JP2004530044A - Micro-engineered reactor - Google Patents

Abstract

The present invention provides a micro-engineered reactor consisting of a tightly coupled reactor and an electrochemical cell, and uses such a device for the synthesis of organic compounds by a process involving an electrochemical reaction. About the method. The synthesis process electrochemically converts the source material into a reactive primary product that is exposed to the precursor material in a channel or reaction zone within the chamber, and reacts the primary product and the precursor material with the secondary product. It is of the kind that gives rise to products.

Description

【０１２０】
約５０％の拡散輸送が約１０番目の上記時間（Ｄｔ／ｄ^２〜０．１に相当する）において起こる。上記表に基づいて、拡散単独による比較的迅速な平衡が１００秒以内に起こり、そこで、要求される運搬距離ｄは１００μｍか又はそれ未満の程度である。２種の流体ストリームの混合のための関連する距離ｄはチャネルの最も遠い端部からのものであり、そこで、２種の流体が合う。電極上の一次生産物の堆積物へのように、物質の表面へのか、又は表面からの輸送のために、ｄは、流体ストリームか、又はその表面に対する層の直径である。距離ｄが小さく作られる微細工学的装置では、距離ｄによって、拡散により制御された運搬、混合、及び反応時間が減少し、及び制御される。
【０１２１】
運搬制御の下に操作される処理のために、反応物質消耗及び装置の反応域からの生産物流束(flux)は、反応域中の流体流のための運送時間及びその域における横断流拡散処理に依存する。反応域の流体流の運送時間及び横断流の拡散完了時間が同様になるような流れ割合の選定は、距離ｄが減少するように改善する装置の単位容積当たりの反応流束(reaction flux)を招く。これは、反応及び／又はオーム（ジュール）加熱からのより一層大きい熱流束を招くことがあるが、熱時定数がｄと共に同様に減少するように、装置内の温度は過剰に上昇しない。１０００〜５０μｍの範囲内の寸法ｄの値は、０．００１〜１Ａｍｐ／ｃｍ^２の電流密度値に等しい拡散制限された反応流束、微細工学的装置中の電極のために受け入れられる範囲にほぼ相当する。ｄについてより一層大きい値を有する装置のために、反応流束の割合は、拡散制限のためにより一層低くなる傾向があり、及びそれで単位装置容積当たりの生産の割合がより一層低くなる。したがって、反応性堆積物に対する試薬の混合又は輸送のためのチャネル又はチャンバの直径が小さく及び本発明の装置中のこの寸法が１０〜３０００μｍ、及び好ましくは３０〜３００μｍの範囲内であるべきことは有利である。
【０１２２】
拡散混合以外の混合処理が有効でない場合、チャネル、又はチャンバの好ましいほぼ最大の直径は、その方向で、物質が拡散するように求められ、３００μｍである。チャネル又はチャンバ内で拡散混合をさせるのに十分な所要の滞留時間は、その寸法の値に依存する。チャネルの幅に沿ったこの寸法は、チャネルの断面積を決定し、及び流体処理量はチャネル又はチャンバの断面積及び長さに、及び流体流の速度に依存する。チャネルの長さは、特に、引き出された管状構造が構成において用いられる場合、著しく伸ばすことができる。しかし、チャネル又はチャンバが電極のような微細工学的構造を組み込むのを要求される場合、及び特に、それらが通常の微細工学的技術によって実質的に平坦な基材上に与えられる場合、全体の長さ及び幅を制限するのが望ましい。代表的に、液体について、微細流体の系において、過剰な圧力運動をかけずに容易に達成できる流速は、１０ｃｍ／ｓまで変動し、及び好ましくは、０．０１〜１ｃｍ／ｓの範囲である。拡散処理を完了まで進行させるのが可能なチャネル又はチャンバのための適切な長さは、１０ｃｍまで変動し、及び好ましくは、０．１〜３ｃｍの範囲にある。
【０１２３】
層流の条件が装置内の流体流のために維持されることは、本発明の目的に必要ではない。チャネル又はチャンバは、０．１ｃｍより大きい、及びより一層通常、１ｃｍ又はそれより大きいことが求められるチャネルの直径を用いて乱れた混合を支持するのに十分大きく作ることができる。混合がチャネル及びチャンバを介した単純な流れによって誘導されるべきである場合、混合及び流れを横切る物質輸送は、これらの寸法で効率的でなくなる。しかし、効率的な混合は、パルス流又は往復流を用いることによるか、又は撹拌パドル又は磁気撹拌棒のような構造による流体の機械的かき混ぜを用いることによって誘導することができる。
【０１２４】
混合機／反応段階における寸法は、電気化学的な一次生産物生成段階及び前駆体を用いて二次生産物を生じさせる反応のための上記のものと同じ目的の拡散処理によって規定される。２種の層流ストリームが一緒に運転される場合、混合時間を制御する拡散距離ｄはこの場合もチャネル深さになる。反応が極めて迅速であり、及び１種のストリームが過剰の試薬を有する場合、そのとき、拡散距離を制限する割合は、第２のストリームからの流体に相当するチャネルの幅のその画分にまで減少する傾向がある。これは単純な及び複合的な相の流れの場合である。複合的な相処理について、制限される物質輸送距離及び時間は、いくらか変えることができるが、相が不混和性の液体である場合、すべての結果が、上述の場合を除くか、又は間期(inter-phase)輸送が力学的に妨げられる場合を除き、実質的に変わることがないと思われる。１種の相がガスである場合、そのとき、物質輸送の制限は液相中に完全に存在し、及びその相の直径によって設定されると思われる。反応はもちろん、物質輸送を制限しないことがある。力学的制限が単純な相反応のために適用される場合、微細工学的構造中での部分的な又は完全な混合を遂行し、及び次いで生産物を処理の完了のために保有容器に輸送するのが適切である。複合的な相処理のために、相の再分割及び界面の幾何学的配列の程度は、どのように流体を含み及び動かすかに決定的に依存する。
【０１２５】
上述のことは、０．１〜１０秒の範囲における反応時間について、〜１０〜１０００μｍのチャネル深さが表示されること、及び好ましくは、チャネルの深さが３０〜３００μｍの範囲であることを示す。拡散混合時間についての先の表は、ミリ秒時間規模における混合及び反応が液体試薬に求められる場合、そのとき、チャネルの深さは〜１μｍでなけらばならないことを示した。それらの条件下に達成され得るすべての流れの割合は、著しく低い（１ｃｍの広いチャネルについて〜１ｃｃ／ｈ又はそれより少ない）。以下の表は、流体の処理量についての値及びチャネルのいくつかの例の寸法についての運送時間を示す。運送時間及び拡散距離の組合せは、適切な分子量の種についての十分な拡散混合に対し有意義であることに相当する。チャネルの長さに対する制限、及び従って任意の与えられた流れの割合での利用可能な運送時間は、都合よく作製することができる構造の大きさに依存する。これらのチャネルでの層流のための所要の運転圧力についての値を、以下の表に表示する。
【０１２６】
【表２】

【０１２７】
これらの短いものから適切なものまでの運送時間について、チャネルの長さ又は圧力降下が過剰でない場合、流れの割合が、概して、１００ｃｃ／時間未満に制限される必要があることが明らかである。これらの流れの割合は、１ｃｍ幅のチャネルについてであり及びチャネルの幅に直接関連する。
【０１２８】
複合的な相の反応は、有用な間期接触面積を維持することができることに依存する。これは、寸法が減少するのでより一層困難になる。上述した種類の微細接触機及び網構造（国際特許公開第ＷＯ９７／３９８１４号参照）は、チャネルの深さが２０μｍか、又はそれより大きい場合に適用され得、流れを動かすのに求められる圧力及びその点未満の表面張力の間の均衡は、相中での緩慢な流れ(slugging flow)を生産する傾向がある。反応は緩慢な流れにおいて維持され得るが、スラッジの寸法は、割合及び流速及びスラッジ内で誘導され、及び単純な層流に適切な拡散処理によらない再循環を制御する。
【０１２９】
電解セルは、再充電可能であり、及び又は解体可能なカートリッジを構成することができ、カートリッジは、除去でき、一次生産物（例えば、金属堆積物）又は原料物質を二次生産物（例えば、有機金属生産物）が生じる処理から離れて補充されるようにすることができ、あるいはまた、一次生産物（金属堆積物）を、電気化学的処理の位置から離れて二次生産物（例えば、有機金属生産物）が生じる際に消費されるようにすることができる。
【０１３０】
流体ポンピング（圧送）手段を、好ましくは、電気化学セルを含む反応装置に接続し、そこで、流体電解質又は酸化還元活性の物質の原料を用いる。かかる流体圧送手段は、選定された流体に適切なように、遠心力ポンプ、ダイヤフラムポンプ、蠕動ポンプ、エレクトロスモティック流生成構造、磁気流体ポンプ、シリンジポンプ、及び流体力学ヘッドを維持し、流体流を動かすように位置する流体貯蔵機を含むことができる。弁及び流量調整機を、装置に及び装置から導かれる流体経路中に含ませることができる。
【０１３１】
図１ａ〜１７に記載された反応装置において、一次生産物が形成される電極１３は“作用電極”と称され、及び負の電位で保持される（すなわち、負極）一方、電極１４は正の電位で保持される（正極）。これは、アルカリ金属のそれらの化合物及び塩からの生成と整合するが、作用電極は電位が原料物質の一次生産物への変換と整合すれば何でも保持することができ、及びこれは、正の電位を含むことができる。図は概して、単純な平坦なアセンブリとして示すが、円筒形のアセンブリ及び積層シートを含む他の幾何学的配列を用いることができる。
【０１３２】
複合的な正極及び負極及びかかる電極の配列を用いることができ、及び装置は他の電極の電位を監視又は制御する１種又はそれより多い参照電極を組み込むことができる。
【０１３３】
本発明にかかる電気化学セルを組み込む合成装置において遂行することができる化学反応の種類の例は、以下に例示して説明するが、本発明を制限するものではない。
【０１３４】
１ ナトリウム、リチウム、又はカリウムのアルコキシド又はフェノキシドの形成。
電解を第１又は第２の種類の反応装置中で遂行し、一次生産物としてリチウム金属を生産する。リチウム塩又はリチウムイオン固体又は重合体導体の溶液を用い、イオン伝導性物質及び原料物質を提供する。溶液中の前駆体反応物質としてのハロゲン化アルキルが流れ、負極上に電着したリチウム金属に接触し、リチウムと反応し及び溶媒によって溶液中で運び去られ得るリチウムアルキルを形成する。化学反応の段階は以下に表す。この処理は、ナトリウム／リチウム／カリウムが直接に有機基の部分か又は他の置換基を攻撃しない限り、ナトリウム又はカリウム又はリチウムのような他の有機ハロゲン化物の前駆体物質に適用することができる。この処理を以下に示す。
Na／K／Li⁺Y^- ＋ ｅ^-（負極で） → Na／K／Li⁰（金属）
（式中、Y^-はCF₃CO₂-のような陰イオンである。）
Na／K／Li⁰（金属） ＋ R⁻OH → Na／K／Li^＋−OR ＋ H₂
（式中、R＝CH₃、C₂H₅、C₃H₇、C₄H₉、フェニル、置換されたフェニル、又はヘテロアリール、又は置換されたヘテロアリール。）
【０１３５】
リチウム前駆体を用い、副産物ハロゲン化リチウムの溶解度を供給することができる。リチウム臭化物及びヨウ化物は多くの有機溶媒中に比較的可溶であり、リチウムアルキルのその後の反応を妨げないことができ、及び有機ヨウ化物及び臭化物は、従って好ましい前駆体反応物質である。過剰なＬｉ金属が入手でき、前駆体との追加の反応（Ｒ−Ｘ ＋ Ｌｉ−Ｒ → Ｌｉ^＋Ｘ⁻ ＋ Ｒ−Ｒ）によって生産されたリチウムアルキルの消耗を避けるのを確実にするのが好ましく、及びこれは、最初の電極荷電処理を遂行してＬｉ^０堆積物を構築することによってか、又は不連続モードの操作を用いることによって達成することができる。リチウム塩電解及びリチウムアルキルの形成は、第１の種類の装置の連続操作を可能にするエーテル溶媒中で遂行することができるが、不連続操作及び第２の種類の装置でも用いることができる。
【０１３６】
生産されたナトリウム、カリウム又はリチウムのアルキルは、流体流によって混合機段階に運ばれ、それらの試薬について確立された広範な化学反応を遂行することができる。
【０１３７】
２ ナトリウムナフタレニド(Sodium Napthalenide)の形成
ナトリウム金属を堆積する電解をナフタレン溶液の流れと組合せ、その後に試薬として用いることができるナトリウムナフタレニド生産物を生じさせることができる。この処理は低い溶解度のハロゲン化物、又は生産物及び前駆体（ナフタレン）の反応での問題を含まない。イオン導体としてのナトリウムベータアルミナに基づく第２の種類の装置が適切である。すべての反応は以下に記載することができる：
Na⁺+ e^-(作用電極から) →Na⁰
Na⁰+ C₁₀H₈(ナフタレン) →Na⁺C₁₀H₈ ^-(ナトリウムナフタレニド)
【０１３８】
ナトリウムナフタレニドは、ラジカル陰イオンと関連するＮａ^＋として存在すると思われる。同様の試薬はアントラセンから導かれ〔従ってナトリウムアントラセニド(Sodium anthacenide)〕、及び芳香族前駆体に関連する他のものから導かれる。同様の試薬は、リチウム及び他の電気的陽性の金属から導くことができる。
【０１３９】
同様に、カリウムナフタレニドは、原料物質としてのカリウム、及び前駆体としてのナフタレンを用いて合成することができる。また、ナトリウムナフタレニドは、原料物質としてのナトリウム及び前駆体としてのナフタレンを用いて合成することができる。
【０１４０】
３ ナトリウム／カリウム／リチウムのアントラセニドの合成
本発明は、原料物質としてのナトリウム、カリウム、又はリチウム及び前駆体としてのアントラセンを用いることによって、ナトリウムアントラセニド、カリウムアントラセニド、又はリチウムアントラセニドの合成のために用いることができる。
【０１４１】
４ ナトリウム／カリウム／リチウムのフェナントレニド(phenanthrenide)の合成
本発明は、原料物質としてのナトリウム、又はカリウム、又はリチウム及び前駆体としてのフェナントレンを用いることによって、ナトリウムフェナントレニド、又はカリウムフェナントレニド、又はリチウムフェナントレニドの合成のために用いることができる。
【０１４２】
５ 有機スズ化合物の変換
例としての反応は以下の種類である：
Na⁺+ e^-(電極から) →Na⁰
(CH₃)₃Sn -Sn(CH₃)₃+ 2 Na⁰→2 (CH₃)₃Sn^-Na⁺
次いで、ナトリウム化合物を後の混合機／反応装置段階で、例えば、有機ハロゲン化物と反応させ、スズに追加の有機基を加える。
(CH₃)₃Sn^-Na⁺+ CH₂=CH-CH-Cl →(CH₃)₃Sn-CH₂-CH=CH + Na⁺Cl^-
【０１４３】
６ ナトリウム／カリウム／リチウムのアルコキシド又はフェノキシドの生成
ナトリウムアルコキシド又はカリウムアルコキシド又はリチウムアルコキシドを、本発明を用いて合成することができる。次の処理に基づく。
Na/K/Li⁺+ e^-(電極から) →Na/K/Li⁰
Na/K/Li⁰+ R^-OH→Na/K/Li^{+ -}OR +H₂
（式中、R=CH₃、C₂H₅、C₃H₇、C₄H₉、フェニル、置換されたフェニル、ヘテロアリール、又は置換されたヘテロアリール）
同様に生産することができるナトリウムエトキシド及び他のアルコキシド、例えば、イソプロポキシドは、化学合成において広範に用いられる。合成中に導き出される水素ガスは、概して他の反応を妨げないが、不要な流れの妨害を起こすことがある。アルコキシド及び塩の混合物は水素を発生させることなくエステルから生産することができる。
【０１４４】
７ ナトリウム金属による芳香族化合物からのハロゲン化物の除去
本発明を用いて次の処理により芳香族化合物からハロゲン化物を除去することができる。
Na⁺+ e^-(電極から) →Na⁰
_6-nNa⁰+ C₆H_nCl_6-n+ 溶媒→C₆H₆+ Na Hal + 溶媒
（式中、Hal = Cl、Br、又はI。）
例えば、Na + C₆H_nCl_6-n+ ナトリウム金属 + (プロトン供給源溶媒、例えば、アルコール) →C₆H₆+ NaCl
プロトン供給源の添加は、混合機段階それを添加し、次いで芳香族ハロゲン化物と電着したナトリウム(sodum)金属との反応によって空間的に分離されなければならない場合がある。
【０１４５】
８ バーチ還元
【化２】

この種の反応は、溶媒との適合性が確立される場合、あるいはまた、液体アンモニアに可溶なナトリウム塩が第１の種類の装置において電解質及び原料物質として用いられる場合、固体ナトリウムイオン導体と共に第２の種類の装置の種類で可能である場合がある。
例には：−
C₆H₆〔ベンゾン(benzone)〕+ 2 Na + C₂H₅OH (液体アンモニア中) →C₆H₈〔1,4シクロヘキサジエン(cyclohexadiene)〕
反応は、アルコールからプロトンを取り出すラジカル陰イオンによって進む。
【０１４６】
９ グリニャール試薬の生成
全体の反応は：
RX + Mg (エーテル中) →R-Mg-X (式中、R = C₆H₅及びX = Cl、Br、又はI)
例は、C₆H₅Br+ Mg →C₆H₅MgBr
である。
反応は、エーテル溶媒、及びエーテルのように反応を促進する溶媒中で遂行し、それらはＭｇを配位し、及び試薬を安定化させる。有機溶液からのＭｇ^０の電解堆積は可能である一方、また、それは、ナトリウムのような、従って他の反応配列のために表示したように一次生産物として用いられるアルカリ金属による溶解したマグネシウム化合物の還元によって生産することができる。
【０１４７】
同様に、イオンが適度に導電性の固体相内で可動しない金属、例えば、Ｍｇ、Ｚｎ、Ｃｄ、Ｓｎ、Ａｌのような多価イオンを有する金属のための有機金属試薬を作製するために、好ましい方法は、溶液中にそれらの金属を提供し、及び直接電着するか、又は電着したアルカリ金属を用いて第１又は第２の種類のいずれかの装置中で変換を遂行するかのいずれかである。
【０１４８】
１０ ハロゲン化生産物の生成
これは、フッ素、塩素、臭素又はヨウ素を含有する生産物の生成を含むことができる。一次生産物は、可溶性ハロゲン化物の電気化学的酸化によって生産される塩素のような元素のハロゲンでよい。
2Cl^- -2 e^-(正極で)→Cl₂
塩素は、各種の有機種と反応し、付加（不飽和結合への）又は置換によって直接に塩素化生産物を生産することができる。あるいはまた、塩素は、無機反応性中間体に変換することができる。例えば、ＰＣｌ_３及びＰＣｌ_５を、塩素と流体ストリーム中に供給され懸濁するか又は溶解するリンとの反応によって二次生産物として形成される。これらの二次生産物は装置内でカルボン酸のような追加の試薬と反応し、塩化アシルのような生産物を生産することができる。
【０１４９】
１１ ウィッティヒ(Wittig)反応によってホスホニウム塩陽イオンからのイリドの生成及びイリド及びアルデヒドの反応によるアルカンの生成。例えば：

【０１５０】
上述のカートリッジ及び方法を大（マクロ）規模で実行するのが高く評価されるが、特に、微細加工されたカートリッジ又は系を生じさせることによって微細規模上に適用することができる。
【０１５１】
本明細書の開示では、用語“流体”は気体又は超臨界液体又は水性又は非水性液体のいずれかを意味する。好ましくは、流体は液体である。好ましくは、電着されるべき金属の塩又は他の酸化還元活性の化合物は、イオン伝導性であるが、イオン伝導性物質が作用電極及び対極に結合されるように設けられる場合、導電性でなくてもよい。
【０１５２】
追加の混合要素を、必要に応じて、例えば、チャンバ中に、及び／又はチャンバへの入口、又はチャンバからの出口中に形成され及び位置させる小さな翼又はそれせ板(deflector)のようなものを、反応装置に添加し、流体を回転させるか、又は混合することができる。
【０１５３】
多数の化学反応が記載した反応装置中での操作のために考えられるが、電気化学的なアルカリ金属の生成及びナトリウムナフタレニド又はリチウムアルキルのような有機金属試薬を形成するための有機試薬とのそれらの反応が好ましい。
