JP2004059600A - Reactor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a reactor which is equipped with a membrane separation device capable of selectively separating water vapor and hence is excellent in thermal efficiency. <P>SOLUTION: This reactor produces a synthesis gas. The synthesis gas formed in the reactor contains at least either water vapor supplied for reaction or water vapor generated by the reaction. In the reactor 10, a water vapor permeable membrane as a membrane separation means is installed to selectively separate and remove the water vapor contained in the synthesis gas formed in the reactor; and the water vapor separated and removed with the water vapor permeable membrane and the synthesis gas after the water vapor removal are discharged out of the reactor through different systems. <P>COPYRIGHT: (C)2004,JPO

Description

【００３３】
次に、第１の実施形態の変形例として、水蒸気を供給しない反応操作を行う反応器１０について、図１を参照して説明する。
反応器１０に水蒸気を供給することなく反応操作を行い、合成反応過程で水蒸気を副生する場合には、反応器１０内に存在する水蒸気を合成ガス中から選択的に分離するため、合成反応における平衡状態が崩れる。その結果、合成反応が水蒸気を生成する方向に加速されて進行するため、結果的に反応速度が増加したことになる。
【００３４】
これを下記に記載の反応式〔２〕に基づいて説明する。
原料ＡとＢとの反応により生成物Ｃと水蒸気Ｈ_２　Ｏとを合成する反応の場合、生成物である合成ガス中から膜分離装置５０を用いて水蒸気（Ｈ_２　Ｏ）を選択的に分離すると、平衡反応〔２〕が崩れるため、右方向への反応が促進される。その結果、生成物であるＣの合成速度が増加したことになる。
一般に、このような水蒸気透過膜を使用して合成反応速度を向上させる反応器をメンブレンリアクターと呼ぶ。このメンブレンリアクターで使用される膜分離装置５０は、耐熱性が必要である。
Ａ　＋　Ｂ　→　Ｃ　＋　Ｈ_２　Ｏ　・・・・・〔２〕
【００３５】
この実施形態における反応器１０の構成は、実質的には上述した第１の実施形態と同じであるが、原料となる有機物を原料供給ライン３１から、反応ガスを反応ガス供給ライン３６から、そして、空気または酸素を空気供給ライン３７から反応器１０の反応領域１１へ供給する点が異なっている。
上述した反応器１０内で水蒸気を発生する反応が進行する場合、図２に示した膜分離装置５０でエレメント５２を透過した水蒸気は、水性ガス化反応時と同様に、透過ガス出口ライン３４を経て反応器１０の外部へ排出される。この後、三方弁２１の流路切換操作によって水蒸気排出ライン３５へ導かれ、この水蒸気排出ライン３５に設けられている熱交換器２３を通過する際に高温の水蒸気が冷却される。この水蒸気はさらに、下流側に設置されている凝縮器２４に捕集され、凝縮水として排水される。
【００３６】
この場合には、反応器１０がメンブレンリアクターとしての機能を有することになる。また、反応ガスは、反応ガス供給ライン３６から個別に反応器１０内の反応領域１１に供給される。さらに、水蒸気循環経路が形成されないためにスイープガスの回収及び再利用が困難になるといった理由などからスイープガスを使用できないため、透過（分離）効率を上げるために膜分離装置５０の内部を真空ポンプ２５により減圧処理する場合もある。
この減圧処理を具体的に説明すると、エレメント５２のスイープガス室５９側端部を閉鎖し、他端側から真空ポンプ２５で中空部５２ａ内のガスを吸引することで、中空部５２ａ内が外部より低圧になるよう減圧している。
【００３７】
上述したメンブレンリアクターにおける具体的な反応例を下記に示す。
Ｃ　＋　Ｏ_２　　→　ＣＯ_２　　・・・・・〔３〕
ＣＯ_２　＋　Ｈ_２　　→　ＣＯ　＋　Ｈ_２　Ｏ　・・・・・〔４〕
なお、本実施形態においては、水蒸気循環経路を選択切換する三方弁２１、そして、水蒸気循環経路を形成するブロアー２２及び反応ガス循環供給ライン３２は必須の構成要件ではない。
【００３８】
ところで、上述した第１の実施形態（変形例を含む）においては、スイープガス供給ライン３３または空気供給ライン３７から供給される空気は、大気をそのまま導入してもよいが、酸素濃度の高い酸素富化空気（または酸素）を供給することにより、空気に含まれる窒素ガス量が減少する。このため、窒素ガスの減少分だけ、反応器１０から排出される合成ガス中に含まれる可燃性ガス成分の濃度が上昇する。
【００３９】
上述した酸素富化空気は、公知技術である圧力スイング吸着装置（ＰＳＡ）により生成して供給することができる。この圧力スイング吸着は、圧力を高くすることにより吸着剤による吸着を行い、圧力を低くすることで脱着を行う。これによって吸脱着サイクルを繰り返し、空気中の脱湿やガスの回収などを行うことができる。
【００４０】
酸素富化空気の生成に圧力スイング吸着を採用する場合、一般に工場内等にある余剰圧縮空気を使用して消費電力を抑えることが好ましい。これは、通常の圧力スイング吸着では、すなわち、余剰圧縮空気の供給を受けない運転では付設の圧縮機を運転して圧縮空気を供給する必要があるので、この圧縮機における消費電力が大きいためである。従って、反応器１で生成した合成ガス（可燃性ガス）を燃料として使用し、内燃機関発電機を運転して発電しても、結局外部へ供給できる発電量が減少してメリットは少ない。
【００４１】
＜第２の実施形態＞
続いて、本発明の第２の実施形態を図３に基づいて説明する。
この実施形態は、図１に示した第１の実施形態において反応器１０の内部に膜分離装置５０を配設した構成と異なり、反応器１０Ａの外部に図２に示した膜分離装置５０を配設してある。なお、上述した実施形態と同様部分には同じ符号を付し、その詳細な説明は省略する。
【００４２】
反応器１０Ａから排出された合成ガスは、出口ガスライン３８を経て熱交換器２６で一次冷却され、さらに、出口ガスライン２８の下流側に設置されている補充熱交換器２７で二次冷却される。この後、出口ガスライン３８のさらに下流側に設けられている膜分離装置５０に供給される。すなわち、膜分離装置５０は、反応器１０Ａの出口に接続された配管部である出口ガスライン３８に設けられている。
【００４３】
膜分離装置５０で合成ガスから分離された水蒸気は、ガス循環ブロアー２８に吸引されてスイープガスと共に透過ガス出口ライン３４を通過する。
