JP3801807B2

JP3801807B2 - Supercritical water reactor

Info

Publication number: JP3801807B2
Application number: JP09063199A
Authority: JP
Inventors: 慎一朗川崎; 裕志鈴垣; 明鈴木
Original assignee: Organo Corp
Current assignee: Organo Corp
Priority date: 1999-03-31
Filing date: 1999-03-31
Publication date: 2006-07-26
Anticipated expiration: 2019-03-31
Also published as: JP2000279795A

Description

【０００１】
【発明の属する技術分野】
本発明は、水溶性有機物を含む被処理液に加えて、疎水性有機物を反応器に送入して超臨界水反応により有機物を処理する超臨界水反応装置に関し、更に詳細には、有機物のチャーリングを引き起こすことなく、被処理液及び疎水性有機物を含む流体を安定して反応器に送入し、安定した反応温度で超臨界水反応を持続させるようにした超臨界水反応装置に関するものである。
【０００２】
【従来の技術】
環境問題に対する認識の高まりと共に、有機物の酸化、分解能力の高い超臨界水反応を利用して、環境汚染物質を分解、無害化する試みが注目されている。すなわち、超臨界水の高い反応性を利用した超臨界水反応により、従来技術では分解することが難しかった有害な難分解性の有機物、例えば、ＰＣＢ（ポリ塩素化ビフェニル）、ダイオキシン、有機塩素系溶剤等を分解して、二酸化炭素、窒素、水、無機塩などの無害な生成物に転化する試みである。
【０００３】
超臨界水反応装置とは、超臨界水の高い反応性を利用して有機物を分解する装置であって、例えば、難分解性の有害な有機物を分解して無害な二酸化炭素と水に転化したり、難分解性の高分子化合物を分解して有用な低分子化合物に転化したりするために、現在、その実用化が盛んに研究されている。
超臨界水とは、超臨界状態にある水、即ち、水の臨界点を越えた状態にある水を言い、詳しくは、３７４．１℃以上の温度で、かつ２２．０４ＭＰａ以上の圧力下にある状態の水を言う。超臨界水は、有機物を溶解する溶解能が高く、有機化合物に多い非極性物質をも完全に溶解することができる一方、逆に、金属、塩等の無機物に対する溶解能は著しく低い。また、超臨界水は、酸素や窒素などの気体と任意の割合で混合して単一相を構成することができる。
【０００４】
ここで、図６及び図７を参照して、従来の超臨界水反応装置の基本的な構成を説明する。図６は従来の超臨界水反応装置の構成を示すフローシートである。図７（ａ）は二流体ノズルの部分縦断面図、図７（ｂ）は図７（ａ）の線III −III での横断面図である。
超臨界水反応装置１０は、有機物を含む被処理液を超臨界水の存在下で超臨界水反応により処理する装置であって、図６に示すように、超臨界水反応を行う反応器として、縦型の耐圧密閉型反応器１２を備え、反応器１２から処理液を流出させる処理液管１４に、順次、処理液を冷却する冷却器１６、反応器１２内の圧力を制御する圧力制御弁１８、及び、処理液をガスと液体とに気液分離する気液分離器２０を備えている。
尚、縦型反応容器は、通常、固形物の含有率が低い被処理液を処理する際に適しており、固形物の含有率が高い被処理液を処理する際には、パイプ状のチューブラー反応器を使用することが多い。
【０００５】
超臨界水反応装置１０は、超臨界水反応に供する反応物を反応器１２に供給する供給系統として、有機物を含む被処理液を被処理液管２２を介して反応器１２に送入する被処理液ポンプ２４と、酸化剤として空気を空気送入管２６を介して反応器１２に送入する空気圧縮機２８とを備えている。
更に、超臨界水反応装置１０は、必要に応じて、反応器１２での超臨界水反応を維持するのに必要な熱エネルギー源として石油系炭化水素油等の疎水性有機物からなる補助燃料を反応器１２に送入する補助燃料管３０、反応器１２で超臨界水反応により処理液中の有機物から発生した塩素等を中和するアルカリ剤を反応器１２に送入するアルカリ剤送入管３１を被処理液管２２に合流させさせている。なお、被処理液中の水分が不足し、超臨界水反応が維持できない場合は、被処理液管２２に補給水を加えるための補給水管（図示せず）を接続することもある。
【０００６】
被処理液管２２と空気送入管２６とは、二流体ノズル３４を介して反応器１２に接続されている。
二流体ノズル３４は、図７に示すように、内管３６と外管３８とからなる二重管として構成され、外管３８の先端部３８ａが縮径して、先端の環状開口面積が上流の環状面積より急激に小さくなっている。そして、被処理液管２２は二流体ノズル３４の内管３６に接続され、空気送入管２６は内管３６と外管３８とからなる環状部３９に接続されている。