【０１５４】
したがって、かかる反応装置は、合成化学者の実験ベンチ上での用途を見つけることができ、及び製造方法のための複合的な装置又は配列装置の使用によって拡大するか、又は範囲を超えることができる。例えば、本発明の第１の反応装置の出口導管を流れの連続中に本発明に従って構成される他の反応装置の入口導管に接続することができる。
【０１５５】
同様に、複数の連続して接続された反応装置は共通の構造上に設けることができる。１種又はそれより多い配列の連続して接続された反応装置は、共通の構造上で他の１種又はそれより多い配列の連続して接続された反応装置に関連して配置することができる。この概念は、集積回路チップ上に構築される構成要素のものとは似てないことはないが、この場合、構成要素は微細工学的反応装置である。
【０１５６】
重要なことには、本発明の反応装置は、危険な廃棄化学物質及び溶媒をより少ない危険性の形態に変換するのに適用することができるが、特に、ＰＣＢ（ポリ塩化ビフェニル）及びＣＦＣ（塩化フルオロカーボン）のようなハロゲン化生産物の変換及び浄化に制限されない。かかる変換は、ナトリウムのような一次生産物と変換すべき化学物質との直接的反応によってか、ナトリウムナフタレニドのような二次生産物の生成、次いで変換すべき化学物質との混合及び反応によって続けることができる。ＰＣＢのための分解／浄化試薬としてのナトリウムナフタレニドの使用は、ナトリウム金属によるＣＦＣの反応性の脱ハロゲン化を有するように報告されている。これらの廃棄物は、電気化学的に生じるアルカリ金属（例えば、ナトリウム）を用いるか、本発明にかかる電気化学的に生じるアルカリ金属を用いるカートリッジによって、本発明の装置において直接の処理を受けさせることができる。
【図面の簡単な説明】
【０１５７】
【図１】１ａ及び１ｂは、本発明を組み入れた２種の微細工学的反応装置を図解的に示す図である。
【図２】本発明の具体例を組み入れた微細工学的反応装置を図解的に示す図である。
【図３】本発明の具体例を組み入れた微細工学的反応装置を図解的に示す図である。
【図４】本発明の具体例を組み入れた微細工学的反応装置を図解的に示す図である。
【図５】本発明の具体例を組み入れた微細工学的反応装置を図解的に示す図である。
【図６】本発明の具体例を組み入れた微細工学的反応装置を図解的に示す図である。
【図７】本発明の具体例を組み入れた微細工学的反応装置を図解的に示す図である。
【図８】本発明の具体例を組み入れた微細工学的反応装置を図解的に示す図である。
【図９】本発明の具体例を組み入れた微細工学的反応装置を図解的に示す図である。
【図１０】本発明の具体例を組み入れた微細工学的反応装置を図解的に示す図である。
【図１１】本発明の具体例を組み入れた微細工学的反応装置を図解的に示す図である。
【図１２】本発明の具体例を組み入れた微細工学的反応装置を図解的に示す図である。
【図１３】本発明の具体例を組み入れた微細工学的反応装置を図解的に示す図である。
【図１４】本発明の具体例を組み入れた微細工学的反応装置を図解的に示す図である。
【図１５】本発明の具体例を組み入れた微細工学的反応装置を図解的に示す図である。
【図１６】本発明の具体例を組み入れた微細工学的反応装置を図解的に示す図である。
【図１７】本発明の具体例を組み入れた微細工学的反応装置を図解的に示す図である。【Technical field】
[0001]
The present invention relates to micro-engineered reactors for use in the synthesis of organic compounds by processes involving electrochemical reactions, and to methods of using such micro-engineered reactors. The synthesis process electrochemically converts the source materials into reactive primary products, precursor materials that are exposed in the reaction area within the channel or chamber, and reacts the primary products and precursor materials to form a secondary product. It is of the kind that gives rise to products.
[Background Art]
[0002]
Electrochemical reactions have been used relatively little in the synthesis of organics. This is due to various limitations, including the lack of cleanliness of most organic species and the identification of direct electrochemical conversion, limitations on polar ionically conductive media that are incompatible with many organic synthesis processes. And the relatively low ionic conductivity of organic solutions, which can limit current and throughput. The current can be increased by increasing the applied potential, which increases the heating of the ion-conducting fluid body and makes it difficult to achieve a controlled potential and clean electrochemical treatment at the electrodes. Tends to give.
DISCLOSURE OF THE INVENTION
[Means for Solving the Problems]
[0003]
However, many are widely used in synthesis reactions, which utilize reactive high energy reactants. Examples of such reactants are organometallic materials such as lithium or sodium alkyls, and Grignard reagents. Long-term storage of such materials may be impractical or harmful, and they are often synthesized from precursor reagents and active metals shortly before use. Active metals are used in the synthesis of organometallics, especially alkali metals, which themselves are harmful or difficult to handle and which accumulate during storage corrosion products which prevent their use in organic synthesis. There is. The active metals are usually supplied by the producer as sheets, rods, or granules, which are cut in an oxygen-free dry state or otherwise in a protected environment prior to use in organic synthesis. Or otherwise mechanically treated to produce a sufficiently clean and active surface area. The handling and processing of these active metals can be detrimental and can add to the difficulty of processing and the expense of producing the desired organometallic reagent. Active metals for use in synthesizing organometallic species according to conventional methods can or can be generated electrochemically. An advantage of the proposed device is that such a substance is generated at that location as a primary product for reaction with the precursor reagent. The proposed device allows for the controlled production of active metals and their derivatives in an encapsulated device that minimizes the risks associated with handling excess material and exposure to contaminants.
[0004]
Microfabrication techniques are known in the semiconductor industry for the manufacture of integrated circuits and miniaturized electronic devices. In addition, micron (10^-6Complex fluid flow systems having channel sizes as small as meters. These devices can be mass-produced inexpensively, and widespread use for simple analytical tests is immediately expected. For example, Ramsey, JM et al. (1995), "Microfabricated chemical measurement Systems", Nature Medicine 1: 1093-1096; and Harrison, DJ et al. 1993), "Micro-machining a miniaturized capillary electrophoresis-based chemical analysis system on a chip", Science 261: 895-897. Miniaturization of experimental techniques is not a simple matter of reducing their size. On a small scale, the different effects become important, making some processes inefficient and otherwise useless. Replicating smaller deformations of some devices is difficult due to material or process limitations. For these reasons, it is necessary to develop new methods for miniaturizing common laboratory work.
[0005]
Devices made with micro-machined planar substrates have been made and used for chemical separation, analysis, and detection. See, for example, Manz, A. et al. (1994), "Electro-osmotic pumping and electrophoretic separations for miniaturized chemical analysis systems." ", J. Micromech. Microeng. 4: 257-265. In addition, devices have been proposed for preparative, analytical and diagnostic methods of laminating two streams of fluid and diffusing molecules from one to the other into one another, Examples thereof are proposed in WO96125541, WO9700442 and US Pat. No. 5,716,852.
[0006]
For the purposes of this disclosure, the terms "microfabrication" and "microengineering" include plastic, glass, silicon wafer or photolithography, screen printing, wet or dry isotropic and anisotropic etching, Ion etching (RIE), laser assisted chemical etching (LACE), laser and mechanical cutting of metal, ceramic, and plastic substrates, plastic lamination technology, LIGA, thermoplastic micropattern transfer, resin-based microcasting, in capillaries Devices fabricated on any other material readily available to those performing microfabrication techniques, such as micromolding (MIMIC) and / or other techniques known within microfabrication techniques Is included. As in the case of silicon micromachining, multiple inventive devices can be adapted in multiple configurations using even larger wafers. Some standard wafer sizes are 3 "(7.5 cm), 4" (10 cm), 6 "(15 cm), and 8" (20 cm). The application of principles using the new and emerging microfabrication methods presented herein is within the scope and intent of the present invention. The microfabricated device comprises (1) photolithography, optical processing to create a microscopic pattern, (2) etching, processing to remove substrate material, and (3) deposition, whereby the material has a specific function. Can be made by a combination of manufacturing processes, such as a process capable of coating on the surface of a substrate.
[0007]
The connection of the device to an external liquid reservoir can be made by adhesive bonding to fine tubes and capillaries, other connections to the cathode structure or to a manifold structure connected to a macroscopic union, or Proceedings of Mourlas, NJ, etc. It can be made by various means, including methods according to the μTAS'98 Workshop, Kluwer Academic Publishers 27-, and methods according to the literature cited therein.
[0008]
It is an object of the present invention to provide micro-engineered reactors and methods of using such micro-engineered reactors, which are provided by electrochemical means which overcome at least some of the problems encountered in the past. Suitable for the synthesis of organic compounds, including reaction with in situ produced materials, and take advantage of micro-engineered flow passage.
[0009]
By using micro-engineered sized reactors, it is possible to achieve short ion conducting paths that limit resistive voltage drop and heating. The short diameter of the fluid relative to the surface that can be cooled avoids excessive temperature rise either from ohmic (Joule) heating or from high energy products. The flow of reagents through relatively narrow channels or chambers allows for rapid, diffusive transport of reagents to the surface, allowing the precursor reagents to be efficiently and quickly converted to primary electrochemical chemicals such as reactive metal layers. Given to the product. Producing active primary and subsequent products in the reactor on demand avoids harmful inventory accumulation, provides equipment with a limited level, and poses inherent risks in material handling. can avoid.