補充水蒸気ライン３９から供給される水蒸気は、補充熱交換器２７で合成ガスを二次冷却することで廃熱を回収して昇温し、三方弁２９において透過ガス出口ライン３４に合流することで不足分の水蒸気が補充される。
【００４４】
三方弁２９で補充を受けた水蒸気は、熱交換器２６でさらに合成ガスの廃熱を回収して高温に加熱された後、反応ガス循環供給ライン４０から反応器１０Ａに供給される。ここで供給される水蒸気は、第１の実施形態における反応ガス循環供給ライン３２と同様に、スイープガスを含んでいる。
【００４５】
上述した熱交換器２６及び補充熱交換器２７を設けて廃熱利用を行うと、反応器１０Ａに投入する水蒸気やスイープガス（酸素富化空気等）の温度を高く設定できるので、反応器１０Ａ内の温度を高温に維持する部分燃焼の割合を低く抑えることができる。また、廃熱を有効利用するため、装置全体としての熱効率を向上させることができる。
なお、上述した熱交換器２６、補充熱交換器２７を設けなくても反応器１０Ａの運転は可能であり、また、少なくとも一つの熱交換器を設けたり、あるいは設置順序を変えるなど、諸条件に応じて適宜変更が可能である。
【００４６】
上述した本発明の反応器１０Ａにおいては、合成ガスに含まれている水蒸気を膜分離装置５０で分離除去して回収し、反応器１０Ａへ戻す水蒸気循環経路が形成されている。
図３に示した水蒸気循環経路は、熱交換器２６及び補充熱交換器２７を経て合成ガスと共に膜分離装置５０に流入した水蒸気を分離させて回収し、ブロアー２８及び熱交換器２６を経て反応器１０Ａへ戻すように構成されている。この水蒸気循環流路を流れる水蒸気は、凝縮されることなく循環するので、凝縮させて系外へ捨てていた従来と比較すれば、凝縮潜熱の損失が減少して熱効率がよい。
また、水蒸気をリサイクルしながら使用して水性ガス化反応を行わせるので、系外へ排出される水蒸気量を最小限に抑えることができ、従って、ボイラで生成する補充水蒸気量も最小限となる。
【００４７】
このため、補充水蒸気を発生させるために必要なボイラ用燃料の消費量節約、装置の小型化及び低コスト化に有効である。また、合成ガスから水分を分離するための除湿装置（ＰＳＡ方式等）やガスホルダーの必要容量も小さくすることができるので、同様に装置の小型化や低コスト化に有効である。
また、反応器１０Ａへ投入する空気に酸素富化空気または酸素を使用し、これを膜分離装置５０のスイープガスとして使用すれば、水蒸気の膜透過量が増加して回収水蒸気量を増すことができる。なお、このスイープガスには他のガスを使用することも可能であるが、その場合には新たなガス供給系が必要になるなど装置の小型化や低コスト化を阻害する要因となる。
【００４８】
さらに、合成ガスの廃熱を利用し、投入水蒸気や補充水蒸気、そして部分燃焼用の酸素富化空気や酸素（空気）を加熱して昇温させるので、反応器１０Ａ内の温度を維持する部分燃焼を最小限とすることができる。このようにして部分燃焼が最小限に抑えられると、部分燃焼に必要な窒素を含む空気量も減少するので、空気や酸素富化空気を投入する場合には生成される可燃性ガスに含まれる窒素ガス量が減少し、可燃性ガス成分は内燃機関燃料として好都合な高発熱量のガスとなる。
【００４９】
［実施例２］
図３に示す構成の装置を使用し、以下の条件で水性ガス化反応を行う運転を実施した結果、膜分離装置を使用しない場合に比べて、水蒸気の発生に必要なボイラー用燃料を約３１％削減することができた。

【００５０】
＜第３の実施形態＞
次に、本発明の第３の実施形態を図４及び図５に基づいて説明する。なお、以下の説明では、上述した実施形態と同一の部分には同じ符号を付し、その詳細な説明は省略する。
この実施形態では、図１に示した第１の実施形態の反応器１０に類似した構成の反応器１０Ｂと、触媒層間に膜分離装置５０を設置した触媒反応器７０とを直列に接続した構成が示されており、たとえば原料の有機物からメタノールを得ることができる。
【００５１】
上流側に配置した反応器１０Ｂは、反応領域１１に伝熱管４１を配設した構成が反応器１０と異なっている。この伝熱管４１は、管内部を流れる冷却流体により反応領域で生成された合成ガスを冷却するものである。ここで使用する冷却流体は、スイープガス供給ライン３３でスイープガスに合流する。従って、この冷却流体には、スイープガスと同様に酸素富化空気など反応ガスとして反応器１０Ｂ内に投入されるガス流体が好ましい。
【００５２】
反応器１０Ｂで合成され、膜分離装置５０で水分を分離・除去された合成ガスは、出口ガスライン３８及びその途中に設けられた熱交換器４２を通って触媒反応器７０へ導かれる。熱交換器４２では、高温の合成ガスが冷却される。
触媒反応器７０は、触媒充填層内に、具体的には触媒層７１，７２間に膜分離装置５０が配設されており、合成ガスが触媒層７１に導入されると、同触媒層７１ではメタノール合成反応が進行する。
このメタノール合成反応で副生した水蒸気は、膜分離装置５０で分離・除去され、透過ガス出口ライン４５から反応器外部へ排出される。こうして水蒸気を分離・除去された合成ガスは、触媒層７２を経た後に、合成物（たとえばメタノール）として合成物出口ライン４３から反応器外部へ取り出される。
【００５３】
一方、反応器１０Ｂ側の膜分離装置５０で分離された水蒸気は、透過ガス出口ライン３４及びブロアー２２を経て、反応ガス循環ライン３２から反応器１０Ｂに循環して再使用される。また、過剰の水蒸気は、水蒸気排出ライン３５、熱交換器２３及び凝縮器２４を経て、凝縮水として排出される。同様にして、触媒反応器７０側の膜分離装置５０で分離・除去された水蒸気は、透過ガス出口ライン４５、熱交換器４６及び凝縮器２４を経て、凝縮水として排出される。
また、凝縮器２４で凝縮しなかった非凝縮ガスは、真空ポンプ２５から大気等へ排気される。
なお、図中の符号４７は、合成物の一部をポンプ４８により出口ガスライン３８へ戻して合流させるラインである。
【００５４】
図５は、触媒反応器の一実施形態として、いわゆるメンブレンリアクターを示したものである。この触媒反応器８０は、外周面に加熱ガス流路８１が設けられているケーシング８２の内部に、触媒８３が充填されている。円筒形状としたケーシング８２の軸方向両端面には、それぞれ原料ガス入口８４及び合成ガス出口８５が設けられている。
【００５５】
また、触媒８３が充填されたケーシング８２の内部（触媒充填層内）には、上述した膜分離装置５０のエレメント５２と同様のエレメント８６が多数設置されている。円筒形状とした各エレメント８６の端部は、それぞれが入口ヘッダー部８７及び出口ヘッダー部８８に連結されている。
一方の入口ヘッダー部８７には、ケーシング８２の外部からスープガスを供給するスイープガス供給管８９が連結されている。
また、出口ヘッダー部８８には、エレメント８６を透過した水蒸気及びスイープガスをケーシング８２の外部へ導く透過ガス出口管９０が連結されている。
【００５６】
このように構成された触媒反応器８０では、原料ガス入口８４から供給された原料ガスが触媒８３を充填した領域で反応して合成ガスを生成する際、同時に副生される水蒸気が水蒸気透過膜のエレメント８３を選択的に透過して分離・除去され、エレメント８３内の中空部から出口ヘッダー部８８及び透過ガス出口管９０を通って外部へ導かれる。この結果、合成ガス出口８５から触媒反応器８０の外部へ流出してくる合成ガスは、水蒸気を除去されて合成ガスの濃度が高い良質のガスとなる。
［実施例３］
図４に示す構成の装置を使用し、以下の条件で運転を実施した結果、膜分離装置を使用しない場合に比べて、メタノールの収率が３５％向上した。

【００５７】