【０００７】
以上の構成により、二流体ノズル３４は、外管３８の先端部３８ａから噴出する空気のアトマイジング効果により、内管３６から被処理液を噴霧状で反応器１２内に噴射させることができる。
また、二流体ノズル３４で被処理液を内管３６に流し、環状部３９に空気を流しているのは、二流体ノズル３４と反応器１２との接続部で、内管３６を流れる被処理液中の有機物が反応器１２の熱によって加熱され、チャーリング（炭化）することがないように、環状部３９を流れる空気によって反応器１２から内管３６を断熱する効果もある。
【０００８】
なお、被処理液と処理液とを熱交換させて処理液を冷却するとともに被処理液を昇温して熱回収を図る熱交換器（図示せず）を冷却器１６の上流の処理液管１４に、又は被処理液を予熱する予熱器を反応器１２の上流の被処理液管２２に設けることもある。また、超臨界水の補給水管を被処理液管２２に接続することもある。
更には、反応器１２の下部に亜臨界水領域を設け、反応器１２内で生じた無機塩類を亜臨界水領域に沈降させ、除去する機構を設けることもある。
【０００９】
【発明が解決しようとする課題】
しかし、ベッセル型の反応器を反応器として使用している従来の超臨界水反応装置で、処理対象として水溶性有機物を含む第１の被処理液と、処理対象として疎水性有機物を含む第２の被処理液とを同時に同じ被処理液管及び二流体ノズルを介して反応器に送入するときには、反応器の反応温度が安定しないという問題があった。例えば、ある時には反応温度が上限温度に近くなり、あるときには反応温度が下限温度に近くなり、超臨界水反応の進行が極めて不安定になって、超臨界水反応を安定して持続させることが難しかった。
これは、第１の被処理液と、疎水性有機物を主成分とする補助燃料とを同時に同じ被処理液管及び二流体ノズルを介して反応器に送入するときにも、第２の被処理液の場合と同様に、反応温度が不安定で変動するという問題があった。
【００１０】
そこで、本発明の目的は、水溶性有機物を含む被処理液及び疎水性有機物を同時に反応器に送入する際にも、安定した反応温度で超臨界水反応を持続させるようにした超臨界水反応装置を提供することである。
【００１１】
【課題を解決するための手段】
本発明者は、実験を重ねた過程で、水溶性有機物を含む被処理液と疎水性有機物とを同時に反応器に送入した際に反応温度が不安定になるのは、次の現象に起因することを見い出した。
従来の超臨界水反応装置では、被処理液と疎水性有機物とを同時に送る被処理液管内で、水不溶性で水から分離し易いという疎水性有機物の性質に起因して、疎水性有機物が被処理液の水から分離して被処理液中でブロック化し、被処理液と、疎水性有機物ブロックとが、プラグ流れに近い形態で被処理液管から反応器に流入する。即ち、有機物濃度が高いブロックと、有機物濃度が低いブロックとに分離して、反応器に流入する。
その結果、有機物濃度が高いブロックが反応器に流入すると、超臨界水反応が急激に進行して反応温度が上昇する。逆に、有機物濃度が低いブロックが流入し続けると、発熱量が不足して、反応温度が低下するということを見い出した。即ち、反応温度の不安定性は、有機物が被処理液中に分散した状態で反応器に流入しないからであることを見い出した。
【００１２】
そこで、本発明者は、被処理液と補助燃料とを別々に反応器に送入することを着想し、本発明を完成するに到った。本発明を実現する第１の手段は、二流体ノズルに代えて三流体ノズルを使用し、反応器内で超臨界水に分散流入する被処理液中に疎水性有機物を分散させる、又は疎水性有機物と被処理液とを同時に超臨界水中に分散させる。
第２の手段は、二つの二流体ノズルを使い、一方の二流体ノズルでは被処理液と空気とを送入し、他方の二流体ノズルでは、補助燃料と空気とを送入する。
なお、二流体ノズルの環状部に、空気と、水、又は水溶性有機物とを供給し、内管に疎水性有機物を流通させたところ、反応温度は多少安定するものの、環状部を流れる流体の断熱効果が乏しく、内管を流れる疎水性有機物が加熱されて、チャーリングを引き起こし、内管を閉塞させるおそれがあることが判った。
【００１３】
上記目的を達成するために、上述の知見に基づいて、本発明に係る超臨界水反応装置（以下、第１の発明という）は、超臨界水を収容する縦型反応器を備え、主として水と水溶性有機物を含み、疎水性有機物を実質的に含まない第１の被処理液に加えて、主として疎水性有機物を含む第２の被処理液と、主として疎水性有機物からなる補助燃料の少なくともいずれか一方を反応器に送入し、かつ、酸化剤として酸素含有ガスを反応器に供給して、超臨界水の存在下で有機物と酸素との超臨界水反応を行う超臨界水反応装置であって、
第１の被処理液を反応器に送入する第１の送入手段、第２の被処理液及び補助燃料の少なくともいずれか一方を反応器に送入する第２の送入手段、並びに酸素含有ガスの送入手段として、反応器の反応物入口に三流体ノズルを設け、