[0010]
By using micro-engineering techniques, depth features can usually be defined by etching or depositing material and forming conduits or flow channels with depth dimensions down to １1 μm. In general, for the purposes of the present invention, the term “microtechnical” refers to a channel having a depth of 0.1 to 1000 μm. Channel depths of up to 1000 μm allow for significantly higher throughput and lower viscosities, but the preferred range size is between 1 and 500 μm and especially between 30 and 300 μm. The width and length of the channel are generally defined by lithographic techniques and may be of a size from a few μm to cm. By using such a conduit and flow channel combination, transport and mixing times from on the order of seconds to milliseconds in liquids and microseconds in gases can be achieved.
[0011]
The use of electricity to drive redox reactions is well known and is applied in electrolytic extraction of aluminum metal from ore using molten electrolytes, electroplating and rechargeable batteries. Electrochemical redox treatment involves transporting one or more electrons between an electrode and a chemical species in an electrochemical cell. Chemical species capable of gaining or losing electrons in this way are redox-active species. Such species are converted to other species by transport of charge and may undergo additional conversions, including rearrangements, reactions, and phase changes.
[0012]
An additional object of the present invention is to provide a new use of the basic technology of using electricity to direct a redox treatment in a reactor and to produce reactive products in situ that react in the reactor as part of a synthesis reaction. It is to be.
[0013]
The operation of the reactor of the present invention involves a number of transport operations that are affected by the configuration and dimensions of the reactor, with preferred dimensions being within the range appropriate for microtechnology. Processes typically involved include electromigration, electrodeposition, and diffusion of substances and reagents to reaction sites such as electrodes and electrodeposits, mixing of fluidic reagent streams, reaction, and heat generation or consumption and heat transport. Is included. As described below, conditions for rapid ion transfer, mass transport by diffusion, and heat transport across the fluid layer in the reactor can be improved, and increasing the ratio of reaction flux to reaction zone volume. Where the thickness of the intersecting layers is in the micro-engineered range from 1 μm to 1000 μm, and preferably in the range from 30 μm to 300 μm.
[0014]
In one aspect of the invention, a micro-engineered reactor suitable for electrochemical synthesis of organic compounds is provided.
[0015]
In another aspect of the present invention, there is provided a method of using a micro-engineered reactor for the purpose of producing an organic compound.
BEST MODE FOR CARRYING OUT THE INVENTION
[0016]
The present invention will now be described by way of example with reference to the accompanying drawings.
1a-17, the reactor is shown in cross-section, and schematically illustrates the height and length of the channel. The width of the channel is not shown, but is similar to or greater than the height of the reactor, up to the limit imposed by the width of the material or substrate used to fabricate the reactor.
[0017]
In general terms, the present invention is broadly applicable to the synthesis of organic compounds by reactions using reactive primary products that are electrochemically generated from raw materials. In general terms, the source material is electrochemically converted to a reactive primary product, which is exposed to the precursor material in a reaction area within the channel or chamber, where the primary product and the precursor material react and react. Produce the next product. For example, the precursor material can consist of or contain a fluid organic reagent. Organic reagents can be dissolved in a solvent. In one example, the primary product is a reactive metal that is electrochemically generated from a source material that can be a salt or other redox-active compound of the metal. The precursor and the primary product react to form a secondary product, which may be an organometallic compound.
[0018]
Source material can be present at or adjacent to the electrode and can be transported to the electrode area by a fluid stream. Preferably, the source material is one that is mobile and can be dissolved in a solvent as much as possible. The source material is preferably a salt or other redox-active compound that can be converted by electrolysis to form a primary product.
[0019]
The reactor may include equipment in any of the channels, or chambers, for the reaction of the secondary product with additional reactants, where the secondary product is formed or otherwise. Channels or chambers in which the secondary products are carried by the fluid stream. The device has two or more separate electrodes, a working electrode and a counter electrode, between which an ion-conducting substance is provided and an electric current is applied during the electrochemical production of the primary product to the electrodes and the intervening ionic conduction. It flows by the sexual substance (or phase). The primary product is formed electrochemically at the working electrode. Other redox treatments occur at the other end.
[0020]
The ion-conducting material can consist of or contain a source material, and can include a solvent and a supporting electrolyte and a redox-active material to support electrochemical processing at the counter electrode. The solvents used for the source material, the supporting electrolyte, and the precursor material can be the same or different materials and can be miscible or immiscible. Polar aprotic solvents work particularly advantageously to provide an ion-conducting phase.
[0021]
The processes performed in the micro-engineered reactor are electrochemical redox processes that produce primary products such as reactive metal deposits or other highly reactive or electrochemically generated unstable species, and A reaction between a primary product and a supplied reagent or precursor material, wherein the secondary product, such as an organometallic species, is in the same micro-engineered reactor or in a similar micro-engineered reactor. Can be combined.
[0022]
A preferred embodiment of the present invention is directed to the synthesis of organometallics by electrochemically producing a reactive metal as a primary product and producing an organometallic as a secondary product by the reaction, Includes the production of non-metallic primary products for subsequent reaction. Such a primary product may be an electrochemically generated non-metallic material, including components and compounds, and including species or materials generated by direct electrochemical oxidation or reduction of organic species, including organic ions. And can include free radical species. The primary product is formed at or adjacent to the electrode, exposed to the precursor material and reacted at least temporarily until it forms a secondary product that is processed from the reaction location by the fluid stream. Can remain. Alternatively, the primary product produced in the first part of the reactor, or a similar micro-engineered reactor, is dissolved or as a suspension, in a fluid phase (eg as particulate or colloidal metal). ) And can be conveyed by a fluid stream from a first portion of the reactor or reactors to a second portion for mixing and reaction to form a secondary product. Secondary products are themselves used as reactants and can produce tertiary products either in their equipment or after transport to other equipment or the environment.
[0023]
In some cases, the process of forming the primary and secondary products and any intermediate forms may not be elucidated, and it is not necessary that the objects of the present invention be achieved by elucidating them.
[0024]
In a preferred embodiment of the present invention, the proposed micro-engineered reactor comprises a conduit and carries one or more reactant solutions to a chamber containing one or more electrodes, and a product solution. Transport from The conduits and chambers are formed by micro engineering.
[0025]
A reaction apparatus in which the active metal used for the synthesis of the organometallic species can be generated electrochemically, and it is proposed that such a material be generated in situ as a primary product for reaction with a precursor material. Is the advantage. The application of the precursor reagent to the electrochemically generated primary product occurs immediately or after a short delay, resulting in a secondary product such as a reactive organometallic species. The reactor can be a convenient source to meet the demand for reagents such as organometallics from readily available and non-hazardous precursors. An additional advantage is that secondary products can be used in that location, avoiding storage losses and dangers.
[0026]
The proposed reactor combines a series of raw materials or precursor materials or reagents in a controlled manner with electrolysis applied only on demand. Thus, it is possible to control the use of redox-active reagents and the production of redox-active products, while exposing them to an electrochemical conversion process.
[0027]
The electronic circuitry for passing charge through the reactor can be manipulated, the potential and current can be controlled, and these can be varied over time. These include a constant voltage circuit and a constant current circuit.
[0028]
The reactor of the present invention can be operated in two ways. In the first embodiment (hereinafter, referred to as “continuous mode”), the electrochemical production of the primary product and the supply of the precursor are simultaneously performed to perform the continuous reaction and the production of the secondary product. In a second embodiment, hereinafter referred to as "discontinuous mode", the electrochemical production of the primary product is performed during a first time period and the precursor supply is performed during a second time period. The primary product accumulates in a first time period, and the reaction between the accumulated primary product and the precursor occurs to produce a secondary product in a second time period. The first and second periods can be alternately repeated. Other time periods can separate the first and second, and the second and first periods. The flushing or washing solution can be applied to the reactor during these other periods. By operating in discontinuous mode, different solvent systems can be used during the processing of the primary product formation and the reaction of the primary product with the precursor to form the secondary product. This extends the range of chemical reactions, which can be used as optimal conditions, and the solvent environment is treated with primary products and precursors to form the primary product and to form secondary products. It is not necessary to make the same for the treatment of the reaction.
[0029]
Two basic geometries or types are preferred for the reactor of the present invention. Devices of the first type or geometry (illustrated schematically in FIG. 1a) incorporate an electrochemical cell, wherein at least some of the space between the working electrode and the counter electrode contains source material, ions Occupied by a fluid containing a conductive material, and a redox-active material, supporting the electrochemical treatment at the counter electrode, the materials can be the same or different, and an ion-conducting passage connects the electrodes. The current between the electrodes and the space is also occupied by the precursors for the reagents to be generated, either simultaneously, as described above, or at different times. The electrodes can be arranged on opposite sides of the chamber or flow channel, or side by side on the walls of the chamber or flow channel, as shown diagrammatically in FIGS. 1a and 1b.
[0030]
Devices of the second type or geometry (illustrated schematically in FIG. 1b) incorporate an electrochemical cell, where space is used for ionic conduction during the electrochemical production of the primary product. And the space for the addition and transport of the precursors are separated by a structure comprising at least the electrode structure giving rise to the primary product, and where by such a separation structure the primary product and the precursor to be attracted to each other Material transport is realized.
[0031]
The device of the second type or geometry can be operated in a continuous or discontinuous mode, as for the device of the first type or geometry. With a second type of geometry, there is no need to clean the electrolyte outside the precursor or product fluid flow passages. However, in a discontinuous or pulsed manner, it is convenient to operate the device so that sufficient primary product (such as an alkali metal) is built up on the working electrode or the precursor material, and Alter the feed of the source material, where the source material is fed into the fluid and the fluid is different from that for the precursor feed, or to transport the precursor to the working electrode and product therefrom. Vary in the solvent used. Structures with multiple fluid inlets and outlets can also be used for devices of the second type or geometry.
Embodiment 1
[0032]
Referring to FIGS. 1a and 1b, a first type of reactor is shown schematically in FIG. 1a, which comprises two types of conductive structures or substrates forming two electrodes, a working electrode 13 and a counter electrode 14. Includes a chamber 11 in which is installed. The electrodes 13, 14 are used to connect to a power supply and a potential is applied between the electrodes 13, 14. Chamber 11 has an inlet 12 for receiving one or more fluids, which uses the fluid or fluids for forming and reacting electrochemical products in chamber 11.
[0033]
The first fluid entering the chamber 11 comprises or contains an ionically conductive material and a source material, such as, for example, a metal salt dissolved in an organic fluid, and the chamber 11 between the electrodes 13 and 14. There is an ion conductive path through Following the passage of current between the electrodes 13 and 14, the electrochemical formation of a primary product, such as a metal, deposits the metal 16 on the electrode 13.
[0034]
The second fluid entering the chamber 11 can be the same as the first fluid or can be combined with the first fluid stream and consists of a precursor reactant, such as, for example, an alkyl halide; Or it can be contained. The precursor reagent reacts with the primary product to form a secondary product, such as, for example, an organometallic compound. The second fluid (precursor reactant) flows through the chamber 11 along a fluid path 17 adjacent to the electrode 13, which may occupy all or only part of the chamber 11.
[0035]
The primary product 16 electrochemically deposited on one or more surfaces of the substrate 13 is exposed to a precursor reagent in the chamber 11 for use. Primary product 16 reacts with the precursor reagent to form a secondary product. The source material and the ion-conducting material may be the same or different materials, and for different materials, they must both be present in the chamber 11 when current is passed to form the primary product 16. Must.
[0036]
The source and precursor materials can be delivered in the same or different fluids, either simultaneously or at different times. The chamber 11 has an outlet 15 through which reactive products such as, for example, organometallic compounds can be removed. Used fluid or fluids containing reduced source material and precursor reagents can exit chamber 11 via outlet 15. The function of the inlet 12 and the outlet 15 can be changed from time to time by reversing the flow of fluid through the chamber 11.
[0037]
A second type or geometry of reactor is shown schematically in FIG. 1b. In this type of device, the volume used for ion conduction is separated from that used for precursor addition and transport.
[0038]
The second type of reactor comprises a chamber 11 in which two electrically conductive substrates forming an electrode, a working electrode 13 and a counter electrode 14 are installed. The electrodes 13 and 14 are used to connect to a power supply, and a potential is applied between the electrodes 13 and 14. Chamber 11 has an inlet 12 for receiving one or more fluids carried through chamber 11 to an outlet 15 along a fluid path 17 adjacent to electrode 13 but not between electrodes 13 and 14. .
[0039]
A second type of reactor, shown in FIG. 1 b, involves a volume separation in the chamber 11. The volume 11a is used for ion conduction and is used for the addition of precursors and reagents and for transporting the product of the reaction by the permeable electrode 13 which allows substances to be transported across the working electrode 13. 11b. In this way, the primary product and the precursor reactant come into contact within the volume 11b, forming a secondary product that can be transported into the adjacent fluid flow passage 17.
[0040]
The permeability of the electrode 13 can be determined by using a structure such as a perforated structure or a mesh or strip arrangement, or to the primary product, or to contain the precursor reagents and secondary products. This can be achieved by using an electrode material that is essentially permeable to the fluid to be made.
[0041]
An additional requirement for a second type of geometry is that the counter electrode 14 is located within the chamber 11 but outside the flow path 17 of the precursor reagent, and the chamber between the electrodes 13 and 14 11 is that its region 18 contains at least an ion-conducting substance during the electrolytic production of the primary product 16 at the electrode 13.
[0042]
Region 18 may comprise inlet and outlet tubes not shown in FIGS. 1a and b, or may be occupied by a static ionic conducting phase, which may be a fluid, semi-solid, or solid ionic conductor. it can. The ion-conducting phase can contain or consist of raw materials. Raw materials for electrochemical conversion to primary products can be introduced into region 18 or channel 17 depending on the chemical reaction selected. Preferably, this arrangement allows the primary product produced at the working electrode 13 by an electrochemical reaction on the source material by the passage of current through the ionically conductive material between the electrodes 13 and 14 to pass through the electrode 13 And interacts with the precursor reagent in the adjacent channel 17.
[0043]
The passage of current between the electrodes 13 and 14 through the region 18 of the chamber 11 causes an electrochemical formation at the electrode 13 of a primary product, such as, for example, a metal deposit 16. The fluid entering the chamber 11 along the flow path 17 adjacent to the electrode 13 is, for example, a precursor reactant such as an alkyl halide, or contains it and a secondary reactant such as an organometallic compound. The product is formed by reaction with the primary product.
[0044]
Fluid path 17 may not occupy that portion of chamber 11 between electrodes 13 and 14. A primary product 16 that is electrochemically deposited on one or more surfaces of a substrate 13 is used and exposed to a precursor reagent in chamber 11. Primary product 16 reacts with a precursor reagent to form a secondary compound, such as, for example, a sacrificial layer of metal on electrode 13.
