fluids having the same viscosity can be supplied at a predetermined liquid sending speed. In the speed range, each of the fluids can be discharged from the discharge port through the discharge flow path without mixing other fluids.
[0135]
In addition, the product of the liquid transfer speed and the viscosity coefficient of the fluid having a high affinity for the fluid having a relatively low affinity for the fluid and the fluid having a relatively low affinity for the fluid of the adjacent fluid among the fluids to be introduced into the minute flow channel. If they are different, by making the shortest distance between the partition wall and the partition wall with respect to the fluid traveling direction smaller than a certain distance, the adjacent fluid among the fluids introduced into the minute flow path has a relatively amphiphilic property with respect to the flow path wall face. Even if the product of the flow rate wall surface of the low-fluid and the liquid-feeding speed of the highly amphiphilic fluid and the viscosity coefficient fluctuates by about 30 to 40%, the discharge flow path is formed without mixing other fluids into each fluid. Can be discharged from the discharge port, and even if the viscosity of each fluid fluctuates due to the progress of the chemical reaction, if the fluctuation of the viscosity is within the above range, the stable fluid of the laminar flow formed by each fluid Boundary can be maintained and each fluid can be drained without mixing other fluids It can be discharged from the discharge port through.
[0136]
In the microchannel structure of the present invention, the affinity of the inner wall of the microchannel partitioned by the partition wall is different from the affinity of the inner wall of the adjacent microchannel via the partition wall. By doing so, it is possible to further effectively prevent the fluid having an affinity for the inner wall of the microchannel from wrapping around by covering the fluid having no affinity for the inner wall of the microchannel. Is more reliably separated and discharged without contamination of other fluids.
[0137]
According to the above-mentioned effects that can be realized only by using the microchannel structure of the present invention, two or more types of fluids introduced into the microchannel can be maintained at their respective fluid boundaries stably, and each fluid can be adjacent to each other. It is very easy to discharge the fluid from the microchannel without mixing the fluid, and by utilizing this effect, the following dependent effects can be further obtained.
[0138]
First, as a first subordinate effect, after two or more types of fluids pass through the microchannel, the fluids can be sufficiently separated without mixing adjacent fluids, so that the mixing time and / or the time of the chemical reaction are reduced. The contact time of adjacent fluids in the microchannel determined by the channel length of the microchannel and / or the liquid sending speed can be determined only in the microchannel, and therefore, the mixing and And / or the chemical reaction can be stopped, and a chemical reaction utilizing original features such as control of a sequential reaction and suppression of a side reaction of the microchannel can be realized. Further, it is possible to recover and reuse the catalyst while maintaining the activity of the catalyst specified in the catalytic reaction or the like.
[0139]
As a second dependent effect, since each fluid can be sufficiently separated and discharged without mixing adjacent fluids, the time for solvent extraction can be reduced by the flow path length of the micro flow path and / or the liquid sending speed. Accurate control can be performed, so that the extraction of the solvent can be stopped only in the microchannel in the microchannel. It is possible to sufficiently separate from the extraction solvent.
[0140]
As a third subordinate effect, a film is formed at an adjacent fluid boundary formed when two or more kinds of fluids are flown in the microchannel, and the fluid in the fluid is formed between the two adjacent fluids in the microchannel via the membrane. When performing a catalytic reaction or an enzymatic reaction due to the selective permeation of a substance or the carrying of a catalyst or an enzyme on the membrane, the membrane described above may be formed in a practical flow length of several cm to several tens cm. Catalysts and enzymes can be immobilized on the membrane.
[0141]
As a fourth subordinate effect, it becomes possible to send adjacent fluids that have become laminar flows in the microchannel in opposite fluid traveling directions, and to shift the equilibrium of chemical reaction and solvent extraction. For the first time, it is possible to conduct an experiment to verify whether it can be performed. In addition, it can be performed simultaneously with the formation of the shape of the micro flow channel by using a method such as etching, machining, molding, etc. without going through a number of steps such as a method by flow channel modification. Compared with this, the time and cost for manufacturing the flow channel can be significantly reduced. In particular, when the microchannel structure of the present invention is manufactured by molding a resin, ceramic, glass, or the like, the maximum time and cost reduction effect of manufacturing the channel can be obtained. Furthermore, basically, since the above-mentioned effects are realized by the shape of the microchannel of the microchannel structure of the present invention, the continuation of the above-mentioned effects can be realized, that is, the effect, Can be realized for the first time by the microchannel structure of the present invention.