上述した本発明の反応器及び触媒反応器によれば、反応器内で生成された合成ガス中に含まれている水蒸気、すなわち、反応ガスとして投入した水蒸気の反応未使用分及び反応により副生された水蒸気のいずれか一方、または両方を選択的に分離除去する水蒸気分離膜を設けたので、同水蒸気を冷却することなく高温のまま分離・除去することができる。
そして、この水蒸気分離膜で分離除去された高温の水蒸気を反応器へ戻して循環させる水蒸気循環経路を形成したことにより、反応器内の水性ガス化反応に必要な水蒸気を凝縮させることなく、排出量を少なくしてリサイクルしながら使用することが可能になる。
【００５８】
上述した本発明の反応器においては、反応器内の状態は、固体／気体反応、液体／気体反応、気体／気体反応のいずれの状態でもよく、気相または液相で使用可能な分離膜の適用が好ましい。
なお、本発明の構成は上述した各実施形態に限定されるものではなく、本発明の要旨を逸脱しない範囲内において適宜組み合わせるなど、種々の変形例が可能である。
【００５９】
【発明の効果】
上述した本発明の反応器によれば、以下の効果を奏する。
請求項１に記載の反応器によれば、反応器内で生成された合成ガス中に含まれている水蒸気を選択的に分離除去する水蒸気透過膜（膜分離手段）を反応器内部に設け、水蒸気透過膜で分離除去された水蒸気と、水蒸気除去後の合成ガスとをそれぞれ別系統で反応器外へ排出するように構成したので、生成された合成ガスの温度を下げることなく高温のまま水蒸気を分離除去することができるようになり、熱効率のよい反応器を提供することができる。すなわち、水蒸気を分離・除去するために冷却や加熱をする必要がなくなるので、加熱源に要する燃料等を節約することができる。
【００６０】
請求項２に記載の反応器によれば、反応器内で生成された合成ガス中に含まれている水蒸気を選択的に分離除去する水蒸気透過膜（膜分離手段）を反応器出口に接続された配管部に設け、水蒸気透過膜で分離除去された水蒸気と、水蒸気除去後の合成ガスとをそれぞれ別系統で導くように構成したので、生成された合成ガスの温度を下げることなく高温のまま水蒸気を分離除去することができるようになり、熱効率のよい反応器を提供することができる。すなわち、水蒸気を分離・除去するために冷却や加熱をする必要がなくなるので、加熱源に要する燃料等を節約することができる。
【００６１】
請求項３に記載の反応器によれば、反応器内で生成された合成ガス中に含まれている水蒸気を選択的に分離除去する水蒸気透過膜（膜分離手段）を触媒充填層内に設け、水蒸気透過膜で分離除去された水蒸気と、水蒸気除去後の合成ガスとをそれぞれ別系統で反応器外へ排出するように構成したので、生成された合成ガスの温度を下げることなく高温のまま水蒸気を分離除去することができるようになり、熱効率のよい反応器を提供することができる。すなわち、水蒸気を分離・除去するために冷却や加熱をする必要がなくなるので、加熱源に要する燃料等を節約することができる。
【００６２】
また、上述した水蒸気透過膜で分離除去された水蒸気を反応器へ戻して循環させる水蒸気循環経路を形成することにより、分離した水蒸気を高温のままで循環させて再使用することが可能になるので、反応器内の水性ガス化反応に必要な水蒸気を凝縮させることなく、排出量を少なくしてリサイクルしながら使用することが可能になる。このため、熱効率のよい装置となり、補充水蒸気を供給するボイラや除湿装置等を小型化することもできるので、装置全体を小型化が可能になり、機器のコストだけでなく、建設費や敷地面積の低減により安価な装置を提供できるという顕著な効果を奏する。
【００６３】
また、本発明の装置で得られた合成ガスは内燃機関の燃料として使用可能なため、この内燃機関を駆動源として発電を行うと、中小量規模の炭化物を処理してデイリースタート・ストップ運転を実施することが可能になるので、炭化物の処理量から制約を受けることなく熱分解ガス化装置装置を広範囲に使用できるようになる。
また，メタノールやジメチルエーテル等を合成するための原料ガスとして使用する場合、ガス中の水蒸気濃度を１％以下に低減することが可能である。一方、メンブレンリアクターとして、合成反応速度を向上させる効果も期待できる。
【００６４】
また、水蒸気分離膜で分離除去された水蒸気にスイープガスを投入するようにすれば、水蒸気分離膜の内外で水蒸気の分圧差が大きくなるので、膜水蒸気分離膜を透過して分離除去される水蒸気量を増すことができ、結果として回収できる水蒸気量を増すことができる。
【図面の簡単な説明】
【図１】本発明に係る反応器の第１の実施形態を示す構成図である。
【図２】図１における膜分離装置の構成例を示す図で、（ａ）は断面図、（ｂ）は水蒸気の分離除去を説明するための斜視図である。
【図３】本発明に係る反応器の第２の実施形態を示す構成図である。
【図４】本発明に係る反応器の第３の実施形態を示す構成図であり、触媒反応器への適用例が示されている。
【図５】触媒反応器の構成例を示す断面図である。
【図６】従来の反応器を示す構成図である。
【符号の説明】
１０，１０Ａ，１０Ｂ　　反応器
１１　　反応領域
１２　　出口ガス領域
２２　　ブロアー
２３，２６　　熱交換器
２４　　凝縮器
２５　　真空ポンプ
２７　　補充熱交換器
２８　　ガス循環ブロアー
３１　　原料供給ライン
３２，４０　　反応ガス循環供給ライン
３３，４４　　スイープガス供給ライン
３４，４５　　透過ガス出口ライン
３５　　水蒸気排出ライン
３６　　反応ガス供給ライン
３７　　空気供給ライン
３８　　出口ガスライン
３９　　補充水蒸気ライン
４１　　伝熱管
４２，４６　　熱交換器
４３　　合成物出口ライン
５０　　膜分離装置（水蒸気分離装置）
５２　　エレメント（水蒸気透過膜）
５２ａ　中空部
７０，８０　　触媒反応器
７１，７２　　触媒層
８３　　触媒
８６　　エレメント（水蒸気透過膜）[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a reactor for producing a synthesis gas from organic matter, organic waste, waste plastic, coal, and the like.
[0002]
[Prior art]
Conventionally, as a method of producing a synthesis gas, a method of supplying a raw material such as organic matter, organic waste, waste plastic, and coal together with water vapor and air (or oxygen) of a reaction gas to perform a water gasification reaction, There is known a method of supplying hydrogen, hydrocarbon, or the like as a reaction gas instead of steam. The synthesis gas produced by these methods contains excess water vapor not consumed in the water gasification reaction and water vapor generated in the reaction process.