[0045]
As mentioned above, with respect to the first type of device, if one has the second type of device, the source material and the precursor material can be transported in the same or different fluids simultaneously or at different times. can do.
[0046]
The chamber 11 has an outlet 15 through which reaction products such as, for example, organometallics are removed. The spent fluid or fluids containing reduced source material and precursor reagents can exit chamber 11 via outlet 15. The function of the inlet 12 and the outlet 15 can be changed from time to time by reversing the flow of fluid through the chamber 11.
[0047]
For both devices of the first and second types, the source material and the ion-conducting material may be the same or different, and if different, both pass current between the electrodes 13,14. Must be present in chamber 11 when forming primary product 16. Source and precursor materials may enter the chamber in the same or different fluids, either simultaneously or at different times.
[0048]
Primary products 16 are generated from the source material by charge transport at the working electrode 13. If the primary product 16 is produced by a reduction process, the working electrode is connected as a negative electrode, as if the primary product was a metal produced by electrochemical reduction of a metal salt or compound at the working electrode 13 . This is achieved by connecting the electrodes 13 and 14 of the electrochemical cell to an external electrical circuit, which maintains a potential bias between the electrodes and normal current flows from the working electrode 13 to the external circuit. Most commonly, this corresponds to the fact that the working electrode 13 as the negative electrode is potentially negatively biased with respect to the counter electrode 14 as the positive electrode, as shown diagrammatically in FIGS. 1a and 1b.
[0049]
Alternatively, if the primary product 16 is produced by an oxidation process, the working electrode is connected as a positive electrode, such as when the primary product is a halogen generated at the working electrode 13 from a halide salt source material. This is achieved by connecting the electrodes 13 and 14 of the electrochemical cell to an external electrical circuit, which maintains a potential bias between the electrodes and normal current flows from the counter electrode 14 to the external circuit. Most commonly, this corresponds to the working electrode 13 as the negative electrode being potentially positive and biased with respect to the counter electrode 14 as the negative electrode.
[0050]
In operation, for example, a primary product 16 such as a sacrificial metal layer is electrochemically deposited on the electrode 13 by connecting the electrode 13 as a negative electrode and the electrode 14 as a positive electrode in an electrical circuit. . The ion-conducting substance is present in the space between the electrodes 13 and 14 and the raw material, which can be a metal salt or a redox-active compound, is provided at least to the working electrode 13. The application of a potential difference between the electrodes 13, 14 generates a current and flows between the positive and negative electrodes, whereby the primary product 16 (such as a metal) is electrodeposited on the working electrode 13 You.
[0051]
In the discontinuous mode of operation, the electrochemical production of the primary product 16 is performed in a precursor reagent deficient state until sufficient primary product has been deposited on the working electrode 13. The potential that maintains the current between the positive and negative electrodes through the cell is removed, and the organic precursor reagent flows along the flow path 17 through the chamber 11 and reacts with the primary product 16. Operation in this mode is an efficient "discontinuous" or batch process.
[0052]
In the embodiment described herein, primary product 16 is deposited prior to introducing the precursor reagent into chamber 11. In an alternative embodiment, in a continuous mode of operation, the primary product 16 is electrochemically coupled with the passage of the precursor reagent through the channel 17 and the reaction of the precursor reagent with the primary product 16 at the same time. Can be caused. Operation in this mode is an efficient "continuous" process.
[0053]
The operation of various embodiments of the present invention and the construction of various micro-engineered reactors constructed in accordance with the present invention is illustrated in FIGS.
[0054]
FIG. 2 schematically illustrates a continuous process in a first type of reactor, showing a continuous flow of an ion-conducting reagent mixture containing source materials through a chamber 11, which comprises a salt (eg, , M⁺Y⁻) And precursor reagents (e.g., RX). Raw material (eg, M⁺Y⁻) Is flowed in a flow path 17 between the excited electrodes 13 and 14 and a primary product 16 (eg, M⁰) Is produced at the electrode 13 or in the flow path 17 adjacent thereto, and the primary product is then reacted with an organic precursor reagent (e.g. RX) to produce a useful secondary product (e.g. M- R). The primary product is formed on the working electrode as an adherent deposit (as shown schematically in the upper half of FIG. 2), or it is a solution or as shown schematically in the lower half of FIG. It can be a fluid stream as a suspension. Primary products 16 of intermediates by electrolysis (eg, M⁰) Need not be identifiably formed. Useful secondary products (e.g., MR) are carried by the fluid stream to the next junction 19, where additional reactants (e.g., R'-W) are mixed and reacted (e.g., M-R). → RR ′) is carried in via conduit 20. The tertiary product R-R 'is carried off in the stream via the output conduit 21. Reagents R'-W and the tertiary product R-R'mat are compounds and when they pass through the electrochemical cell section, for example, R'-W is introduced into the feed stream to the electrochemical cell. If not, they will be subject to modification. The simplest structure that accomplishes the above is illustrated schematically in FIG. 2, where the process shown is based on M with a negatively polarized working electrode 13 operated as a negative electrode.⁺Including the reduction of
[0055]
An alternative treatment is an oxidation treatment (eg, Cl 2) formed when the positively biased working electrode 13 is operated as the positive electrode.⁻Generated from the raw material containing₂) May include a reaction with the primary product 16 formed.
[0056]
Monovalent cation M⁺Although the electrochemical conversion of is shown, the treatment is applicable to raw materials containing polyvalent, negatively charged, and even neutral species as long as they are electrochemically active. is there. The charge and relative importance of electrophoresis, diffusion, and advective processes can affect mass transport to electrodes. In the simple configuration illustrated schematically in FIG. 2, both the positive and negative electrodes are in direct contact with the reagent stream, and the products from both the positive and negative electrode regions are conveyed to the subsequent reaction zone. These may include side products from the positive and negative electrode areas. By-products from the counter electrode 14 that are not directly involved in the required reaction can be diverted from the subsequent reaction zone by appropriate flow configuration.
[0057]
The manner in which unwanted products are diverted from the reaction zone is represented graphically in the apparatus of FIG. This separates the desired product exiting the chamber 11 via the outlet 15 and around the counter electrode 14 and working electrode 13 with unwanted product from the area adjacent to the electrode 14 passing along the output conduit 22. It can include a separating flow.
[0058]
The electrodes can be located outside the flow stream that is directed to a subsequent reaction location as shown in FIG.
[0059]
As shown in FIG. 4, the counter electrode 14 should be located in the outlet conduit 22 outside of the flow stream 17 adjacent to the electrode 13 as long as a sufficient ion conductive path can be maintained between the electrodes 13 and 14. Can be. Unwanted products are conveyed via conduit 22 without contaminating the desired products via outlet 15.
[0060]
As shown in FIG. 5, the feed streams to the positive electrode 14 and the negative electrode 13 can be different, and the flow of raw materials and precursor reagents from the inlet 12 flowing into the chamber 11 adjacent to the electrode 13 and the flow of the electrode 14 It may have fluid from the inlet 23 flowing off. The two fluids may be of different compositions and may be immiscible as long as they both have sufficient ionic conductivity and maintain a conductive path between the cathode 14 and the anode 13.
[0061]
The fluid path can be controlled by adding an ion-permeable barrier between the positive and negative electrode regions, as well as separating the products from the two electrodes by the flow arrangement as indicated above. This may be a porous sheet (unglazed plate), a dialysis membrane, an ion exchange membrane, or a region of the immobilized electrolyte that is gelled or not.
[0062]
As well as separating the products from the two electrodes 13, 14 by the flow arrangement as indicated above, the fluid passages define the location of the ion-permeable barrier 24 between the areas adjacent to the electrodes 13, 14. Can be controlled. This barrier 24 divides the chamber 11 into negative and positive compartments, as shown in FIG. This barrier 24 may be a porous sheet, a dialysis membrane, an ion exchange membrane, or an area of immobilized electrolyte, gelled or not.
[0063]
The one or more electrodes can be constructed as a porous or reticulated type of conductive structure, as shown in FIG. This can increase the surface area of the electrode, and the porous body can be used to establish an area within the chamber 11 through which a portion of the fluid passes. Within the porous electrode structure, the diffusion and heat transfer distance from the solution to the electrode material is reduced. In the apparatus of FIG. 7, the working electrode 13 for primary product formation and reaction takes the form of a conductive porous body. Such a porous electrode can be used in combination with an ion permeable membrane of the type shown in FIG.
[0064]
In the reactor shown in FIGS. 2-17, the dimensions of the channel through which the fluid flows are such that the reagent flowing off the working electrode 13 or the electrode 14 is efficiently carried to the electrode surface, for example by diffusion, and reacts with each electrode. It is something. The electrodes 13, 14 may form part of the channel wall (as shown in FIGS. 2-6) or may be a separate structure separate from the channel or chamber walls. The electrodes can additionally be configured as porous blocks or nets of conductive material. Fluid may pass over the surface of the porous electrode or flow through the porous electrode by a pump, and electrode treatment and electrode location may occur in the pore wall.
[0065]
Improved versions with porous electrodes can be based on other options described herein and can be used by continuous or discontinuous operation.
[0066]
Although shown for continuous operation, the structures of FIGS. 2-7 described above can also be used for discontinuous operation. In this mode, current flows between the electrodes 13, 14 to produce a primary product, for example, a metal such as lithium, which is held at or adjacent to the working electrode 13. Therefore, the area adjacent to the electrode 13 is loaded with the primary product. Thereafter, a precursor reagent, or a solution of the precursor reagent, is applied to the electrode 13, which is loaded by the primary product, and the reagent reacts with the primary product to produce a secondary product.
[0067]
The reaction between the primary product and the precursor reagent need not involve the current passing through the device, and the precursor reagent solution need not be ionically conductive. This secondary product can be dissolved in the fluid containing the precursor reactants and can be carried by the fluid to additional reaction locations in the device. Alternatively, as formed, the primary product can be deposited in the reservoir at or at the outlet from the outlet channel 15 or the chamber 11.
[0068]
Other fluids pass in contact with the secondary product and either accumulate in the device or are retained in the fluid in which it occurs, and are separated by multiple fluids or transported by multiple fluids. The secondary product can be received and the secondary product can be carried from the electrode area, and the stream can carry the secondary product from outside the device or within the device to an additional reaction location.
[0069]
Operation of the reactor in discontinuous mode using two fluids passing alternately through the reactor is illustrated in FIG.
[0070]
8A, the ion conductive solution (M⁺Y⁻, For example, a solution of a lithium salt) flows through the chamber 11 and an electric current passes between the electrodes 13, 14, where the primary product 16 (M⁰For example, lithium metal deposition at the negative electrode). Once sufficient deposition has been established, the current stops and the fluid flow changes as shown in FIG. 8B, the flow of electrolyte from the inlet 23 ends, and the precursor reagent fluid (R-X solution) Is introduced via the inlet 12. The reagent fluid reacts with the primary product 16 deposited on the negative electrode 13 that produces the product, and the product flows from the inlet conduit 20 where it can mix and react at the junction 19 and beyond. To the joint 19 having
[0071]
As shown in FIGS. 8A and 8B, the junction between the different fluid flows is open and flow control is exerted by varying the pressure and flow at inlets 12, 23 and 20. For microdevices this is often appropriate and can be used to tolerate a low degree of contamination of one fluid with another. However, it is advantageous to insert the valve structure at one or more junction inlets 12, 23 and 20 to control the flow of multiple fluids and control the contact between multiple fluids. it can.
[0072]
In those cases, if the solution carrying the precursor reagent to the electrode 13 loaded with the primary product does not dissolve or remove the secondary product formed, a third fluid is indicated in FIG. It can be introduced into the circulation via an inlet 24 as described below. The use of a third fluid stream indicates that the product is useful even if it does not dissolve or is removed in the second fluid. Greater control and flexibility in the operation of the system is achieved by introducing a solvent or a different fluid between the ion-conducting fluid introduced via inlet 23 and the precursor introduced via inlet 12. can do. This can also ensure that mixing between these fluids is minimized, thereby reducing product contamination and side reactions.
[0073]
The arrangement for coupling the inlets 12, 20, 23, or 24 of the various fluid feedstocks can be chosen for convenience in manufacturing or in an arrangement of operations as shown in FIG. 10, and as shown in FIG. The use of a simple valve 25 may be included. In FIG. 11, the valve is shown as a rotary valve for selectively connecting one of the inlets 12, 23 or 24 to the chamber 11.
[0074]
FIG. 12 shows a second type or geometry of reactor based on the design depicted in FIG. 1b. In the reactor of FIG. 12, the chamber 11 is divided by the electrode 13 into a region 18 containing an ion-conducting substance providing an ion-conducting passage for electrolysis and a fluid passage 17 for carrying the precursor reagent. Regions 17 and 18 are separated, but adjacent and separated by a permeable working electrode 13, which must be porous or otherwise permeable, the primary product 16 and the precursor The body reagents are contacted and reacted to form a secondary product.
[0075]
As shown in FIG. 12, the fluid flow along path 17 carries the secondary product to junction 19 where it mixes and reacts with other reagents from inlet 20. The working electrode 13 can be in the form of a porous block through which the fluid flowing along the flow path 17 passes in a manner similar to that shown for the first type of device in FIG. Similarly, the counter electrode 14 can be in the form of a porous block, through which the ion-conducting fluid containing the substance flows and supports the electrochemical treatment at the counter electrode. Similarly, a compound inlet can be provided in that portion of the chamber 11 occupied by the fluid stream 17, with the reactants and solvents changing in a manner similar to that described above for the apparatus of FIGS. Such an arrangement may incorporate a valve as in FIG.
[0076]
In a reactor of the type shown in FIG. 12, the ion-conducting material can contain primary products and other types of raw materials for electrolytic production, support the electrolytic reaction at the counter electrode 14, and provide a contact electrode. 14 can flow. This fluid enters and exits the area 18 of the chamber 11 by conduits 26 and 27. The ion-conducting fluid occupies the region 18 up to the electrode 13 or may be provided with a solid or semi-solid ion conductor layer 28 interposed between the ion-conducting fluid and the electrode 13 as shown in FIG.
[0077]
FIG. 13 schematically illustrates a variation of the reactor of FIG. 12, provided with a fluid ionic conductive solution in contact with the electrode 14 and a permeable layer of ionic or electrical conductor 29 between ionic conductor layers 28. , They can be fluid, solid, or semi-solid, and contact the electrode 13. Also shown in FIG. 13 is a variation on the configuration of the electrode 13, which is a combination of a net or interconnect strip that deposits the primary product 16 on the surface of the ion conductor 28 during biasing through the electrode 13. Take the form. The permeable layer 29 can be, for example, an electrical conductor such as mercury (or a structure containing mercury or amalgam), wherein the species transported is a mercury-soluble metal such as sodium. As indicated for layer 29, the presence of the selectively permeable layer employs a chemically incompatible ion conducting material on either side of the layer. For example, an aqueous salt solution can contact the electrode 14 and sodium beta-alumina can contact the electrode 13, but the two electrolytes are subject to hydrolysis reactions that can damage sodium beta-alumina. Do not make direct contact. The intervening layer is chemically compatible with both ion-conducting layers, and this transports sodium or sodium ions, allowing the use of such chemically incompatible layers in combination. Basically, multiple layers of conductors with appropriate permeability and chemical compatibility can be used.