[0142]
As a fifth subordinate effect, by forming projections protruding to the extent that the flow of the fluid can be maintained in the minute flow path or mixing fine particles, the fluid boundary of the laminar flow formed by each fluid can be stably formed. It is possible to stir each fluid while keeping it, so that the substances contained in each fluid can be uniformly dispersed in each fluid.
[Brief description of the drawings]
FIG. 1 is a conceptual diagram showing a laminar flow in a Y-shaped microchannel.
FIG. 2 is a conceptual diagram showing a laminar flow in a double Y-shaped microchannel. FIG. 4 is a conceptual diagram of a microchannel used in Comparative Examples 2 and 3.
FIGS. 3A, 3B, and 3C are conceptual diagrams showing how the position of a fluid boundary fluctuates.
FIGS. 4A and 4B are conceptual diagrams for explaining the Hagen-Poiseuille equation.
5A is a conceptual diagram of an internal structure of a microchannel used in Comparative Example 1, and FIG. 5B shows a configuration of a microchannel structure used in Comparative Example 1. FIG.
6A is a conceptual diagram of the internal structure of a microchannel used in Example 1, Example 2, Example 3, Example 5, and Example 6, and FIG. The configuration of the microchannel structure used in Example 2, Example 3, Example 4, Example 5, and Example 6 is shown.
FIG. 7 is a schematic plan view of the shape of a partition wall in a curved portion of a microchannel in the present invention.
FIG. 8 is a schematic plan view of some aspects of a partition wall in the vicinity of a junction of a microchannel and a branch in the present invention. FIG. (B) shows the case where the partition wall closest to the branch of the microchannel is in communication with the branch of the microchannel, and (c) and (d) show the junction of the microchannel. The case where the partition wall is continuous with the junction in the vicinity and the partition wall is continuous with the branch in the vicinity of the branch of the microchannel is shown.
FIG. 9 is a conceptual diagram of a case where adjacent fluids flow in opposite directions from each other in a microchannel according to the present invention.
FIG. 10 is a schematic flow chart for forming a thin film of an inorganic material between partition walls in the fluid traveling direction of the microchannel structure of the present invention.
FIGS. 11A, 11B and 11C are schematic cross-sectional views of a microchannel when a metal film is arranged in the microchannel of the microchannel structure of the present invention. 11 is a view as seen from above.
12 (a) to 12 (d) are schematic views showing some embodiments of a projection for stirring a fluid while maintaining a fluid boundary formed in a microchannel in the present invention.
FIG. 13 is a conceptual diagram showing a means for introducing, discharging, and recovering a fluid using a microchannel in the present invention. FIG. 13 (a) is a liquid sending pump in which a fluid is installed outside a microchannel structure. FIG. 3B is a conceptual diagram showing a means for sending a liquid by a micro pump in which a fluid is embedded inside a microchannel structure.
FIG. 14 is a diagram showing an example of a reaction system using a phase transfer catalyst.
FIG. 15 is a view showing the concept of a reaction system using a temperature-dependent phase transfer catalyst.
FIG. 16 is an example of a reaction using a temperature-dependent phase transfer catalyst.
FIG. 17 is a view showing the concept of a microchannel structure used for a temperature-dependent phase transfer catalyst.
FIG. 18 is a schematic view of a microchannel structure for supplying energy by irradiating light to a part of the microchannel inside the microchannel structure.
FIGS. 19 (a) to (d) show chemical treatments by forming a laminar flow of a catalyst-containing fluid and a substrate-containing fluid in a microchannel in the microchannel structure of the present invention. It is a figure which shows some aspects to perform.
FIG. 20 is a conceptual diagram showing an example in which fine particles are mixed into a fluid on one side of a microchannel in the present invention.
FIG. 21 (a) is a SEM photograph of a plan view of the internal structure of the microchannel used in Examples 4 and 7, and FIG. 21 (b) is a microchannel used in Examples 4 and 7. It is a conceptual diagram of the internal structure of.
FIG. 22 (a) is a conceptual diagram showing the internal structure of a microchannel used in Examples 8, 9 and 10, and FIG. 22 (b) is Example 7, 8 and 9 The configuration of the microchannel structure used in Example 10 is shown.