三流体ノズルが、内管と、内管を挿入させた中管と、内管及び中管を挿入させた外管とによって、流路として外管と中管とからなる第１環状部と、中管と内管とからなる第２環状部と、内管とを備えた三重管として構成され、三重管の先端部で外管が縮径し、第１環状部の先端環状開口部の面積が、上流の第１環状部の面積より小さく、
酸素含有ガスの送入手段として設けられたガス送入管が第１環状部に、第１の送入手段として設けられた第１の送入管が第２環状部に、第２の送入手段として設けられた第２の送入管が内管に、それぞれ、接続されていることを特徴としている。
【００１５】
酸素含有ガス、第１の被処理液、及び、第２の被処理液と補助燃料との少なくともいずれかを三流体ノズルに別々に供給し、酸素含有ガスによってアトマイジングさせることにより、第２の被処理液及び補助燃料を超臨界水中に又は超臨界水中に分散する第１の被処理液中に均一に分散させることできる。
また、酸素含有ガスを送入するガス送入管が外管と中管とからなる第１環状部に、第１の被処理液を送入する第１の送入管が中管と内管とからなる第２環状部に、第２の被処理液及び補助燃料の少なくともいずれ一方を送入する第２の送入管が内管に、それぞれ、接続されていることにより、第１環状部を流れる酸素含有ガスの断熱効果により、内管を流れる第２の被処理液又は補助燃料のチャーリングを防止することができる。
【００１６】
第１の発明の好適な実施態様では、内管の外周面又は内周面に沿って断熱層が設けてある。断熱層の断熱効果により、内管を流れる疎水性有機物への熱伝導を防止して、一層効果的に疎水性有機物のチャーリングを防止することができる。なお、断熱層は、熱伝導性の低い物質層であれば良く、例えば空気層や、多数の独立気泡を有するセラミックやパーミキュライトなどの層を使用することができる。
【００１７】
また、本発明に係る超臨界水反応装置（以下、第２の発明という）は、超臨界水を収容する縦型反応器を備え、主として水と水溶性有機物を含み、疎水性有機物を実質的に含まない第１の被処理液に加えて、主として疎水性有機物を含む第２の被処理液と、主として疎水性有機物からなる補助燃料の少なくともいずれか一方を反応器に送入し、かつ、酸化剤として酸素含有ガスを反応器に供給して、超臨界水の存在下で有機物と酸素との超臨界水反応を行う超臨界水反応装置であって、
第１の被処理液を反応器に送入する第１の送入手段、第２の被処理液及び補助燃料の少なくともいずれか一方を反応器に送入する第２の送入手段、並びに酸素含有ガスの送入手段として、反応器の反応物入口に２個の二流体ノズルを設け、
２個の二流体ノズルは、それぞれ、内管と、内管を挿入させた外管とによって、流路として外管と内管とからなる環状部と、内管とを備えた二重管として構成され、二重管の先端部で外管が縮径し、環状部の先端環状開口部の面積が、上流の環状部の面積より小さく、
第１の送入手段として設けられた第１の送入管が一方の二流体ノズルの内管に、第２の送入手段として設けられた第２の送入管が他方の二流体ノズルの内管に、それぞれ、接続され、かつ、酸素含有ガスの送入手段として設けられたガス送入管から分岐した２本の分岐管が、それぞれ、一方の二流体ノズルの環状部及び他方の二流体ノズルの環状部に接続されていることを特徴としている。
【００１８】
【発明の実施の形態】
以下に、実施形態例を挙げ、添付図面を参照して、本発明の実施の形態を具体的かつ詳細に説明する。
実施形態例１
本実施形態例は、第１の発明に係る超臨界水反応装置の実施形態の一例であって、図１は本実施形態例の超臨界水反応装置の構成を示すフローシート、図２（ａ）は本実施形態例で使用する三流体ノズルの構造を示す縦部分断面図、図２（ｂ）は図２（ａ）の線Ｉ−Ｉでの横断面図である。図１に示す部品のうち、図６と同じものには同じ符号を付し、その説明を省略する。
本実施形態例の超臨界水反応装置４０は、二流体ノズルに代えて三流体ノズルを使用すること、三流体ノズルの使用に伴う変更を除いて、反応器及び反応器以降の流出系統の構成は、前述の従来の超臨界水反応装置と同じ構成を備えている。
【００１９】
超臨界水反応装置４０は、図１に示すように、主として水と水溶性有機物を含み、疎水性有機物を実質的に含まない第１の被処理液を反応器１２に送入する第１の送入管４２、第１の送入管４２を介して第１の被処理液を反応器１２に送入する第１の被処理液ポンプ４４と、疎水性有機物からなる補助燃料を反応器１２に送入する第２の送入管４６とを備えている。アルカリ剤送入管３１は、第１の送入管４２に接続されている。
第１の送入管４２、第２の送入管４６及び空気送入管２６は、三流体ノズル５０を介して反応器１２に接続されている。
【００２０】