[0078]
Basically, a second type of reactor can be used with both solid and fluid electrolytes, but it is advantageous to use an ionic conductor adjacent to the working electrode 13, which can be solid or porous. It is a semi-solid, such as an electrolyte fluid immobilized by a crystalline structure or gel. The arrangement depicted in FIGS. 12 and 13 can be used to perform processes such as the production of organometallic reagents. The electrolysis in the ion conduction path section is the reduction product M⁰(Eg, lithium metal) is generated at the porous electrode, which reacts with a precursor RX (eg, an alkyl halide) that yields a reagent MR (eg, an alkyllithium compound). By-products containing MX (eg, lithium halide) may also be produced. Products MR and by-products that originate in the same area can be removed in a fluid stream as shown in FIGS.
[0079]
As long as ionic or electrical continuity between the electrodes 13 and 14 is maintained, a variety of structures and materials can be used to form electrolytic cells and ionic conductive pathways, and allow for transport of desired species To enable the electrolytic formation of the primary product at the electrode 13.
[0080]
In practice, solid-state ionic conductors based on ceramics or crystalline materials tend to have a transport number of 1 or near as mobile ions, which reduces problems with concentration polarisation in the electrolyte. Let it. Examples such as β-alumina or Nasicon are Na with a transport number of 1⁺Attractive as a conductor. The conductivity increases with temperature, but at room temperature^-3Height values on the order of Siemens / cm have been achieved and throughput limitations due to low conductivity are not extreme. Analogs of the lithium and potassium analogs of the ceramic sodium ion conductor also usually have somewhat lower conductivity. Li₃N crystals have high lithium ion conductivity perpendicular to the c-axis. Various lithium conductors based on mixed oxide (Si, Ge, P, Zn, Ge, and V) media are also known. Another actual solid ionic conductor is Ag⁺, Cu⁺, H⁺Cation and F⁻, And O^2-About the anion. The conductor of the positive electrode is LaF₃, And doped ZnO₂And the limited utility for organic synthesis is likely to be demonstrated due to the relatively low conductivity at appropriate temperatures, but can be applied for high temperature reactions. Some Ag + ion conductors, especially those related to AgI (eg, rubidium silver iodide) have very high conductivity and other sources for forming organosilver compounds or for generating other organometallics It may be useful as an electrolyte for use in combination with a substance. Cu⁺Conductors are also known, but generally have lower conductivity than similar Ag + conductors. Solid-state proton conductors often have conductivity that depends on the presence of water, and for the most part have been restricted for use with chemical reactions compatible with water, and have a second type or geometry. It provides a means to carry out electrochemical hydrogenation or even dehydrogenation in a device of a specific arrangement.
[0081]
The ionic conductor polymer is particularly Li⁺Widely applied in battery industry for ions.
They are, perhaps, even more practically immobilized liquid electrolytes where there is some migration of anions that can lead to polarization. The example applies to a rechargeable system, where the Li metal is deposited either as a free metal or in graphite matrices. There may be even more limitations with the use of such polymer systems, which include polymers in the fluid used to carry the precursor to the working electrode and the product from the working electrode. May result from the solubility of lithium salts. Polymers and solvent systems may be generally characterized as ether / polyether type materials, which may be compatible with lithium metal in various organic synthetic processing systems. Lithium-ion conductors in combination with graphite media to form lithium or other types of permeable electrodes are suitable for use in devices of the second type or geometry.
[0082]
Using the same liquid electrolyte used in a reactor of the first type or geometry in a device of a second type or geometry having a porous working electrode, possibly on a porous substrate Which is retained at the interface between the electrode and the precursor / product carrying fluid (s). This can be an immiscible fluid interface, or it can exist as a stepped interface in a porous electrode where the fluid is miscible or has some mutual solubility.
[0083]
The reactor of the present invention can be coupled to a mixer / reactor stage for rapid consumption of product reagents, as shown in FIGS.
[0084]
The counter electrode 14 in the electrochemical cell requires a source of ions to be transported. This can be provided by the electrode material itself (eg, if it is an alkali metal, or an alloy or amalgam of an alkali metal, or an electrically conductive intercalation compound of an alkali metal). A solution of the relevant ions can be provided as a layer adjacent to the counter electrode and the waste product to be removed, avoiding polarization and contamination problems. This replenishment, either continuously or intermittently, can be accomplished via conduits 26, 27, as shown in FIGS.
[0085]
Although the number of types of ions that can be used in the ion-conducting phase in an electrochemical cell is significantly limited, in some cases, organometallic reagents of other metals may be used to place those metals adjacent to electrodes 13. By providing it in the compound in the flowing stream 17. These source materials in solution can be used alone or simultaneously with the precursor reagents, as described above for discontinuous or continuous mode operation of the synthesizer.
[0086]
1a-12 and the description relating to those figures show only two electrodes in each device. It should be understood that the reactor of the present invention can have and can be configured with multiple electrodes performing the functions of the working electrode 13 and the counter electrode 14 shown in FIGS. is there.
[0087]
As illustrated schematically in FIG. 14, additional electrodes 30, 31 can be incorporated to perform other functions. One or more reference electrodes can be incorporated into the device to monitor and control the potential of the working electrode. Such a reference electrode contacts the ion-conducting phase between the electrodes 13 and 14, where it should be used as part of a circuit to control the working electrode, and then the reference electrode 30 is most commonly used. , As shown in FIG. Another electrode 31 is located in the fluid stream, monitors the potential to allow detection of the fluid composition, and other non-electrochemical detectors can be used, for example, optical or thermal detectors. . In operation, the output from the detector in the device can be used to control the applied potential and current through the device, and to control the input and output ratio of the fluid.
[0088]
As shown schematically in FIG. 15, a heat exchanger structure 32 can be incorporated into the device. Such thermal control structures can include fluid cooling or heating structures, as well as electric heaters and Peltier coolers, and multiple heating control structures can be distributed throughout the device. Such a thermal control structure can be located adjacent to the reaction zone, as shown diagrammatically in FIG. 15, where the heat exchanger is adjacent to the chamber 11 and especially one or more. Shown adjacent to the electrodes, and an additional heat exchanger structure 33 is adjacent to the reaction zone following junction 19.
[0089]
As shown diagrammatically in FIG. 16, where the primary product 16 does not stick to the working electrode 13, it is taken up in the fluid stream 17 and consists of the precursor reagent or a fluid containing it. Passes through the reaction chamber via an inlet conduit 35 downstream of the primary product production region at a junction 34 where it mixes and reacts with the primary product at and adjacent to the junction 34.
[0090]
As illustrated schematically in FIG. 17, the area where the primary product is formed and / or reacts with the precursor reagents may be exposed to some radioactive stimuli, such as UV light from a source 37 through a window or opening 36. Exposed to Such a stimulus enhances the formation or response of the primary product or monitors the response as part of a detector system.
[0091]
The use of additional electrodes, thermal control structures, and supplemental radioactive stimuli as depicted in FIGS. 14, 16 and 17 can be applied to both first and second types of devices.
[0092]
In the second type of device, the surface or surface of the electrode on which the primary product is formed can be different from the one where the precursor material is initially provided. In such an arrangement, the electrode structure on which the primary product is formed must allow the transport of material between the surfaces or surfaces of the electrode to allow contact between the primary product and the precursor material. An electrode that is permeable to the primary product can accomplish this, or if the electrode is formed of a material or structure that provides a bias through the hole or electrode, thereby producing the primary product or Precursors or primary products or fluids containing precursors can pass through. Physical holes or biases can be provided by forming the electrodes from a porous material or as a mesh or strip.
[0093]
If the primary product is an amalgam-forming metal, the electrode permeable to the primary product can be formed, at least in part, as a mercury film or layer. A sheet of porous body or substance wetted by mercury can support the mercury layer. Graphite is permeable to some metallic and some non-metallic species such as lithium and fluorine, and layers or membranes of graphite can be used to form permeable electrodes, where: Such species are primary products. If the primary product is hydrogen, the electrode permeable to the primary product will be a membrane or layer of palladium or other metal with high hydrogen permeability (eg, lanthanides and their alloys, misch metal). Can be formed. The hydrogen permeable metal can serve as a catalyst for the hydrogenation or reduction of the precursor reagent.
[0094]
Most commonly, the materials used for the electrode configuration in the device can conduct charge exclusively by electronic means. Such electrode materials include metals, many semiconductors, conductive carbon, and some conductive polymers and ceramics. In devices of the second type of geometry having such electrodes, the primary product must be formed at the contact between the electrodes and the ionically conductive material. In such a case, the electrode is permeable to the primary product, or through an electrode capable of passing a primary product or precursor and a secondary product, or a fluid containing the product or precursor. , Holes or vias.
[0095]
Alternatively, the material used for the electrode configuration can be a mixed conductive material. A mixed conducting material is one that can conduct electricity by both ionic and electronic pathways. In a device of the second type of geometry, the ionic conductivity of such mixed conduction type electrodes is turned away from the ionic conductive material comprising the electrolyte layer in the electrochemical cell to produce a primary product. Let it. If such mixed conducting electrodes are used, the electrodes in the device of the second type of geometry need to be permeable to primary products or precursors or secondary products or their solutions. do not do. Tungsten bronze is a well-known class of mixed conducting materials. Tungsten bronze sodium has the formula Na_xWO_yRepresented by the electron and Na⁺It has a composition range in which conduction of both ions occurs.
[0096]
In the reactor shown in FIGS. 1 a to 17, the surface, or surface, of the electrode on which the primary product is formed can be the same as that provided with the raw material. This is usually the case when the source material is supplied to the same surface or surface as that of the ion conducting phase interposed between the electrodes carrying the electrolytic current. This includes the case where the raw material constitutes a part of the ion conducting phase.
[0097]
Alternatively, in a second type of reactor, the surface, or surface, of the electrode, where the primary product is formed, allows the electrode structure, or material, to be transported to the location of the primary product formation of the source material. As long as the source material is different from that initially provided. This may be an electrode permeable to the source material or the fluid containing the source material, or the electrode may be a hole or via an electrode through which the source material or the fluid containing the source material may pass. May be achieved by the case formed by Physical holes or vias can be provided by forming the electrodes from a porous material or as a mesh or strip.
[0098]
The source material may be a salt or a redox-active compound for conversion to the primary product, or a fluid containing the source material, and preferably intervenes between the electrodes during the electrochemical production of the primary product. It is at least a part of an ion conductive material. The source material, which is electrochemically converted to the primary product, can provide all or part of the ionic conductivity, or the ionic conductivity can be improved by electrochemical treatment with one or more electrodes. It can be provided by supporting electrolyte ions that may not be included therein.
[0099]
Alternatively, the source material or its fluid containing the source material, and the ion-conducting material between the electrodes can be different, in which case during the electrolysis process, the source material forms the ion-conducting material and the primary product. Access can be made at least at a portion of the junction between any electrodes to be made. This can be achieved when the source material and the ion-conducting material, each of which can be in solid or fluid form, but both contact the same electrode surface. The source material and the ion-conducting material can be either mixed miscible phases or immiscible, or can contact the electrodes as strips or streams.
[0100]
Alternatively, access by the source material to at least a portion of the junction between the ion-conductive material and any electrode on which the primary product is to be formed may be based on the source material, or a fluid containing the source material, and a strip. Alternatively, this can be achieved by electrodes formed at the interface between ion-conducting materials formed as a mesh or having holes or vias through the electrodes, or when the electrode material is permeable to the source material. The ionically conductive material can be a fluid, or can be a solid, such as a ceramic ionic conductor, or a semisolid material, such as an ionically conductive polymer or gel. Alternatively, a combination of solids or semi-solids, and the ionically conductive phase of the fluid can be used as an ionically conductive structure or collection of phases interposed between the electrodes to electrochemically produce the primary product. Solid or semi-solid ionically conductive materials can include mobile species that are converted to primary products at the electrodes. The mobile species in the solid or semi-solid ionic conductor that converts to the primary product at the electrode can include ions that maintain conductivity, such as, for example, sodium ions in sodium beta alumina. If those mobile species constitute the source material, for example, in the fluid phase, another supply of the source material is optional. In addition, as long as the electrode material can be replenished from an admixed ion-conducting and conductive material, and an adjacent phase that can be a fluid containing the ion-conducting material or related ions or their related ions or source materials. And mobile ions in the constituent materials.
[0101]
The reactor of the present invention can include a region for the electrochemical production of the primary product and for producing a secondary product in the reaction of the primary product and the precursor. These zones can be the same or different, and additional zones and reaction zones and those for mixing products and reagents and for reactions can be incorporated into the device. The apparatus can include an area for controlling the temperature of the electrochemical production and reaction zone. Heat can be generated in electrochemical cells by a combination of current and cell resistance, by electrochemical conversion, and by chemical reactions such as those between primary products and precursor reagents.
[0102]
The operation of the reactor of the present invention involves a number of transport processes that are affected by the configuration and size of the reactor, and preferred device dimensions are within the range appropriate for microtechnology. Processing typically includes electromigration, electrodeposition, and diffusion of substances and reagents to reaction sites such as electrodes and electrodeposits, mixing of fluidic reagent streams, reaction, and exothermic or heat consumption and heat transport. It is. In general, as shown below, the rate of mass transport and formation, and the transfer of heat from or to the fluid and reaction sites, is small for structural and fluid flow diameters, and applies to microtechnology. It is improved by making the device to fall within the range.
[0103]
Typically, the production of a primary product includes the electro-migration of ions carrying the electrolytic current and the electromigration or diffusion of the source material to the electrode where the primary product is formed. The primary product may remain, where it is formed or transported into a fluid stream to be conveyed to a separate reaction site. Within the ionic conductor or its layers, heat is drawn at a rate given by the product of current and voltage drop due to the resistance heating method. Heat may also be generated or, less frequently, absorbed as a result of electrochemical reactions at the electrodes, including conversion of the source material to primary products. Maintaining the desired temperature regime is aided by minimizing the diameter of the fluid and wall to the heat exchanger, heat sink, or heat source.
[0104]
The precursor material is brought to the primary product by a fluid stream, either at a deposition location or a separate reaction location. In each case, the precursor material comes into contact with the primary product, and this typically involves diffusive transport across the stream carrying the precursor material, and transfers the precursor material to the primary product. Either transport to the surface or mix the precursor material and primary product streams, where they are held together in the fluid phase. The rate of reaction between the primary product and the precursor may be limited by transport, and such transport limitations in rate are reduced by minimizing the diameter of the fluid transport mass transport.