[0003]
In the conventional technology, after syngas in a high-temperature state containing these water vapors is extracted out of the reactor, the temperature of the synthesis gas is cooled through a heat exchanger or a condenser, and the water vapor in the synthesis gas is condensed. It has been practiced to increase the concentration of synthesis gas by separation. In this case, the cooled synthesis gas contains steam having a partial pressure of steam pressure corresponding to the gas temperature. Therefore, when this synthesis gas is used as a raw material gas in the next step, water vapor is further adsorbed and separated by an adsorbent such as a pressure swing adsorption device (PSA).
[0004]
Here, a configuration example of a conventional reactor will be briefly described with reference to FIG.
In this case, the reactor 1 synthesizes (generates) a synthesis gas by an aqueous gasification reaction by receiving a supply of the raw material organic matter, air or oxygen, a reaction gas (steam, hydrogen, hydrocarbon, or the like) and a supplementary steam. Since this synthesis gas has a high temperature and contains steam, it is cooled by passing through the heat exchanger 2 and then further condensed in the condenser 3 to be separated from the synthesis gas.
The synthesis gas from which the water vapor is separated is dehumidified by the dehumidification device 4 and then used as a raw material gas, fuel, or the like.
On the other hand, the steam separated in the condenser 3 becomes condensed water, and the steam generated by being guided to the heater 6 by the pump 5 is supplied to the reactor 1 and reused as, for example, supplementary steam.
[0005]
[Problems to be solved by the invention]
By the way, the above-mentioned conventional technology has the following problems.
(1) The amount of water vapor used in the water gasification reaction needs to be supplied in excess so as to be 1.5 times or more the required reaction equivalent in consideration of the reaction efficiency. As a result, excess steam not used in the reaction will be discharged from the reactor together with the synthesis gas. This excess steam is generally condensed and separated, and then boiled and evaporated by a heater from the state of condensed water again and supplied to the reactor. Therefore, a large amount of heat (sensible heat and latent heat of evaporation) necessary for generation of steam is generated. Have been consumed.
[0006]
(2) When using the synthesis gas discharged from the reactor as the next raw material gas, the high-temperature synthesis gas is once cooled to condense and separate water vapor, and then the synthesis gas is heated again to obtain a large amount. Is consuming energy. For example, when synthesizing methanol or dimethyl ether from a synthesis gas containing a high concentration of hydrogen / carbon monoxide, a high-temperature synthesis gas of about 700 to 900 ° C. is cooled to about 100 ° C. or lower, and then about 300 to 350 ° C. Used by heating to ° C.
[0007]
(3) When syngas is used as a fuel, about 30 to 50 vol. % Steam is contained and the calorific value is low in this state, so a method of cooling and synthesizing the synthesis gas to condense and separate the steam is used. Further, even when dehumidifying with an adsorbent such as PSA, the adsorbent cannot be used at a high temperature, so that it is necessary to cool down to about 300 ° C. or less before processing, and in this case, a large amount of energy loss occurs.
[0008]
The present invention has been made in view of the above circumstances, and provides a reactor capable of separating and removing steam in a synthesis gas at a high temperature and further circulating and using the separated steam at a high temperature. It is an object.
[0009]
[Means for Solving the Problems]
The present invention employs the following means in order to solve the above problems.
The reactor according to claim 1 is a reactor for producing a synthesis gas in which at least one of steam introduced for the reaction and steam produced by the reaction is contained in the produced synthesis gas, Membrane separation means for selectively separating and removing steam contained in the synthesis gas generated in the reactor is provided inside the reactor, and the steam separated and removed by the membrane separation means and the synthesis after removing the steam are provided. The gas is discharged to the outside of the reactor by separate systems.
[0010]
According to such a reactor, a membrane separation means for selectively separating and removing steam contained in the synthesis gas generated in the reactor is provided inside the reactor, and the separation and removal is performed by the membrane separation means. The steam and the synthesis gas after the removal of the steam are configured to be discharged to the outside of the reactor in separate systems, so that the steam can be separated and removed at a high temperature without lowering the temperature of the generated synthesis gas. . As a preferred membrane separation means, there is a so-called water vapor permeable membrane (steam separation membrane).
[0011]
The reactor according to claim 2 is a reactor for producing a synthesis gas in which at least one of steam introduced for the reaction and steam produced by the reaction is contained in the produced synthesis gas, Membrane separation means for selectively separating and removing water vapor contained in the synthesis gas generated in the reactor is provided in a pipe connected to the reactor outlet, and the water vapor separated and removed by the membrane separation means is provided. , And the synthesis gas from which the water vapor has been removed is led by different systems.
[0012]
According to such a reactor, a membrane separation means for selectively separating and removing water vapor contained in the synthesis gas generated in the reactor is provided in the pipe connected to the reactor outlet, and the membrane is provided. Since the steam separated and removed by the separation means and the synthesis gas after the removal of the steam are configured to be led in different systems, the steam can be separated and removed at a high temperature without lowering the temperature of the generated synthesis gas. it can.
[0013]
The reactor according to claim 3, further comprising a catalyst-packed layer therein, wherein at least one of steam supplied for the reaction and steam generated by the reaction is contained in the generated synthesis gas. A membrane separation means for selectively separating and removing water vapor contained in the synthesis gas generated in the reactor, wherein the separation and removal is performed by the membrane separation means. The steam and the synthesis gas from which the steam has been removed are discharged to the outside of the reactor in separate systems.
[0014]
According to such a reactor, a membrane separation means for selectively separating and removing water vapor contained in the synthesis gas generated in the reactor is provided in the catalyst packed bed, and separated by the membrane separation means. Since the removed steam and the synthesis gas after the removal of the steam are configured to be discharged to the outside of the reactor in separate systems, the steam can be separated and removed at a high temperature without lowering the temperature of the generated synthesis gas. Can be.
[0015]
In the reactor according to any one of claims 1 to 3, it is preferable to form a steam circulation path for circulating the steam separated and removed by the membrane separation means back to the reactor, thereby forming the separated steam. Can be circulated at a high temperature and reused.
[0016]
In the reactor according to any one of claims 1 to 4, it is preferable that a sweep gas is supplied to the steam separated and removed by the membrane separation unit, whereby a partial pressure difference between the steam inside and outside the membrane separation unit is reduced. Since it becomes large, the amount of water vapor that passes through the membrane separation means and is separated and removed can be increased.
Further, in the reactor according to the fifth aspect, it is preferable to use a gas that does not contain water vapor, such as oxygen-enriched air or a reaction gas such as oxygen or hydrogen, as the sweep gas.
[0017]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, embodiments of a reactor according to the present invention will be described with reference to the drawings.
<First embodiment>
In the first embodiment shown in FIG. 1, reference numeral 10 denotes a reactor, 50 denotes a membrane separation device (steam separation device), 21 denotes a three-way valve, and 22 denotes a blower.
In this embodiment, an organic material as a raw material is supplied from a raw material supply line 31 to a reactive gas (steam, hydrogen, hydrocarbon, or the like) or air or oxygen or a mixed gas thereof (hereinafter, these are collectively referred to as “reactive gases”). ) Are supplied from the reaction gas circulation supply line 32 to the reaction region 11 in the reactor 10.
In the reaction zone 11 of the reactor 10, a synthesis reaction such as a water gasification reaction proceeds, and a synthesis gas is produced.