本実施形態例の反応器で使用する三流体ノズル５０は、図２に示すように、内管５２と、内管５２を挿入させた中管５４と、内管５２及び中管５４を挿入させた外管５６とからなる三重管として構成されていて、流路として、中管５４と外管５６とによって区画された第１環状部５８、内管５２と中管５４とによって区画された第２環状部６０、及び、内管５２の３流路を有する。
三重管の先端部６２で外管５６が縮径し、第１環状部５８は、先端の環状開口部の面積が上流の環状流路の面積より小さくなっている。
第１環状部５８は空気送入管２６に、第２環状部６０は第１の送入管４２に、及び、内管５２は第２の送入管４６に、それぞれ、接続されている。
【００２１】
以上の構成により、本実施形態例では、内管５２から流れ出た補助燃料が、反応器１２内で第１環状部５８から流れ出た空気によりアトマイジングされて、超臨界水中に分散し、又は第２環状部６０から流出し、同じく空気によりアトマイジングされて超臨界水中に分散した第１の被処理液中に分散する。
よって、補助燃料が十分に分散して反応器１２内に導入されるので、従来の超臨界水反応装置のように反応温度が変動するようなことは生じない。即ち、一定の有機物濃度で有機物を導入できるので、反応温度の変動が生じない。
【００２２】
本実施形態例の超臨界水反応装置４０と同じ構成の実験装置を作製し、補助燃料としてＡ重油を使って、有機物濃度の低い被処理液に超臨界水反応処理を施し、反応器の反応温度を測定したところ、反応温度の変動幅は、図３のグラフ（１）で示すように、５℃であった。
一方、前述の従来の超臨界水反応装置１０と同じ構成の実験装置を作製し、同じように、補助燃料としてＡ重油を使って、有機物濃度の低い被処理液に超臨界水反応処理を施し、反応器の反応温度を測定したところ、反応温度の変動幅は、図３のグラフ（２）で示すように、３０℃にも達した。
この実験からも、本実施形態例の超臨界水反応装置４０が反応温度の変動を抑制する上で有効であると評価できる。
【００２３】
本実施形態例では、疎水性有機物として補助燃料を反応器１２に送入しているが、補助燃料に加えて疎水性有機物を主として含む第２の被処理液を第２の送入管４６で三流体ノズル５０に送入しても良く、又は補助燃料に代えて疎水性有機物を主として含む第２の被処理液を送入しても良い。
【００２４】
実施形態例２
本実施形態例は、実施形態例１の改変例であって、図４（ａ）は本実施形態例で使用する三流体ノズルの構造を示す縦部分断面図、図４（ｂ）は図４（ａ）の線II−IIでの横断面図である。図４に示す部品のうち、図２と同じものには同じ符号を付し、その説明を省略する。
本実施形態例の超臨界水反応装置は、三流体ノズルの構成が異なることを除いて実施形態例１の構成と同じであって、本実施形態例の三流体ノズル７０は、図４に示すように、内管５２の外周面にパーミキュライトからなる断熱層７２を備えていることを除いて、実施形態例１の三流体ノズル５０と同じ構成を備えている。
【００２５】
断熱層７２を設けて、その断熱効果により、内管５２を流れる疎水性有機物への熱伝導を防止して、一層効果的に疎水性有機物のチャーリングを防止することができる。尚、断熱層７２は、内管５２の内周面に設けても良い。
【００２６】
実施形態例３
本実施形態例は、第２の発明に係る超臨界水反応装置の実施形態の一例である。図５は本実施形態例の超臨界水反応装置の構成を示すフローシートである。
本実施形態例の超臨界水反応装置８０は、図５に示すように、三流体ノズルに代えて２個の二流体ノズル８２、８４を使用することを除いて、実施形態例１の超臨界水反応装置４０と同じ構成を備えている。
本実施形態例の超臨界水反応装置８０は、前述した図７で示した二流体ノズル３４と同じ構成の２個の二流体ノズル８２、８４を反応器１２の反応物入口に備えている。第１の送入管４２が一方の二流体ノズル８２の内管に、第２の送入管４６が他方の二流体ノズル８４の内管に、それぞれ、接続され、かつ、空気送入管２６から分岐した２本の分岐管８６、８８が、それぞれ、一方の二流体ノズル８２の環状部及び他方の二流体ノズル８４の環状部に接続されている。
これにより、第１の被処理液及び補助燃料をそれぞれ別個に分散させて、反応器１２に導入することができるので、実施形態例１と同様に、一定の有機物濃度で有機物を導入し、反応温度が安定する。
【００２７】
【発明の効果】
本発明によれば、第１の被処理液を反応器に送入する第１の送入手段と、第２の被処理液及び補助燃料の少なくともいずれか一方を反応器に送入する第２の送入手段とを設けて、それぞれ、反応器に流入させることにより、一定の有機物濃度で有機物を導入し、反応温度を安定させることができる。
すなわち、反応器への流入口に三流体ノズルを設け、酸素含有ガスを送入するガス送入管を外管と中管とからなる第１環状部に、水溶性有機物を主成分とする第１の被処理液を送入する第１の送入管を中管と内管とからなる第２環状部に、疎水性有機物を送入する第２の送入管を内管に、それぞれ、接続し、疎水性有機物を超臨界水中又は第１の被処理液中に分散させて反応器に送入することにより、安定した反応温度で超臨界水反応を持続させることできる。