[0105]
Some production or absorption of heat is associated with the primary products and precursors reacting to produce secondary reaction products. When the primary product is a reactive material, such as an alkali metal deposit, the reaction is generally exothermic. Whether heat is derived or absorbed, maintenance of a stable temperature regime is improved by a short heat transfer distance from the reaction location to the heat exchanger, sink, or source intervening across the fluid layer and wall material. Is done.
[0106]
The reaction of secondary reactive products carried by the flow to additional reaction sites also includes mixing, heat generation or heat absorption and heat transport, and by minimizing the associated transport distance, An increased rate of diffusive transport and heat transfer is achieved.
[0107]
The speed and efficiency of each described process is affected by the geometry and dimensions of the equipment, and preferably, micro-engineered sized equipment is used, allowing for fast and efficient compaction and heat transfer become.
[0108]
For electrochemical reagent production, preferred dimensions are dictated, inter alia, by the need to avoid excessive voltage drops in the body of the electrochemical cell and at the electrodes, and heat generation, while maximizing current and increasing production rates. You. Although the adhesion of the electrochemical cell to the cooling surface allows for rapid heat removal, the ion-conducting electrolyte layer must be sufficiently thin to ensure that the heat generated within the electrolyte is efficiently removed. To be. For devices using non-aqueous electrolyte phases with relatively poor ionic conductivity, it is desirable to minimize the electrical resistance between the electrodes by the arrangement in which the thickness of the electrolyte layer is to be reduced. This condition applies when the electrolyte is a fluid or for a polymer immobilized electrolyte.
[0109]
Seramic ion conductors typically operate at elevated temperatures, have increased ionic conductivity, and their thermal conductivity is generally relatively high. However, it is more preferred that such a layer of electrolyte be used in the synthesizer as a suitably thin structure to reduce the operating voltage required at relatively low temperatures compatible with synthetic organic chemistry. The electrochemical reaction is located at or very close to the electrode surface, and the transport of ions and source materials for the production of primary products is a controlling factor in the rate of product production for the device of the present invention. is there.
[0110]
As mentioned above, micro-engineering techniques can be used to form conduits or flow channels with depth dimensions down to 〜1 μm. However, in general, channels having a depth of 10-100 μm are more conveniently made and allow for significantly higher throughput and lower resistance. The width and length of the channels are generally defined by lithographic techniques and vary from a few micrometers to centimeter dimensions. By using such a combination of conduits or flow channels, transportation and mixing times on the order of milliseconds for liquids and microseconds for gases can be achieved.
[0111]
Mass transport to and from the ion-conducting electrolyte or electrode across the flow stream can occur by either electromigration or diffusion. For thin electrochemical cells, it is convenient to provide a relatively high electric field gradient with only the appropriate potential applied across the cell; under such conditions, electromigration transport is faster. Typically, ion mobility is 移動 10 for an electric field gradient of 1 V / cm.^-4cm²V^-1s^-1Or about 1 μm / s. Field gradients of 10-1000 V / cm are difficult to provide in relatively thin (~ <1 mm) electrochemical cells with readily available electromigration times of less than 1 second across a fluid or solid electrolyte layer. is not.
[0112]
The area for reaction or mixing can be estimated as the depth d and length 1 of the channel or chamber, where t is the transit time for the fluid flowing along the length of the channel. The change in temperature can be caused by the dwell time t before a process that causes heat generation or heat consumption occurs, the rate of heat generation or heat consumption, the heat capacity of fluids and other materials in the device, and the heat diffusion, It may be related to the thermal time constant for the cooling process as a function of the dimensions, such as the diameter of other layers. It should be ensured that the thermal time constant associated with the zone is low, so that fine control works over the temperature in the mass transport and reaction zone.
[0113]
If any material, such as raw materials, electrolytes, reagents, products or solvents, is thermally unstable, then the temperature rise should be limited. In any case, the yield and rate of processing that results in the first and second products can be temperature dependent, and control of the temperature in the apparatus is desirable. In general, temperature control is improved by short heat transport distances, and thus is easily improved in micro-engineered devices. The performance of the heat transport process is generally μt / d²Where μ is the thermal diffusivity, t is the time allowed for heat transport, and d is the distance to the conductive heat sink surface. Distance. μt / d²If> -1, then thermal equilibrium was largely achieved. μt / d²Using t as the thermal time constant and relocation at = 1 is t = (d²/ Μ), and obviously this decreases for small values of d. Some example values relating to thermal diffusion, conduction length and time constant are tabulated below.
[0114]
These values indicate that for short thermal response times of less than 1 second, the thickness of the liquid layer should be 100 μm or less. These constraints do not apply when the rate of energy transport is low. Indeed, if the structure and its contents form mixed layers with different values of μ and d, the evaluation of the heat transport characteristics is necessarily more complicated, but the most thermally resistant layers and their It is usually appropriate to specify the basic design calculations above. If layers of reagent fluids and solvents are included, they should be thin enough to avoid maintaining excessive temperature differences, and should be replaced by heat sinks or heat exchangers, heat pipes, Peltier coolers, or resistance heaters. It is usually appropriate to ensure that it is included by a more conductive structure, such as a thin metal, glass or ceramic composition, connected to such a source.
[0115]
On a finer scale, even smaller amounts of liquid are used, and the diffusional distance in the liquid is dramatically reduced to allow for rapid diffusion. The rate of diffusion can be affected by a number of different factors, such as chemical mechanics factors and the transport of dissolved material in a solvent by convective, advective, or diffusion processes. Within the microfabrication equipment, the dimensions across the channel generally ensure that low Reynolds laminar flow conditions apply. Mixing and reacting for species that contact and react with species from adjacent flow streams or deposits on walls or electrodes requires that the species traverse the flow stream. Disturbed fluid transport is generally not present in micro-engineered sized devices, and the movement of species across the stream is driven by its molecular movement, such as diffusion or electromigration. If diffusive transport is the limiting factor, then the rate of diffusion is related to the length of the path through which the molecules diffuse and the geometry of the liquid body. The diffusive transport rate is generally inversely related to the length of the passage or the square of the length of the passage depending on whether conditions for steady state or temporary diffusion apply.
[0116]
Diffusive transport is required when the species to be converted electrochemically is unloaded or does not move through the electric field region, and also for unloaded species involved in non-electrochemical treatments that occur at the electrodes. That's right. Diffusive transport is included when the source material is not a loaded species that can be transported to the electrode for conversion by electromigration, and diffusive transport can also include other ionic species, such as supporting electrolytes. If it carries most of the current and reduces the field gradient, the loaded species can be controlled. In addition, the precursor material required to react with the primary product to produce a secondary product is generally not a loaded species. The length of time for diffusively transporting raw and precursor materials that need to be present adjacent to the working electrode is determined by the distance to the electrode surface across the flow carrying such materials, the characteristic distance for the calculation of diffusion. , It can be evaluated on the basis of diffusion processing. A full analysis of the diffusion process can be complex, but in general the diffusion process is a dimensionless parameter Dt / d²When approaching ~> 1, it comes completely close. This corresponds to near equilibrium or completion of the diffusion process. [D is the diffusion coefficient, t is the time allowed for mass transport, and d is the distance across the fluid to the surface (electrode) where the transformation occurs. The value of the residence time based on diffusion provides a minimum guide value, if the reaction kinetics at the electrode surface is not fast enough, and other mass transport processes are delayed, e.g. dissolution of solid reactive products Even longer times may be required when introducing their diffusive transport from the surface.
[0117]
Acceptable values for reactor size and residence time within the electrochemical conversion stage depend on the stability of the reactive product to be formed and on the desired throughput.
[0118]
Typically, in non-viscous fluids, the diffusion coefficient (D) for reducing the appropriate molecular weight species to an interesting size range (chemicals of hundreds of molecular weights) is 10^-5-10^-7cm²s^-1Is within the range. 5 × 10 for D^-6cm²s^-1, The approximate time t for the diffusion transport time across the path length (l) is Dt / d²= 0.01 to 1 type of display, where Dt / d²= 0.01 approaches the diffusion front reaching a distance d from the raw material plane, and Dt / d²= 1 corresponds to near completion of the diffusion process (concentration gradient across d is almost eliminated). Diffusion equilibrium (Dt / d) at different path lengths (d)²= 1), the approximate time t to reach is that the dissolved material must move, but d = 5 × 10^-6Or 5 × 10^-7cm²s^-1In the following table of diffusion mixing times based on
[0119]
[Table 1]

[0120]
About 50% of the diffusion transport is about the 10th time (Dt / d²(Equivalent to ~ 0.1). Based on the above table, a relatively rapid equilibration by diffusion alone takes place within 100 seconds, where the required transport distance d is of the order of 100 μm or less. The associated distance d for the mixing of the two fluid streams is from the farthest end of the channel, where the two fluids meet. For transport of material to or from the surface, such as to deposits of primary products on the electrodes, d is the diameter of the fluid stream or of the layer to that surface. In microengineered devices where the distance d is made small, the distance d reduces and controls the transport, mixing and reaction times controlled by diffusion.
[0121]
For a process operated under transport control, the reactant depletion and product flux from the reaction zone of the unit are reduced by the transport time for the fluid stream in the reaction zone and the cross-flow diffusion process in that zone. Depends on. Selection of the flow rate such that the transport time of the fluid stream in the reaction zone and the completion time of the cross flow are similar, the reaction flux per unit volume of the device which improves so that the distance d is reduced. Invite. This may result in a greater heat flux from the reaction and / or ohmic (Joule) heating, but the temperature in the device does not rise excessively so that the thermal time constant similarly decreases with d. The value of the dimension d in the range of 1000 to 50 μm is 0.001 to 1 Amp / cm.², A diffusion-limited reaction flux equal to the current density value of approximately equivalent to the range acceptable for electrodes in micro-engineered devices. For devices having higher values for d, the rate of reaction flux tends to be lower due to diffusion limitations, and so the rate of production per unit volume is lower. Therefore, the diameter of the channel or chamber for mixing or transporting the reagents to the reactive deposits should be small and this dimension in the device of the invention should be in the range 10-3000 μm, and preferably 30-300 μm. It is advantageous.
[0122]
If a mixing process other than diffusion mixing is not effective, a preferred substantially maximum diameter of the channel, or chamber, is determined to allow the substance to diffuse in that direction, and is 300 μm. The required residence time sufficient to cause diffusion mixing in the channel or chamber depends on the value of its dimensions. This dimension along the width of the channel determines the cross-sectional area of the channel, and the fluid throughput depends on the cross-sectional area and length of the channel or chamber, and on the velocity of the fluid flow. The length of the channel can be significantly increased, especially if a drawn tubular structure is used in the configuration. However, where channels or chambers are required to incorporate micro-engineered structures such as electrodes, and especially when they are provided on substantially flat substrates by conventional micro-engineering techniques, the overall It is desirable to limit the length and width. Typically, for liquids, in microfluidic systems, the flow rates easily achievable without excessive pressure movements vary up to 10 cm / s and preferably range from 0.01 to 1 cm / s. . Suitable lengths for channels or chambers that allow the diffusion process to proceed to completion vary up to 10 cm and preferably range from 0.1 to 3 cm.
[0123]
It is not necessary for the purposes of the present invention that laminar flow conditions be maintained for the fluid flow in the device. The channels or chambers can be made large enough to support turbulent mixing with the diameter of the channel required to be greater than 0.1 cm, and even more typically 1 cm or more. If mixing is to be induced by simple flow through channels and chambers, mass transport across the mixing and flow becomes inefficient at these dimensions. However, efficient mixing can be induced by using a pulsed or reciprocating flow, or by using mechanical agitation of the fluid by a structure such as a stirring paddle or magnetic stirring bar.
[0124]
The dimensions in the mixer / reaction stage are dictated by the diffusion process for the same purpose as described above for the electrochemical primary product production stage and the reaction using the precursor to produce a secondary product. If the two laminar streams are operated together, the diffusion distance d controlling the mixing time will again be the channel depth. If the reaction is very rapid and one stream has excess reagent, then the rate limiting diffusion distance is up to that fraction of the width of the channel corresponding to the fluid from the second stream. Tends to decrease. This is the case for simple and complex phase flows. For complex phase treatments, the limited mass transport distance and time can vary somewhat, but if the phase is an immiscible liquid, all results will It is not expected to change substantially unless the (inter-phase) transport is impeded dynamically. If one type of phase is a gas, then the mass transport limitation would be completely present in the liquid phase and would be set by the diameter of that phase. Reactions, of course, may not limit mass transport. If mechanical constraints are applied for simple phase reactions, perform partial or complete mixing in the micro-engineered structure, and then transport the product to a holding vessel for completion of processing Is appropriate. For complex phase treatments, the degree of phase subdivision and interface geometry is critically dependent on how the fluid is contained and moved.
[0125]
What has been described above is that for reaction times in the range 0.1 to 10 seconds, a channel depth of 10 to 1000 μm is indicated, and preferably the channel depth is in the range 30 to 300 μm. Show. The preceding table for diffusion mixing times showed that if mixing and reaction on the millisecond time scale were required for liquid reagents, then the channel depth had to be ~ 1 μm. The rate of total flow that can be achieved under those conditions is significantly lower (〜1 cc / h or less for a 1 cm wide channel). The following table shows values for fluid throughput and transit times for some example channel dimensions. The combination of transit time and diffusion length is significant for sufficient diffusion mixing for species of appropriate molecular weight. The limitation on the length of the channel, and thus the available transit time at any given flow rate, depends on the size of the structure that can be conveniently made. The values for the required operating pressure for laminar flow in these channels are shown in the table below.
[0126]
[Table 2]

[0127]
It is clear that for these short to adequate transit times, if the channel length or pressure drop is not excessive, the flow rate will generally need to be limited to less than 100 cc / hour. These flow rates are for a 1 cm wide channel and are directly related to the width of the channel.
[0128]
Complex phase reactions rely on the ability to maintain a useful interphase contact area. This becomes even more difficult as the dimensions decrease. Microcontactors and networks of the type described above (see WO 97/39814) can be applied when the depth of the channel is 20 μm or more, the pressure and the pressure required to move the flow A balance between surface tensions below that point tends to produce a slugging flow in the phase. Although the reaction can be maintained in a slow stream, the size of the sludge controls the rate and flow rate and the recirculation that is induced in the sludge and does not rely on diffusion treatment appropriate for simple laminar flow.
[0129]
The electrolysis cell can constitute a rechargeable and / or disassemblable cartridge, which can be removed and the primary product (e.g., metal deposits) or source material converted to a secondary product (e.g., The organometallic product can be replenished away from the resulting process, or alternatively, the primary product (metal deposits) can be moved away from the location of the electrochemical process to a secondary product (eg, Organic metal product) as it occurs.