[0018]
Organic substances (raw materials) for producing synthesis gas include biomass such as wood and plants, plastics, and organic wastes (food production by-products such as okara and tea husks, wood chips, manure, garbage, organic sludge, sewage). Sludge), coal, etc. can be used.
The organic substance is not limited to a solid, and organic substances such as liquid hydrocarbons and oils can be used.
[0019]
Here, when a water gasification reaction between organic matter and water vapor that proceeds in the reaction region 11 of the reactor 10 is represented by a chemical formula,
C + H ₂ O → CO + H ₂ ..... [1]
It becomes.
In this water gasification reaction, the internal temperature of the reaction region 11 needs to be set to a high temperature of 800 ° C. or more.
[0020]
A steam separation device (hereinafter, referred to as a “membrane separation device”) 50 is provided at an appropriate place inside the reactor 10, that is, at a synthesis gas outlet side (downstream side) of the reaction region 11. As a result, the inside of the reactor 10 is divided into the upstream reaction region 11 and the downstream outlet gas region 12 by the membrane separation device 50, and the synthesis gas containing water vapor synthesized in the reaction region 11 is subjected to heat exchange. The liquid is directly introduced into the membrane separation device 50 without passing through a vessel or the like.
An element (water vapor permeable membrane) described later is provided in the membrane separation device 50, and the surface of the element has a property of selectively transmitting moisture or water vapor in a mixture (liquid or gas). are doing. For this reason, only the water vapor is separated from the gas (or liquid) synthesized in the reactor 10 by passing through the element in the membrane separation device 50.
[0021]
The structure of the element (water vapor permeable membrane) installed inside the above-mentioned membrane separation device 50 includes a hollow circular tube, a honeycomb structure, and a flat plate type. Hereinafter, a configuration example of the membrane separation device 50 using a tubular element will be described with reference to FIG.
[0022]
The membrane separation device 50 has a function of separating the supplied synthesis gas (inlet gas) into water vapor (membrane permeable gas) contained in the synthesis gas and the remaining hydrogen gas, carbon monoxide, etc. (outlet gas). are doing.
The membrane separation device 50 has a configuration in which a cylindrical element (water vapor permeable membrane) 52 is installed inside a casing 51.
[0023]
The casing 51 includes an inlet nozzle 53 for supplying an inlet gas, a sweep gas nozzle 54 for supplying a sweep gas, a permeate gas nozzle 55 from which a membrane-permeable gas and a sweep gas flow, and a synthetic (flammable) gas from which water vapor has been removed. It is a closed container provided with an outlet nozzle 56 that flows out.
The interior of the casing 51 is partitioned by a pair of upper and lower partition plates 57, 58 into three spaces, a sweep gas chamber 59, an inlet / outlet gas chamber 60, and a permeated gas chamber 61. A sweep gas nozzle 54 is opened in the sweep gas chamber 59, an inlet nozzle 53 and an outlet nozzle 56 are opened in the inlet / outlet gas chamber 60, and a permeable gas nozzle 55 is opened in the permeable gas chamber 61.
In addition, the inlet nozzle 53 introduces the synthesis gas generated in communication with the reaction region 11, and the outlet nozzle 56 opens into the outlet gas region 12 to allow the synthesis gas from which the water vapor has been removed to flow out.
[0024]
A large number of the elements 52 are provided so as to penetrate a pair of upper and lower partition plates 57 and 58 such that one end is opened to the sweep gas chamber 59 and the other end is opened to the permeated gas chamber 61. Examples of the element 52 include an inorganic material such as a silica gel film disclosed in, for example, Japanese Patent Nos. Separation membranes can be used.
The silica gel membrane disclosed herein has heat resistance and acid resistance, and is capable of separating water from an organic acid or an organic solvent / water mixture or separating and removing water vapor from a gas containing water vapor with high performance. .
[0025]
Hereinafter, the operation of the water vapor separation in the membrane separation device 50 will be described.
The synthesis (flammable) gas synthesized in the reaction region 11 of the reactor 10 by receiving the supply of the raw material and the reaction gas is used as an inlet gas of the membrane separation device 50 installed in the reactor 10 as well. From 53, the gas flows into the inlet / outlet gas chamber 60. In the process of flowing toward the outlet nozzle, the water vapor contained in the synthesis gas passes through the element 52 as shown by an arrow 62 (see FIG. 2B) and enters the hollow portion 52a of the element 52. As a result, the synthesis gas is separated into water vapor (membrane permeable gas) in the hollow portion 52a and components other than water vapor that does not pass through the element 52 (outlet gas).
[0026]
Of these, the outlet gas (non-membrane gas) other than the water vapor containing the combustible gas component flows out of the outlet nozzle 56 to the outlet gas region 12 on the downstream side, and is further guided to the outside of the reactor 50. In the membrane separation device 50, since the water vapor may not be completely removed, the outlet gas may contain a certain amount of residual water vapor.
[0027]
On the other hand, the water vapor that has passed through the element 52 flows in from the sweep gas nozzle 54, flows out of the permeate gas nozzle 55 through the hollow portion 52 a, and flows out from the permeate gas nozzle 55 as a driving force, and flows out together with the sweep gas. The water vapor and the sweep gas separated in this way are sucked into the blower 22 through the three-way valve 21 and returned to the reactor 10, so that the sweep gas contains a gas fluid (oxygen-enriched air) which is charged into the reactor 10 as a reaction gas. And the like, and more preferably those containing no water vapor.
[0028]
That is, the steam that has passed through the element 52 in the membrane separation device 50 is discharged to the outside of the reactor 10 via the permeated gas outlet line 34, accompanied by the sweep gas flowing through the hollow portion 52a. In order for the water gasification reaction to proceed in the reactor 10, it is necessary to supply the sweep gas mixed with the water vapor to the reactor 10 via the reaction gas circulation supply line 32. In this state, the temperature of the water vapor that has passed through the membrane separation device 50 is less reduced, and therefore, the high-temperature water vapor can be circulated and reused.
As a result, the water vapor separated and removed by the membrane separation device 50 returns to the reactor 10 via the permeated gas outlet line 34, the blower 22, and the reaction gas circulation supply line 32, and an annular water vapor circulation path that repeats the circulation thereafter is formed. You.
[0029]
Further, in the above-described membrane separation device 50, by using a sweep gas having a low water vapor concentration, the inlet / outlet gas chambers 60 before and after the element 52, that is, outside the element 52, and the hollow inside the element 52. Since the partial pressure difference between the steam and the portion 52a is increased, the permeation efficiency of the steam is improved.
The sweep gas supplied from the sweep gas supply line 33 and flowing through the hollow portion 52a of the element 52 includes the above-described reaction gases, that is, the reaction gas (steam, hydrogen, hydrocarbon, or the like), air, oxygen, or any of these. Can be used, and in any case, a gas having a low water vapor concentration is preferable.
[0030]
The synthesis gas from which the water vapor has been removed in this manner becomes a high-quality fuel having a high calorific value due to an increase in the concentration of the combustible component, and is used, for example, as a fuel for an internal combustion engine generator. In the internal combustion engine generator, a power source (internal combustion engine) for driving the generator to generate power is appropriately selected from a gas engine and a gas turbine.