[Explanation of symbols]
1: water phase
2: Organic phase
3: fluid boundary
4: Branch
5: Linear velocity
6: Diameter
7: Horizontal circular tube
8: Circular pipe end face
9: Width of micro channel
10: Channel length
11: Fluid inlet
12: Fluid outlet
13: Fluid A
14: Fluid B
15: Fluid wraparound
16: Guide shape
17: Channel depth
18: Bottom of micro channel
19: Micro channel
20: protrusion
21: Channel width
22: Partition wall
23: Thickness of partition wall
24: Partition wall height
25: Shortest distance between partition walls in the direction of fluid flow
26: The longest length of the partition wall in the fluid traveling direction
27: Fluid traveling direction
28: Inlet A
29: Inlet B
30: outlet C
31: Outlet D
32: Substrate
33: Fluid width
34: Cover body
35: Small hole
36: Guide-like thickness
37: junction
38: Near the introduction channel
39: Near the discharge channel
40: Near the center of the microchannel
41: Near the vicinity immediately before and / or immediately after the portion where the minute flow path has a shape other than a straight line
42: Near the junction
43: Near the branch
44: Thermosetting resin
45: heater
46: Suspension containing inorganic material
47: Acid or alkali
48: Porous thin film of inorganic material
49: Metal film
50: Upper surface of microchannel
51: Side of the microchannel
52: Microchannel substrate
53: Wall
54: Width of fluid boundary
55: Microchannel structure
56: Liquid sending pump
57: Container
58: Capillary tube
59: Micro pump
60: Recovery channel
61: Reservoir tank
62: nucleophilic anion
63: Alkyl halide
64: Nitrile
65: Quaternary ammonium salt
66: Halogen anion
67: Catalyst D
68: Catalyst phase
69: Reaction phase
70: Reactant A
71: Reactant B
72: Product C
73: heater
74: Insulation material
75: Light irradiation
76: Mask
77: Light irradiation spot
78: Fluid containing catalyst
79: Fluid containing substrate
80: fine particles
81: Movement of fine particles

Claims (34)

Two or more introduction ports for introducing a fluid and an introduction flow path communicating with them, a micro flow path communicating with the junction where the introduction flow paths merge and flowing the introduced fluid, A microchannel structure having two or more discharge channels having a branch portion communicating with the passage and separating a predetermined fluid, and a discharge port communicating with them, and the microchannel includes: A microchannel structure, comprising a plurality of partition walls provided along a boundary formed by two or more types of introduced fluids so that the introduced fluids do not mix with each other. 2. The microchannel structure according to claim 1, wherein the partition wall is discontinuous with respect to a traveling direction of the fluid. 3. The microchannel structure according to claim 1, wherein a height of the partition wall is substantially equal to a microchannel depth. The microchannel structure according to any one of claims 1 to 3, wherein the plurality of partition walls are provided at positions separated from the merging portion and the branch portion. The partition wall closest to a branch portion of the microchannel among the plurality of partition walls is in communication with the branch portion of the microchannel. Micro channel structure. 4. The plurality of partition walls according to any one of claims 1 to 3, wherein there is at least one non-existing portion except for a vicinity of a junction of the introduction flow channel and a vicinity of a branch portion of the discharge flow channel. Micro channel structure. The minute flow path according to any one of claims 1 to 6, wherein the longest length of the partition wall in the traveling direction of the fluid is equal to or less than the distance between the partition walls in the traveling direction of the fluid. Structure. In the portion of the minute flow path other than the straight line, the partition wall is in the vicinity of immediately before the portion of the minute flow path other than the straight line and in the vicinity of immediately after the portion of the minute flow path other than the straight line. The microchannel structure according to any one of claims 1 to 7, wherein the microchannel structure is continuous. In the vicinity of the introduction flow path and / or the vicinity of the discharge flow path in the micro flow path, the distance between the partition wall and the partition wall in the traveling direction of the fluid is set to be close to the introduction flow path and / or the discharge flow path in the micro flow path The microchannel structure according to any one of claims 1 to 8, wherein a distance between a partition wall and a partition wall in a traveling direction of the fluid with respect to a part other than the vicinity is shorter than a partition wall. The partition wall in the direction of travel of the fluid is continuous in the direction of travel of the fluid at a portion near the introduction channel and / or near the discharge channel in the microchannel. The microchannel structure according to any one of the above. The microchannel structure according to any one of claims 1 to 10, wherein a plurality of protrusions protruding to an extent that a fluid flow can be maintained are formed on an inner wall of the microchannel partitioned by the partition wall. body. In the two or more kinds of fluids introduced into the minute flow path, the two or more introduction ports and the introduction flow path communicating with them so that the traveling directions of adjacent fluids via the partition wall are opposite to each other. The microchannel structure according to any one of claims 1 to 11, wherein the two or more discharge ports and the discharge channel communicating with them are arranged. 