また、三流体ノズルに代えて２個の二流体ノズルにより同じ効果を奏することができる。
【図面の簡単な説明】
【図１】実施形態例１の超臨界水反応装置の構成を示すフローシートである。
【図２】図２（ａ）は実施形態例１で使用する三流体ノズルの構造を示す縦部分断面図、図２（ｂ）は図２（ａ）の線Ｉ−Ｉでの横断面図である。
【図３】反応温度の変動を示すグラフである。
【図４】図４（ａ）は実施形態例２で使用する三流体ノズルの構造を示す縦部分断面図、図４（ｂ）は図４（ａ）の線ＩＩ−ＩＩでの横断面図である。
【図５】実施形態例３の超臨界水反応装置の構成を示すフローシートである。
【図６】従来の超臨界水反応装置の構成を示すフローシートである。
【図７】図７（ａ）は従来の超臨界水反応装置で使用する二流体ノズルの構造を示す縦部分断面図、図７（ｂ）は図７（ａ）の線ＩＩＩ−ＩＩＩでの横断面図である。
【符号の説明】
１０従来の超臨界水反応装置
１２縦型の耐圧密閉型反応器
１４処理液管
１６冷却器
１８圧力制御弁
２０気液分離器
２２被処理液管
２４被処理液ポンプ
２６空気送入管
２８空気圧縮機
３０補助燃料管
３１アルカリ剤送入管
３４二流体ノズル
３６内管
３８外管
３８ａ外管の先端部
３９環状部
４０実施形態例１の超臨界水反応装置
４２第１の送入管
４４第１の被処理液ポンプ
４６第２の送入管
５０三流体ノズル
５２内管
５４中管
５６外管
５８第１環状部
６０第２環状部
７０実施形態例２の超臨界水反応装置で使用する三流体ノズル
７２断熱層
８０実施形態例３の超臨界水反応装置
８２、８４二流体ノズル
８６、８８分岐管[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a supercritical water reactor for treating an organic substance by supercritical water reaction by feeding a hydrophobic organic substance into a reactor in addition to a liquid to be treated containing a water-soluble organic substance. A supercritical water reactor in which a liquid containing a liquid to be treated and a hydrophobic organic substance is stably fed into a reactor without causing charring, and the supercritical water reaction is maintained at a stable reaction temperature. It is.
[0002]
[Prior art]
With increasing awareness of environmental issues, attention has been paid to attempts to decompose and detoxify environmental pollutants using supercritical water reactions with high oxidation and decomposition capabilities of organic matter. That is, due to the supercritical water reaction utilizing the high reactivity of supercritical water, harmful and hardly decomposable organic substances that have been difficult to be decomposed by the prior art, such as PCB (polychlorinated biphenyl), dioxin, and organic chlorine It is an attempt to decompose solvents and convert them into harmless products such as carbon dioxide, nitrogen, water and inorganic salts.
[0003]