A synthesis gas having a high concentration of hydrogen and carbon monoxide is used as a raw material gas such as methanol or dimethyl ether.
[0031]
The heat exchanger 23, the condenser 24, and the vacuum pump 25 in the figure are necessary when the reactor 10 functions as a membrane reactor described later. Therefore, the three-way valve 21, the steam discharge line 35, the reaction It is not an essential component together with the gas supply line 36 and the air supply line 37.
[0032]
[Example 1]
The operation of performing the water gasification reaction under the following conditions was performed using the apparatus having the configuration shown in FIG. 1, and as a result, the boiler fuel required for generating steam was reduced by about 30 times as compared with the case where the membrane separation apparatus was not used. % Reduction.

[0033]
Next, as a modified example of the first embodiment, a reactor 10 that performs a reaction operation without supplying steam will be described with reference to FIG.
When the reaction is performed without supplying steam to the reactor 10 and steam is produced as a by-product in the synthesis reaction process, the steam present in the reactor 10 is selectively separated from the synthesis gas. The equilibrium state at is collapsed. As a result, the synthesis reaction proceeds in a direction in which steam is generated in an accelerated manner, and as a result, the reaction rate is increased.
[0034]
This will be explained based on the following reaction formula [2].
Product C and water vapor H by the reaction of raw materials A and B ₂ In the case of a reaction for synthesizing O, water (H ₂ When O) is selectively separated, the equilibrium reaction [2] collapses, and the reaction in the rightward direction is promoted. As a result, the rate of synthesis of the product C has increased.
In general, a reactor using such a water vapor permeable membrane to increase the synthesis reaction rate is called a membrane reactor. The membrane separation device 50 used in this membrane reactor needs to have heat resistance.
A + B → C + H ₂ O ..... [2]
[0035]
The configuration of the reactor 10 in this embodiment is substantially the same as that of the above-described first embodiment, except that an organic substance serving as a raw material is supplied from the raw material supply line 31, a reaction gas is supplied from the reaction gas supply line 36, and , Air or oxygen from the air supply line 37 to the reaction zone 11 of the reactor 10.
When the reaction of generating steam in the reactor 10 described above proceeds, the steam that has passed through the element 52 in the membrane separation device 50 shown in FIG. After that, it is discharged to the outside of the reactor 10. Thereafter, the flow is switched to the steam discharge line 35 by the switching operation of the three-way valve 21, and the high-temperature steam is cooled when passing through the heat exchanger 23 provided in the steam discharge line 35. This water vapor is further collected by the condenser 24 installed on the downstream side and discharged as condensed water.
[0036]
In this case, the reactor 10 has a function as a membrane reactor. Further, the reaction gas is individually supplied from the reaction gas supply line 36 to the reaction region 11 in the reactor 10. Further, since the sweep gas cannot be used because the recovery and reuse of the sweep gas is difficult because the steam circulation path is not formed, the inside of the membrane separation device 50 is vacuum pumped to increase the permeation (separation) efficiency. In some cases, the decompression process is performed by using the pressure reducing process.
More specifically, the pressure reducing process will be described. The end of the element 52 on the side of the sweep gas chamber 59 is closed, and the gas in the hollow portion 52a is sucked from the other end by the vacuum pump 25, so that the inside of the hollow portion 52a becomes external. The pressure is reduced to lower pressure.
[0037]
Specific reaction examples in the above-described membrane reactor are shown below.
C + O ₂ → CO ₂ ..... [3]
CO ₂ + H ₂ → CO + H ₂ O ..... [4]
In the present embodiment, the three-way valve 21 for selectively switching the steam circulation path, the blower 22 forming the steam circulation path, and the reaction gas circulation supply line 32 are not essential components.
[0038]
By the way, in the above-described first embodiment (including the modification), the air supplied from the sweep gas supply line 33 or the air supply line 37 may be introduced as it is, By supplying enriched air (or oxygen), the amount of nitrogen gas contained in the air is reduced. For this reason, the concentration of the combustible gas component contained in the synthesis gas discharged from the reactor 10 increases by an amount corresponding to the decrease in the nitrogen gas.
[0039]
The oxygen-enriched air described above can be generated and supplied by a pressure swing adsorption device (PSA), which is a known technology. In this pressure swing adsorption, adsorption is performed by an adsorbent by increasing the pressure, and desorption is performed by decreasing the pressure. Thus, the adsorption / desorption cycle can be repeated to perform dehumidification in air, recovery of gas, and the like.
[0040]
When pressure swing adsorption is used to generate oxygen-enriched air, it is generally preferable to use surplus compressed air in a factory or the like to reduce power consumption. This is because, in normal pressure swing adsorption, that is, in an operation that does not receive the supply of excess compressed air, it is necessary to operate the attached compressor to supply compressed air, so that the power consumption in this compressor is large. is there. Therefore, even if the synthesis gas (combustible gas) generated in the reactor 1 is used as a fuel and the internal combustion engine generator is operated to generate power, the amount of power that can be supplied to the outside is eventually reduced, and the merit is small.
[0041]
<Second embodiment>
Next, a second embodiment of the present invention will be described with reference to FIG.
This embodiment is different from the first embodiment shown in FIG. 1 in that the membrane separation device 50 shown in FIG. 2 is provided outside the reactor 10A, unlike the configuration in which the membrane separation device 50 is provided inside the reactor 10. It is arranged. The same parts as those in the above-described embodiment are denoted by the same reference numerals, and detailed description thereof will be omitted.
[0042]
The synthesis gas discharged from the reactor 10A is primarily cooled by the heat exchanger 26 via the outlet gas line 38, and is secondarily cooled by the supplementary heat exchanger 27 provided downstream of the outlet gas line 28. You. Thereafter, the gas is supplied to a membrane separation device 50 provided further downstream of the outlet gas line 38. That is, the membrane separation device 50 is provided in the outlet gas line 38 which is a pipe connected to the outlet of the reactor 10A.
[0043]
The water vapor separated from the synthesis gas by the membrane separation device 50 is sucked into the gas circulation blower 28 and passes through the permeated gas outlet line 34 together with the sweep gas.
The steam supplied from the replenishment steam line 39 is subjected to secondary cooling of the synthesis gas in the replenishment heat exchanger 27 to recover waste heat and to increase the temperature, and to join the permeated gas outlet line 34 in the three-way valve 29. The shortage of steam is replenished.
[0044]
The steam replenished by the three-way valve 29 is further recovered by the heat exchanger 26 to recover the waste heat of the synthesis gas and heated to a high temperature, and then supplied to the reactor 10A from the reaction gas circulation supply line 40. The steam supplied here contains a sweep gas, similarly to the reaction gas circulation supply line 32 in the first embodiment.
[0045]
When the waste heat is used by providing the above-described heat exchanger 26 and the supplementary heat exchanger 27, the temperature of the steam or the sweep gas (oxygen-enriched air or the like) to be charged into the reactor 10A can be set high, so that the reactor 10A The rate of partial combustion that maintains the inside temperature at a high temperature can be reduced. Further, since the waste heat is effectively used, the thermal efficiency of the entire apparatus can be improved.
The reactor 10A can be operated without providing the heat exchanger 26 and the replenishment heat exchanger 27 described above, and various conditions such as providing at least one heat exchanger or changing the order of installation are required. Can be changed as appropriate.