13. The surface of the inner wall of the microchannel partitioned by the partition wall has a property of adapting according to the hydrophilicity / hydrophobicity of each of the introduced fluids. Micro channel structure. 14. The microchannel structure according to claim 13, wherein the inner wall surface of the microchannel partitioned by the partition wall is made of a material having a different hydrophilic property on the side where the introduced fluid is sent. body. 15. The microscopic device according to any one of claims 1 to 14, wherein a film having a fine hole equal to or smaller than a distance between the partition walls is present between the partition walls in the direction of travel of the fluid. Channel structure. The microchannel structure according to claim 15, wherein the film is made of a polymer material and / or an inorganic material. The microchannel structure according to any one of claims 1 to 16, wherein a metal film is disposed on all or a part of the inner wall and / or the partition wall of the microchannel. The microchannel structure according to claim 17, further comprising a current supply unit and / or a voltage supply unit to the metal. The microchannel structure according to any one of claims 1 to 18, wherein the microchannel structure has a structure including a reintroduction channel for guiding the fluid discharged from the outlet to the inlet from the outlet. . A pump, which is in communication with the reintroduction flow path and sends a fluid, and a reservoir tank, which is in communication with the reintroduction flow path and temporarily stores the fluid, is provided. Item 20. The microchannel structure according to Item 19. The microchannel structure according to any one of claims 1 to 20, further comprising means for supplying energy to a fluid flowing through the microchannel. 22. The microchannel structure according to claim 21, wherein the means for supplying energy is a heating device and / or a light irradiation device. A microchannel structure comprising a plurality of microchannels according to any one of claims 1 to 22 in a planar or three-dimensional manner. Two or more introduction ports for introducing a fluid and an introduction flow path communicating with them, a micro flow path communicating with the junction where the introduction flow paths merge and flowing the introduced fluid, A microchannel structure having two or more discharge channels having a branch portion communicating with the passage and separating a predetermined fluid, and a discharge port communicating with them, and the microchannel includes: Along the boundary formed by the introduced two or more types of fluids, the introduced fluids are discontinuous in the traveling direction of the fluid and have a height substantially equal to the microchannel depth so that the introduced fluids do not mix with each other. Partition walls are provided, and there is one or more places where the partition walls do not exist, except for the vicinity of the junction of the introduction flow path and the vicinity of the branch part of the discharge flow path. Micro channel structure. 25. A chemistry using the microchannel structure according to any one of claims 1 to 24, wherein two or more types of fluids contacting through the partition wall in the microchannel are mixed by molecular diffusion. Method of operation. 26. The method of claim 25, wherein fine particles are mixed into one or more fluids and the fluids are agitated while maintaining fluid boundaries to promote mixing. 25. A chemical operation method using the microchannel structure according to any one of claims 1 to 24, wherein two or more types of fluids that come into contact with each other through the partition wall in the microchannel are chemically reacted. . Using the microchannel structure according to any one of claims 1 to 24, the extraction target substance is extracted from the solvent to be extracted with the extraction solvent contacting via the partition wall in the microchannel by phase transfer. A method for chemical operation, characterized in that: 25. A chemical operation method using the microchannel structure according to any one of claims 1 to 24, wherein two or more kinds of fluids contacting via the partition wall in the microchannel are separated. The method according to claim 29, wherein the one or more separated fluids are introduced again through the inlet. 31. The chemical operation method according to claim 30, wherein the separated fluid is discharged from a discharge port through a discharge channel, and then the discharged fluid is re-introduced from the inlet. 25. A chemical operation method, comprising supplying energy to a fluid flowing through the microchannel using the microchannel structure according to any one of claims 1 to 24. The method according to claim 32, wherein the energy is heat and / or light. A chemical operation method, wherein the two or more chemical operations according to any one of claims 25 to 33 are arbitrarily combined using the microchannel structure according to any one of claims 1 to 24.

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