[0130]
The fluid pumping (pumping) means is preferably connected to a reactor comprising an electrochemical cell, where a source of fluid electrolyte or redox-active substance is used. Such fluid pumping means maintains the centrifugal pump, diaphragm pump, peristaltic pump, electrosmotic flow generating structure, magnetic fluid pump, syringe pump, and hydrodynamic head as appropriate for the selected fluid, May be included to move the fluid reservoir. Valves and flow regulators can be included in the device and in the fluid path leading from the device.
[0131]
1a-17, the electrode 13 on which the primary product is formed is called the "working electrode" and is held at a negative potential (i.e., the negative electrode), while the electrode 14 is positive. It is held at the potential (positive electrode). This is consistent with the production of alkali metals from their compounds and salts, but the working electrode can hold anything if the potential matches the conversion of the source material to the primary product, and this is positive. Potentials can be included. Although the figures are generally shown as simple flat assemblies, other geometries, including cylindrical assemblies and laminated sheets, can be used.
[0132]
Multiple positive and negative electrodes and arrangements of such electrodes can be used, and the device can incorporate one or more reference electrodes that monitor or control the potential of other electrodes.
[0133]
Examples of the types of chemical reactions that can be performed in a synthesizer incorporating an electrochemical cell according to the present invention will be illustrated and described below, but are not intended to limit the present invention.
[0134]
1 Formation of sodium, lithium or potassium alkoxide or phenoxide.
Electrolysis is performed in a first or second type of reactor to produce lithium metal as a primary product. An ion conductive material and a raw material are provided using a solution of a lithium salt or lithium ion solid or polymer conductor. The alkyl halide as a precursor reactant in the solution flows and contacts the lithium metal electrodeposited on the negative electrode, reacting with the lithium and forming a lithium alkyl that can be carried away in solution by the solvent. The stages of the chemical reaction are represented below. This treatment can be applied to other organic halide precursor materials such as sodium or potassium or lithium, as long as the sodium / lithium / potassium does not directly attack part of the organic group or other substituents. . This processing is described below.
Na / K / Li⁺Y^-    + E^-(At the negative electrode) → Na / K / Li⁰(metal)
(Where Y^-Is CF_ThreeCO_Two-Like an anion. )
Na / K / Li⁰(Metal) + R⁻OH → Na / K / Li^+-OR + H_Two
(Where R = CH_Three, C_TwoH_Five, C_ThreeH₇, C_FourH₉, Phenyl, substituted phenyl, or heteroaryl, or substituted heteroaryl. )
[0135]
A lithium precursor can be used to provide the solubility of the by-product lithium halide. Lithium bromide and iodide are relatively soluble in many organic solvents and can not hinder the subsequent reaction of lithium alkyl, and organic iodides and bromides are therefore preferred precursor reactants. Excess Li metal is available and additional reaction with the precursor (R-X + Li-R-> Li⁺X⁻  + RR) to ensure that the consumption of the lithium alkyl produced is avoided, and this is accomplished by performing an initial electrode charging process to achieve Li⁰This can be achieved by building up the sediment or by using a discontinuous mode of operation. Lithium salt electrolysis and lithium alkyl formation can be accomplished in an ethereal solvent that allows for continuous operation of the first type of device, but can also be used in discontinuous operation and the second type of device.
[0136]
The sodium, potassium or lithium alkyl produced can be carried to the mixer stage by a fluid stream to perform the wide range of chemical reactions established for those reagents.
[0137]
2 Formation of sodium naphthalenide
The electrolysis that deposits sodium metal can be combined with a stream of a naphthalene solution to yield a sodium naphthalenide product that can then be used as a reagent. This treatment does not involve problems with low solubility halides or the reaction of product and precursor (naphthalene). A second type of device based on sodium beta alumina as the ionic conductor is suitable. All reactions can be described below:
Na⁺+ e^-(From working electrode) → Na⁰
Na⁰+ C_TenH₈(Naphthalene) → Na⁺C_TenH₈ ^-(Sodium naphthalenide)
[0138]
Sodium naphthalenide is the sodium anion associated with the radical anion⁺It seems to exist as. Similar reagents are derived from anthracene (and thus sodium anthacenide), and others related to aromatic precursors. Similar reagents can be derived from lithium and other electropositive metals.
[0139]
Similarly, potassium naphthalenide can be synthesized using potassium as a raw material and naphthalene as a precursor. Further, sodium naphthalenide can be synthesized using sodium as a raw material and naphthalene as a precursor.
[0140]
3. Synthesis of sodium / potassium / lithium anthracenide
The present invention can be used for the synthesis of sodium anthracenide, potassium anthracenide, or lithium anthracenide by using sodium, potassium, or lithium as a raw material and anthracene as a precursor.
[0141]
4. Synthesis of sodium / potassium / lithium phenanthrenide
The present invention provides a method for synthesizing sodium phenanthrenide, or potassium phenanthrenide, or lithium phenanthrenide by using sodium or potassium as a raw material or lithium and phenanthrene as a precursor. Can be used.
[0142]
5. Conversion of organotin compounds
Exemplary reactions are of the following types:
Na⁺+ e^-(From electrode) → Na⁰
(CH_Three)_ThreeSn -Sn (CH_Three)_Three+ 2 Na⁰→ 2 (CH_Three)_ThreeSn^-Na⁺
The sodium compound is then reacted in a later mixer / reactor stage, for example with an organic halide, to add additional organic groups to the tin.
(CH_Three)_ThreeSn^-Na⁺+ CH_Two= CH-CH-Cl → (CH_Three)_ThreeSn-CH_Two-CH = CH + Na⁺Cl^-
[0143]
6 Formation of sodium / potassium / lithium alkoxide or phenoxide
Sodium or potassium alkoxides or lithium alkoxides can be synthesized using the present invention. Based on the following processing.
Na / K / Li⁺+ e^-(From electrode) → Na / K / Li⁰
Na / K / Li⁰+ R^-OH → Na / K / Li^{+ -}OR + H_Two
(Where R = CH_Three, C_TwoH_Five, C_ThreeH₇, C_FourH₉, Phenyl, substituted phenyl, heteroaryl, or substituted heteroaryl)
Sodium ethoxide and other alkoxides, such as isopropoxide, which can also be produced, are widely used in chemical synthesis. Hydrogen gas introduced during the synthesis generally does not interfere with other reactions, but may cause unwanted flow interruptions. Mixtures of alkoxides and salts can be produced from esters without generating hydrogen.
[0144]
7 Removal of halides from aromatic compounds by sodium metal
The halide can be removed from the aromatic compound by the following treatment using the present invention.
Na⁺+ e^-(From electrode) → Na⁰
_6-nNa⁰+ C₆H_nCl_6-n+ Solvent → C₆H₆+ Na Hal + solvent
(Where Hal = Cl, Br, or I.)
For example, Na + C₆H_nCl_6-n+ Sodium metal + (proton source solvent, eg, alcohol) → C₆H₆+ NaCl
The addition of the proton source may have to be spatially separated by the mixer stage adding it and then reacting the aromatic halide with the electrodeposited sodum metal.
[0145]
8 Birch reduction
Embedded image

This type of reaction occurs with solid sodium ion conductors when compatibility with the solvent is established, or, alternatively, when a sodium salt soluble in liquid ammonia is used as the electrolyte and source material in a first type of device. It may be possible with a second type of device.
For example:-
C₆H₆(Benzone) + 2 Na + C_TwoH_FiveOH (in liquid ammonia) → C₆H₈(1,4 cyclohexadiene)
The reaction proceeds by a radical anion that removes a proton from the alcohol.
[0146]
9 Generation of Grignard reagent
The overall reaction is:
RX + Mg (in ether) → R-Mg-X (where R = C₆H_FiveAnd X = Cl, Br, or I)
Example is C₆H_FiveBr + Mg → C₆H_FiveMgBr
It is.
The reaction is carried out in ethereal solvents and solvents that promote the reaction, such as ethers, which coordinate the Mg and stabilize the reagent. Mg from organic solution⁰While electrolytic deposition of is possible, it can also be produced by reduction of dissolved magnesium compounds with alkali metals such as sodium and thus used as primary products as indicated for other reaction sequences. it can.
[0147]
Similarly, to make organometallic reagents for metals whose ions do not move within a reasonably conductive solid phase, for example, metals with multivalent ions such as Mg, Zn, Cd, Sn, Al, A preferred method is to provide the metals in solution and directly electrodeposit or to perform the conversion in an apparatus of either the first or second type using the electrodeposited alkali metal. Either.
[0148]
10 Production of halogenated products
This can include producing products containing fluorine, chlorine, bromine or iodine. The primary product may be an elemental halogen, such as chlorine, produced by the electrochemical oxidation of a soluble halide.
2Cl^-  -2 e^-(At positive electrode) → Cl_Two
Chlorine can react with various organic species and produce chlorinated products directly by addition (to an unsaturated bond) or substitution. Alternatively, chlorine can be converted to an inorganic reactive intermediate. For example, PCl₃And PCl₅Is formed as a secondary product by the reaction of chlorine with phosphorus that is supplied or suspended or dissolved in a fluid stream. These secondary products can react with additional reagents such as carboxylic acids in the device to produce products such as acyl chlorides.
[0149]
11 Ylide formation from phosphonium salt cations by Wittig reaction and alkane formation by reaction of ylide and aldehyde. For example:

[0150]
It is appreciated that the cartridges and methods described above can be performed on a large (macro) scale, but can be applied on a fine scale, in particular, by creating a micromachined cartridge or system.
[0151]
For the purposes of this disclosure, the term "fluid" means either a gas or a supercritical liquid or an aqueous or non-aqueous liquid. Preferably, the fluid is a liquid. Preferably, the salt or other redox-active compound of the metal to be electrodeposited is ionically conductive, but is electrically conductive if the ionically conductive material is provided to be bound to the working and counter electrodes. It is not necessary.
[0152]
Additional mixing elements as needed, for example, small wings or deflectors formed and located in the chamber and / or at the entrance to the chamber or at the exit from the chamber Can be added to the reactor and the fluid rotated or mixed.
[0153]
Numerous chemical reactions are contemplated for operation in the described reactor, but with organic reagents to form electrochemical alkali metals and to form organometallic reagents such as sodium naphthalenide or lithium alkyl. Are preferred.
[0154]
Thus, such reactors can find use on synthetic chemists' experimental benches and can be expanded or exceeded by the use of complex or arrayed equipment for manufacturing methods. . For example, the outlet conduit of the first reactor of the present invention can be connected to the inlet conduit of another reactor constructed in accordance with the present invention during a continuous stream.
[0155]
Similarly, a plurality of successively connected reactors can be provided on a common structure. One or more arrays of consecutively connected reactors can be arranged on a common structure in relation to another one or more arrays of serially connected reactors. . This concept is not unlike that of components built on integrated circuit chips, but in this case the components are micro-engineered reactors.
[0156]
Importantly, the reactor of the present invention can be applied to convert hazardous waste chemicals and solvents to less hazardous forms, but especially PCB (polychlorinated biphenyl) and CFC ( It is not limited to the conversion and purification of halogenated products such as fluorocarbon chlorides). Such conversion may be by direct reaction of a primary product, such as sodium, with the chemical to be converted, or formation of a secondary product, such as sodium naphthalenide, followed by mixing and reaction with the chemical to be converted. Can be continued by The use of sodium naphthalenide as a degradation / purification reagent for PCBs has been reported to have a reactive dehalogenation of CFCs with sodium metal. These wastes are treated directly in the apparatus of the present invention by using an electrochemically generated alkali metal (for example, sodium) or by a cartridge using the electrochemically generated alkali metal according to the present invention. Can be.
[Brief description of the drawings]
[0157]
1a and 1b schematically show two micro-engineered reactors incorporating the present invention.
FIG. 2 schematically illustrates a micro-engineered reactor incorporating a specific embodiment of the present invention.
FIG. 3 schematically illustrates a micro-engineered reactor incorporating a specific embodiment of the present invention.
FIG. 4 schematically illustrates a micro-engineered reactor incorporating a specific embodiment of the present invention.
FIG. 5 schematically illustrates a micro-engineered reactor incorporating a specific embodiment of the present invention.
FIG. 6 schematically illustrates a micro-engineered reactor incorporating a specific embodiment of the present invention.
FIG. 7 schematically illustrates a micro-engineered reactor incorporating a specific example of the present invention.
FIG. 8 schematically illustrates a micro-engineered reactor incorporating a specific embodiment of the present invention.
FIG. 9 schematically illustrates a micro-engineered reactor incorporating a specific embodiment of the present invention.
FIG. 10 schematically illustrates a micro-engineered reactor incorporating a specific embodiment of the present invention.
FIG. 11 schematically illustrates a micro-engineered reactor incorporating a specific example of the present invention.
FIG. 12 schematically illustrates a micro-engineered reactor incorporating a specific embodiment of the present invention.
FIG. 13 schematically illustrates a micro-engineered reactor incorporating a specific example of the present invention.
FIG. 14 schematically illustrates a micro-engineered reactor incorporating a specific example of the present invention.
FIG. 15 schematically illustrates a micro-engineered reactor incorporating a specific example of the present invention.
FIG. 16 is a diagram schematically showing a micro-engineered reactor incorporating a specific example of the present invention.
FIG. 17 schematically illustrates a micro-engineered reactor incorporating a specific example of the present invention.