[0046]
In the above-described reactor 10A of the present invention, a steam circulation path is formed in which the steam contained in the synthesis gas is separated and removed by the membrane separation device 50, recovered, and returned to the reactor 10A.
The steam circulation path shown in FIG. 3 separates and collects steam flowing into the membrane separation device 50 together with the synthesis gas through the heat exchanger 26 and the supplementary heat exchanger 27, and reacts through the blower 28 and the heat exchanger 26. It is configured to return to the vessel 10A. Since the steam flowing through the steam circulation channel circulates without being condensed, the loss of condensation latent heat is reduced and the heat efficiency is high as compared with the conventional case where the steam is condensed and discarded outside the system.
In addition, since the water gasification reaction is carried out by using the steam while recycling it, the amount of steam discharged to the outside of the system can be minimized, and therefore, the amount of replenished steam generated in the boiler is also minimized. .
[0047]
For this reason, it is effective to reduce the consumption of boiler fuel necessary for generating supplementary steam, and to reduce the size and cost of the apparatus. In addition, since the required capacity of a dehumidifier (PSA method or the like) for separating moisture from the synthesis gas and a gas holder can be reduced, it is also effective in reducing the size and cost of the device.
Also, if oxygen-enriched air or oxygen is used as the air to be charged into the reactor 10A and this is used as the sweep gas of the membrane separation device 50, the membrane permeation amount of steam increases, and the amount of recovered steam can increase. it can. It should be noted that other gases can be used as the sweep gas, but in this case, a new gas supply system is required, which hinders downsizing and cost reduction of the apparatus.
[0048]
Further, since the waste heat of the synthesis gas is used to heat and raise the temperature of the input steam and supplementary steam, and the oxygen-enriched air and oxygen (air) for partial combustion, the temperature of the reactor 10A is maintained. Combustion can be minimized. When the partial combustion is minimized in this way, the amount of air containing nitrogen necessary for the partial combustion also decreases, so that when air or oxygen-enriched air is injected, it is included in the combustible gas generated The nitrogen gas amount is reduced, and the combustible gas component becomes a high calorific value gas which is favorable as a fuel for an internal combustion engine.
[0049]
[Example 2]
Using the apparatus having the configuration shown in FIG. 3 and performing an operation of performing a water gasification reaction under the following conditions, as compared with a case where the membrane separation apparatus is not used, the boiler fuel required for generating steam is reduced by about 31. % Reduction.

[0050]
<Third embodiment>
Next, a third embodiment of the present invention will be described with reference to FIGS. In the following description, the same parts as those in the above-described embodiment are denoted by the same reference numerals, and detailed description thereof will be omitted.
In this embodiment, a reactor 10B having a configuration similar to the reactor 10 of the first embodiment shown in FIG. 1 and a catalyst reactor 70 having a membrane separation device 50 installed between catalyst layers are connected in series. Is shown, for example, methanol can be obtained from an organic material as a raw material.
[0051]
The reactor 10B arranged on the upstream side is different from the reactor 10 in the configuration in which the heat transfer tube 41 is arranged in the reaction region 11. The heat transfer tube 41 cools the synthesis gas generated in the reaction region by a cooling fluid flowing inside the tube. The cooling fluid used here joins the sweep gas in the sweep gas supply line 33. Accordingly, the cooling fluid is preferably a gas fluid charged into the reactor 10B as a reaction gas, such as oxygen-enriched air, like the sweep gas.
[0052]
The synthesis gas synthesized in the reactor 10B and from which water has been separated and removed by the membrane separation device 50 is guided to the catalyst reactor 70 through the outlet gas line 38 and the heat exchanger 42 provided in the middle thereof. In the heat exchanger 42, the high-temperature synthesis gas is cooled.
In the catalyst reactor 70, a membrane separation device 50 is provided in a catalyst packed layer, specifically, between the catalyst layers 71 and 72. When the synthesis gas is introduced into the catalyst layer 71, the catalyst layer 71 is removed. Then, a methanol synthesis reaction proceeds.
Steam produced as a by-product of the methanol synthesis reaction is separated and removed by the membrane separation device 50, and is discharged from the permeated gas outlet line 45 to the outside of the reactor. The synthesis gas from which the water vapor has been separated and removed in this way passes through the catalyst layer 72 and is then taken out of the reactor from the synthesis product outlet line 43 as a synthesis product (for example, methanol).
[0053]
On the other hand, the steam separated by the membrane separation device 50 on the side of the reactor 10B is circulated from the reaction gas circulation line 32 to the reactor 10B via the permeated gas outlet line 34 and the blower 22, and is reused. Excess steam is discharged as condensed water through the steam discharge line 35, the heat exchanger 23, and the condenser 24. Similarly, the steam separated and removed by the membrane separation device 50 on the catalyst reactor 70 side is discharged as condensed water through the permeated gas outlet line 45, the heat exchanger 46, and the condenser 24.
The non-condensed gas not condensed in the condenser 24 is exhausted from the vacuum pump 25 to the atmosphere or the like.
Reference numeral 47 in the drawing denotes a line for returning a part of the synthesized product to the outlet gas line 38 by the pump 48 and joining them.
[0054]
FIG. 5 shows a so-called membrane reactor as one embodiment of the catalytic reactor. In the catalytic reactor 80, a catalyst 83 is filled in a casing 82 in which a heating gas channel 81 is provided on an outer peripheral surface. A raw material gas inlet 84 and a synthesis gas outlet 85 are provided at both axial end surfaces of the cylindrical casing 82.
[0055]
Further, inside the casing 82 filled with the catalyst 83 (inside the catalyst packed layer), a number of elements 86 similar to the element 52 of the membrane separation device 50 described above are provided. The ends of the cylindrical elements 86 are connected to an inlet header 87 and an outlet header 88, respectively.
The one inlet header 87 is connected to a sweep gas supply pipe 89 for supplying soup gas from outside the casing 82.
Further, a permeated gas outlet pipe 90 for guiding the water vapor and the sweep gas permeated through the element 86 to the outside of the casing 82 is connected to the outlet header portion 88.
[0056]
In the catalyst reactor 80 configured as described above, when the raw material gas supplied from the raw material gas inlet 84 reacts in the region filled with the catalyst 83 to generate the synthesis gas, the water vapor by-produced at the same time generates a water vapor permeable film. Is selectively permeated and separated and removed, and is guided to the outside from a hollow portion in the element 83 through an outlet header 88 and a permeated gas outlet pipe 90. As a result, the synthesis gas flowing out of the synthesis reactor outlet 85 to the outside of the catalytic reactor 80 is removed from water vapor and becomes a high-quality gas having a high synthesis gas concentration.
[Example 3]
Using the apparatus having the configuration shown in FIG. 4 and operating under the following conditions, the methanol yield was improved by 35% as compared with the case where the membrane separation apparatus was not used.

[0057]
According to the above-described reactor and catalyst reactor of the present invention, the steam contained in the synthesis gas generated in the reactor, that is, the unused portion of the steam supplied as the reaction gas and the by-products generated by the reaction. Since a steam separation membrane is provided for selectively separating and removing one or both of the separated steam, the steam can be separated and removed at a high temperature without cooling.
By forming a steam circulation path for returning the high-temperature steam separated and removed by the steam separation membrane to the reactor and circulating the steam, the steam required for the water gasification reaction in the reactor is discharged without being condensed. It becomes possible to use it while reducing the amount and recycling.
[0058]
In the reactor of the present invention described above, the state in the reactor may be any of a solid / gas reaction, a liquid / gas reaction, and a gas / gas reaction, and the separation membrane usable in a gas phase or a liquid phase may be used. Application is preferred.
It should be noted that the configuration of the present invention is not limited to the above-described embodiments, and various modifications can be made, such as an appropriate combination without departing from the gist of the present invention.
[0059]
【The invention's effect】
According to the reactor of the present invention described above, the following effects can be obtained.
According to the reactor according to claim 1, a water vapor permeable membrane (membrane separation means) for selectively separating and removing water vapor contained in the synthesis gas generated in the reactor is provided inside the reactor, Since the steam separated and removed by the steam permeable membrane and the synthesis gas after the removal of the steam are discharged to the outside of the reactor in separate systems, the steam is kept at a high temperature without lowering the temperature of the generated synthesis gas. Can be separated and removed, and a reactor with good thermal efficiency can be provided. That is, since there is no need to perform cooling or heating to separate and remove water vapor, fuel and the like required for the heating source can be saved.
[0060]
According to the reactor of the second aspect, a water vapor permeable membrane (membrane separation means) for selectively separating and removing water vapor contained in the synthesis gas generated in the reactor is connected to the reactor outlet. In the piping section, the steam separated and removed by the water vapor permeable membrane and the synthesis gas after the removal of the steam are configured to be led in different systems, respectively, so the temperature of the generated synthesis gas remains high without lowering the temperature. Water vapor can be separated and removed, and a reactor with high thermal efficiency can be provided. That is, since there is no need to perform cooling or heating to separate and remove the water vapor, fuel and the like required for the heating source can be saved.
[0061]
According to the reactor of the third aspect, a water vapor permeable membrane (membrane separation means) for selectively separating and removing water vapor contained in the synthesis gas generated in the reactor is provided in the catalyst packed layer. Since the steam separated and removed by the steam permeable membrane and the synthesis gas after the removal of the steam are discharged to the outside of the reactor in separate systems, the temperature of the generated synthesis gas is kept high without lowering the temperature. Water vapor can be separated and removed, and a reactor with high thermal efficiency can be provided. That is, since there is no need to perform cooling or heating to separate and remove water vapor, fuel and the like required for the heating source can be saved.
[0062]
Further, by forming a steam circulation path for returning and circulating the steam separated and removed by the above-mentioned steam permeable membrane to the reactor, the separated steam can be circulated at a high temperature and reused. In addition, it is possible to reduce the discharge amount and condense the water vapor required for the water gasification reaction in the reactor, and to use it while recycling. For this reason, the apparatus becomes a heat-efficient apparatus, and the size of the boiler and the dehumidifying apparatus for supplying replenished steam can be reduced, so that the entire apparatus can be reduced in size. This has a remarkable effect that an inexpensive device can be provided by reducing the number of the components.
[0063]
Further, since the synthesis gas obtained by the apparatus of the present invention can be used as fuel for an internal combustion engine, when power is generated by using the internal combustion engine as a drive source, small- and medium-scale amounts of carbides are processed to perform a daily start / stop operation. As a result, the pyrolysis gasifier apparatus can be used in a wide range without being limited by the throughput of the carbide.
When used as a raw material gas for synthesizing methanol, dimethyl ether, or the like, the concentration of water vapor in the gas can be reduced to 1% or less. On the other hand, an effect of improving the synthesis reaction rate as a membrane reactor can also be expected.
[0064]
Also, if a sweep gas is injected into the steam separated and removed by the steam separation membrane, the partial pressure difference of the steam inside and outside the steam separation membrane increases, so that the steam separated through the membrane steam separation membrane is removed. The amount can be increased, and as a result, the amount of water vapor that can be recovered can be increased.
[Brief description of the drawings]
FIG. 1 is a configuration diagram showing a first embodiment of a reactor according to the present invention.
FIGS. 2A and 2B are diagrams showing a configuration example of a membrane separation device in FIG. 1, wherein FIG. 2A is a cross-sectional view and FIG. 2B is a perspective view for explaining separation and removal of water vapor.
FIG. 3 is a configuration diagram showing a second embodiment of the reactor according to the present invention.
FIG. 4 is a configuration diagram showing a third embodiment of the reactor according to the present invention, showing an example of application to a catalytic reactor.
FIG. 5 is a cross-sectional view illustrating a configuration example of a catalytic reactor.
FIG. 6 is a configuration diagram showing a conventional reactor.
[Explanation of symbols]
10,10A, 10B reactor
11 Reaction zone
12 Outlet gas area
22 blower
23, 26 heat exchanger
24 condenser
25 vacuum pump
27 Replenishment heat exchanger
28 Gas circulation blower
31 Raw material supply line
32,40 Reaction gas circulation supply line
33,44 Sweep gas supply line
34,45 Permeated gas outlet line
35 Steam discharge line
36 Reaction gas supply line
37 Air supply line
38 Outlet gas line
39 Replenishment steam line
41 Heat transfer tube
42, 46 heat exchanger
43 Composite exit line
50 Membrane separation device (steam separation device)
52 elements (water vapor permeable membrane)
52a hollow part
70,80 catalytic reactor
71,72 Catalyst layer
83 catalyst
86 element (water vapor permeable membrane)

Claims (6)

A reactor for syngas production, wherein at least one of steam injected for the reaction and steam generated by the reaction is included in the generated synthesis gas,
Membrane separation means for selectively separating and removing steam contained in the synthesis gas generated in the reactor is provided inside the reactor, and the steam separated and removed by the membrane separation means and the synthesis after removing the steam are provided. A reactor characterized in that the gas and the gas are discharged to the outside of the reactor in separate systems. A reactor for syngas production, wherein at least one of steam injected for the reaction and steam generated by the reaction is included in the generated synthesis gas,
Membrane separation means for selectively separating and removing water vapor contained in the synthesis gas generated in the reactor is provided in a pipe connected to the reactor outlet, and the water vapor separated and removed by the membrane separation means is provided. A reactor which is configured to guide the synthesis gas from which steam has been removed through separate systems. A reactor for syngas production, comprising a catalyst-packed layer therein, wherein at least one of steam injected for the reaction and steam generated by the reaction is included in the generated synthesis gas,
Membrane separation means for selectively separating and removing steam contained in the synthesis gas generated in the reactor is provided in the catalyst packed layer, and the steam separated and removed by the membrane separation means, and Wherein the synthesis gas is discharged to the outside of the reactor in separate systems. The reactor according to any one of claims 1 to 3, wherein a steam circulation path for circulating the steam separated and removed by the membrane separation means back to the reactor is formed. The reactor according to any one of claims 1 to 4, wherein a sweep gas is introduced into the steam separated and removed by the membrane separation means. The reactor according to claim 5, wherein the sweep gas is oxygen-enriched air or a reaction gas such as oxygen or hydrogen.

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