Claims (65)

A micro-engineered reactor for performing a chemical synthesis, said reactor comprising:
(A) an electrochemical cell in close communication with the reaction chamber and the interior of the reaction chamber;
(B) said reaction chamber is of micro-engineered size and has micro-engineered inlet and outlet conduits for transferring fluids to and from the reaction chamber;
(C) the cell includes at least two electrodes positioned and arranged in relation to each other to define a space between the electrodes, wherein in at least one aspect of use of the cell, the oxidation Receiving an ion-conducting fluid that is or contains a source material of reducing activity, and forming a conductive path between the electrodes through which a current passes when a potential is applied to the electrodes, to electrolyze the source material , And a primary product at or adjacent to the surface of the electrode within the interior of the reaction chamber;
(D) means for introducing a precursor material into the reaction chamber that reacts with the primary product to produce a secondary product; and (e) unloading the secondary product from the reaction chamber via the outlet conduit. A reaction apparatus comprising means for performing: At least one electrode has a surface on which, in use, a primary product is formed, and that the surface is located within the reaction chamber or forms part of a boundary wall of the reaction chamber. The reactor according to claim 1, characterized in that: At least one of the electrodes has a surface on which a primary product is formed in use, made from a sacrificial material that reacts with a source material to form a primary product, or coated with a sacrificial material. The reactor according to claim 1, wherein the reaction is performed. Further, the cell includes electrodeposition means for selectively applying a charge to each electrode in the presence of an ion-conducting fluid containing the ions of the sacrificial material, thereby either on the single electrode or 4. The reactor according to claim 3, wherein a sacrificial substance to be deposited on the plurality of electrodes is generated and the sacrificial substance consumed by the electrolysis is supplemented. The electrodeposition means operably deposits the sacrificial material on the surface of each electrode or electrodes prior to or during the reaction of the sacrificial material and the source material to form the primary product. The reactor according to claim 3 or 4, characterized in that: The electrodeposition means operably deposits the sacrificial material on the surface of each electrode or electrodes prior to or during the reaction of the sacrificial material and the source material to form the primary product. The reactor according to claim 4 or 5, wherein The electrodeposition means includes means for applying a negative charge to one electrode and applying a positive charge to the other electrode, and the fluid supply means comprises a cation deposited on the negatively charged electrode. Provided for introducing a source of an organic fluid containing a salt which is a sacrificial substance to be effected, and causing an electric field between the two electrodes to deposit the substance on the surface of the negatively charged electrode The reactor according to any one of claims 4 to 6, further comprising means for causing the reaction. The electrodeposition means includes means for applying a negative charge to one electrode and applying a positive charge to the other electrode, and the fluid supply means comprises an anion deposited on the positively charged electrode. Provided for introducing a source of organic fluid containing a salt which is a sacrificial substance to be effected, and causing an electric field between the two electrodes to deposit the substance on the surface of the positively charged electrode The reactor according to any one of claims 4 to 6, further comprising means for causing the reaction. 9. The reaction apparatus according to claim 7, wherein the organic fluid containing ions of the sacrificial substance is also an organic reagent that reacts with the deposited substance to produce a primary product. 10. The reactor according to any one of claims 7 to 9, wherein the organic fluid containing the ions of the sacrificial substance is also a precursor that reacts with the deposited substance to produce a secondary product. . A reaction chamber wherein at least one electrode is made of a fluid permeable material, and wherein the fluid source material is permeable and reacts at a surface of the fluid permeable electrode in communication with the interior of the reaction chamber to form a primary product; The reactor according to any one of claims 1 to 10, wherein a part of the boundary wall is defined. A second chamber is formed on a side of the fluid permeable electrode spaced from the interior of the reaction chamber, and an electrode of the cell is located in the second chamber, wherein the fluid permeable electrode is located within the second chamber. A primary product is created by electrolyzing a source material of the type, and is made from a material that penetrates through the permeable electrode into the interior of the reaction chamber and reacts with the precursor material to form a secondary product. The reactor according to claim 11, characterized in that: The second chamber has an inlet conduit for supplying a fluid containing fresh source material to the second chamber and an outlet for removing fluid depleted of the source material from the second chamber. The reactor according to claim 11, wherein A first region on one side of the conductor, where a fluid permeable ionic conductor or conductor is provided between the electrodes and the ionic conductive solution is held in contact with one of the electrodes, and the other of the conductors 11. A second region on the side surface of which is defined an ion conductive layer, which may be fluid, solid or semi-solid, in contact with the fluid permeable electrode. The reactor according to any one of claims 13 to 13. The reactor according to claim 14, wherein the conductor is mercury or amalgam. The reactor according to claim 1, wherein the cell is a rechargeable cartridge. A reactor according to any one of the preceding claims, further comprising a fluid pump means connected to the reactor for pumping a fluid to the reactor. The reactor according to any one of claims 1 to 17, wherein the raw material and the precursor are present in a common fluid. The reactor according to any one of claims 1 to 17, wherein the raw material is present in the first fluid, and the precursor is present in the second fluid. 20. The reactor according to claim 1, wherein the outlet conduit of the reaction chamber is divided into two or more separate outlet passages. 21. At least one or more separate outlet passages are connected to the inlet conduit of another reactor constituted by the reactor of any one of claims 1 to 20. A reactor as described. One electrode of the cell is located in or forms part of the wall of the reaction chamber, and one electrode of the cell defines one of the separate outlet passages. 22. A reactor according to claim 20 or claim 21, wherein the reactor is installed in or forms part of a wall of a conduit. The reaction chamber is configured, sized and arranged to define a plurality of adjacent flow paths to the reaction chamber via respective pairs of inlet and outlet conduits. The reactor according to any one of claims 1 to 22. Ions located between the positive and negative electrodes of the cell to define a positive electrode section adjacent to the positive electrode on one side of the ion permeable barrier and a negative electrode section adjacent to the negative electrode on the other side of the ion permeable barrier 24. The reactor according to any one of claims 1 to 23, wherein a permeable barrier is provided. 25. The barrier according to claim 24, wherein the barrier is selected from the following substances: porous or permeable sheets, dialysis membranes, ion exchange membranes, areas of gel electrolyte or areas of immobilized electrolyte. Reactor. The reactor according to any one of claims 1 to 25, wherein at least one electrode is a porous block through which a fluid can flow. A first separate inlet conduit for supplying the source material, a second separate inlet conduit for supplying the precursor, and a third for supplying a cleaning fluid for removing secondary products from the reaction chamber. Reactor according to any of the preceding claims, characterized in that a separate conduit is provided. 28. The reactor of claim 27, further comprising valve means for selectively opening and closing each of the first, second, or third inlet conduits. 29. A method according to claim 1, wherein one or more reference electrode means are provided in the reaction chamber or cell for monitoring and controlling the potential applied to the electrodes of the cell. Item 6. The reaction apparatus according to Item 1. 30. A reactor according to claim 29, wherein one or more monitoring electrode means are provided for monitoring the composition of the product produced in the reactor. 31. A heat exchanger according to any of the preceding claims, wherein a heat exchanger is provided in the reaction chamber or adjacent to the reaction chamber for controlling the temperature of at least one region inside the reaction chamber. The reactor according to claim 1. The reactor according to any one of claims 1 to 31, wherein an outlet conduit is connected to an inlet conduit of another reactor configured to continuously flow the reactor. A reactor according to any one of the preceding claims. 33. The reactor of claim 32, wherein a plurality of successively connected reactors are provided on a common structure. Characterized in that one or more arrangements of the serially connected reactors are arranged with respect to one or more other arrangements of the serially connected reactors on a common structure. 34. The reactor of claim 32 or 33. A method for performing chemical synthesis, comprising the following steps:
(A) providing a reactor configured by the reactor according to any one of claims 1 to 34;
(B) providing a source material in a space between at least two electrodes;
(C) electrolyzing the source material to form a primary product at or adjacent to the surface of the electrode in communication with the interior of the reaction chamber; and (d) forming a primary product in the reaction chamber; A method for performing a chemical reaction comprising contacting with a precursor that reacts with and / or is mixed with a primary product to produce a secondary product. 36. The method of claim 35, comprising removing secondary products from the reaction chamber. 37. The method of claim 36, further comprising reacting the secondary product with an additional singular reaction or a precursor material used in a series of additional reactions to produce a final product. . A method for producing a synthetic organic compound, comprising the following steps:
(A) To provide a micro-engineered reactor constituted by the reactor according to any one of claims 1 to 34, wherein at least one electrode reacts with a precursor to form a secondary Made from or coated with sacrificial material forming the product;
(B) providing the source material to at least one electrode consisting of a sacrificial material or having it deposited thereon;
(C) electrolyzing the source material and reacting the electrolyzed source material with a sacrificial material to form a primary product at or adjacent to the surface of the electrode; and (d) A method for producing an organic compound, comprising contacting with a precursor that reacts with a primary product to form the organic compound in a reaction chamber. A method for producing a synthetic organic compound, comprising the following steps:
(A) To provide a micro-engineered reactor constituted by a reactor according to any one of claims 1 to 35, wherein at least one electrode reacts with a precursor to form a secondary Made from or coated with sacrificial material forming the product;
(B) providing the organic source material to at least one electrode comprising at least a sacrificial product or having it deposited thereon;
(C) electrolyzing the source material and reacting the electrolyzed source material with a sacrificial material to form a secondary product at or adjacent to the surface of the electrode; and (d) forming the primary product. Contacting with a precursor that reacts with a primary product to form the organic compound in a reaction chamber. 40. The method of claim 38 or 39, further comprising the step of replenishing the spent sacrificial material with an electrodeposited material on at least one electrode. By connecting the electrodes to a power supply, a sacrificial material is deposited on each electrode or electrodes, whereby one electrode forms a negative electrode and the other forms a positive electrode, and the method comprises: The method of claim 1 further comprising the steps of: applying a fluid containing a salt in which the ions are a sacrificial substance to the negative electrode; and applying an electric field between the negative electrode and the positive electrode, thereby depositing the sacrificial substance on the negative electrode. 40. The method of claim 40. The sacrificial material is deposited on the surface of each electrode by connecting the substrate to a power supply, whereby one electrode forms a negative electrode and the other forms a positive electrode, and the method comprises the steps of: Applying an ion-conductive fluid containing a salt that is a sacrificial substance to the positive electrode, and applying an electric field between the negative electrode and the positive electrode, thereby depositing the sacrificial substance on the positive electrode. 41. The method of claim 40. A fluid containing salt is applied to the electrodes while simultaneously applying a charge to the electrodes, thereby depositing a sacrificial material on at least one electrode, and then providing a source material to the electrodes and reacting electrolytically with the sacrificial materials. 43. A method according to claim 41 or claim 42, wherein the primary product is formed. A salt-containing fluid is applied to the electrode while simultaneously applying a charge to the negative electrode, thereby depositing a sacrificial material on at least one electrode, and providing the source material to the electrode simultaneously with the salt, and depositing the sacrificial material. 43. A method according to claim 41 or claim 42, wherein the primary product is formed by reacting with. The reactor is constituted by the reactor according to any one of claims 12 to 15, and the method comprises the following steps:
(A) introducing a fluid containing the source material into a second chamber; and (b) electrolyzing the source material in the second chamber and communicating the primary product with an interior of a reaction chamber. 36. The method of claim 35, comprising producing on a surface of a fluid permeable electrode that is in use. A process for synthesizing lithium or sodium or potassium alkyl, wherein the source material is derived from a solution of a lithium or sodium or potassium salt, or a solid or polymer ion conductor thereof; and The precursor according to any one of claims 35 to 45, characterized in that the precursor is an alkyl halide which reacts with the raw materials to form lithium, or sodium or potassium alkyl as a secondary product. Method. A method for synthesizing sodium naphthalenide, wherein the raw material is sodium, the precursor is naphthalene, and the secondary product is sodium naphthalenide. A method according to any one of the preceding claims. A method for synthesizing potassium naphthalenide, wherein the raw material is potassium, the precursor is naphthalene, and the secondary product is potassium naphthalenide. A method according to any one of the preceding claims. A method for synthesizing sodium anthracenide, wherein the raw material is sodium, the precursor is anthracene, and the secondary product is sodium anthracenide. A method according to any one of the preceding claims. A method for synthesizing potassium anthracenide, wherein the raw material is potassium, the precursor is anthracene, and the secondary product is potassium anthracenide. A method according to any one of the preceding claims. 35. A method for synthesizing sodium phenanthrenide, wherein the raw material is sodium, the precursor is phenanthrene, and the secondary product is sodium phenanthrenide. 45. The method according to any one of claims 45. 35. A method for synthesizing potassium phenanthrenide, wherein the raw material is potassium, the precursor is phenanthrene, and the secondary product is potassium phenanthrenide. 45. The method according to any one of claims 45. 46. The method according to any one of claims 35 to 45, which is a method for converting an organotin compound, wherein the raw material is sodium and the precursor is an organotin compound. The following types of reaction ^Na + + e ^- (from the electrode) → Na ⁰
_{(CH 3) 3 Sn-Sn} (CH 3) 3 + 2Na 0 → 2 (CH 3) 3 Sn - Na +
54. The method of claim 53, wherein the method is for effecting the conversion of an organotin compound by: Further, the sodium compound is converted to the following formula:
_{^{(CH 3) 3 Sn - Na}} + + CH 2 = CH-CH-Cl → (CH 3) 3 Sn-CH 2 -CH = CH + Na + Cl -
55. The method according to claim 54, wherein the reaction is carried out with an organic halide according to Sodium is a method for producing an alkoxide or phenoxide of lithium or potassium, the following formula ^{Na / K / Li + + e} - ( from the electrode) → Na / K / Li ^{0
Na / K / Li 0 + R} - OH → Na / K / Li + - OR + H 2
Where R = CH ₃ , C ₂ H ₅ , C ₃ H ₇ , C ₄ H ₉ , phenyl, substituted phenyl, heteroaryl, or substituted heteroaryl.
46. The method according to any one of claims 35 to 45, wherein A method for removing halides from an aromatic compound by sodium metal, the following reaction Na ⁺ + e - ^(from the electrode) → Na ^{0
_{6-n Na 0 + C 6}} H n Cl 6-n + solvent → C ₆ H ₆ + NaHal + solvent (wherein, Hal = Cl, Br, or I.)
46. The method according to any one of claims 35 to 45, wherein A method for performing birch reduction of a compound, comprising the steps of:

C ₆ H ₆ (benzone) + 2Na + C ₂ H ₅ OH (in liquid ammonia) → C ₆ H ₈ (1,4 cyclohexadiene)
46. The method according to any one of claims 35 to 45, wherein A method for producing Grignard reagents, the following reaction:
RX + Mg (in ether) → R-Mg-X
(Wherein R = C ₆ H ₅ and X = Cl, Br, or I)
46. The method according to any one of claims 35 to 45, wherein The reaction is:
C ₆ H ₅ Br + Mg → C ₆ H ₅ MgBr
The method of claim 59, wherein A method for producing a halogenated product, wherein the raw material is a soluble halide, the primary product is a halogen produced by electrochemical oxidation of the soluble halide, and the halogen reacts with an organic precursor. 46. The process according to any one of claims 35 to 45, wherein the secondary halogenated product is produced by addition to an unsaturated bond or by substitution. A method for producing a halogenated product, wherein the raw material is a soluble halide, the primary product is a halogen produced by electrochemical oxidation of the soluble halide, and the halogen reacts with an inorganic precursor. 46. The method according to any one of claims 35 to 45, wherein the method produces an inorganic reactive intermediate. Halogen is chlorine, inorganic precursor is phosphorus, and claim 61 or 62 method wherein a secondary product is PCl ₃ or PCl _5. 64. The method of any one of claims 61 to 63, wherein the secondary product is reacted with a carboxylic acid in a reaction chamber to produce an acyl chloride product. A process for producing ylides from the cation of a phosphonium salt by the Wittig reaction and for producing an alkene in the reaction of an ylide with an aldehyde, comprising the following formula:
^{_{(C 6 H 5) 3 P}} + CH 2 C 6 H 4 NO 2 + e - → (C 6 H 5) 3 P + C - HC 6 H 4 NO 2
^{_{(C 6 H 5) 3 P}} + C - HC 6 H 4 NO 2 + HCOC 6 H 4 NO 2 → NO 2 C 6 H 4 CHCHC 6 H 4 NO 2
46. The method according to any one of claims 35 to 45, wherein