A supercritical water reactor is a device that decomposes organic substances using the high reactivity of supercritical water. For example, it decomposes harmful organic substances that are difficult to decompose and converts them into harmless carbon dioxide and water. In order to decompose difficult-to-decompose high-molecular compounds and convert them into useful low-molecular compounds, their practical application is currently being actively studied.
Supercritical water refers to water in a supercritical state, that is, water in a state exceeding the critical point of water, and more specifically, at a temperature of 374.1 ° C. or higher and a pressure of 22.04 MPa or higher. Says water in a certain state. Supercritical water has a high ability to dissolve organic substances, and can completely dissolve non-polar substances that are abundant in organic compounds. Conversely, the ability to dissolve inorganic substances such as metals and salts is extremely low. Supercritical water can be mixed with a gas such as oxygen or nitrogen at an arbitrary ratio to form a single phase.
[0004]
Here, with reference to FIG.6 and FIG.7, the fundamental structure of the conventional supercritical water reaction apparatus is demonstrated. FIG. 6 is a flow sheet showing the configuration of a conventional supercritical water reactor. FIG. 7A is a partial longitudinal sectional view of the two-fluid nozzle, and FIG. 7B is a transverse sectional view taken along line III-III in FIG. 7A.
The supercritical water reaction apparatus 10 is an apparatus for treating a liquid to be treated containing an organic substance by a supercritical water reaction in the presence of supercritical water, and as shown in FIG. 6, a reactor that performs a supercritical water reaction. , A vertical pressure-resistant sealed reactor 12, a processing liquid pipe 14 for flowing the processing liquid out of the reactor 12, a cooler 16 for cooling the processing liquid, and a pressure control for controlling the pressure in the reactor 12. A valve 18 and a gas-liquid separator 20 for separating the processing liquid into gas and liquid are provided.
The vertical reaction vessel is usually suitable for processing a liquid to be processed having a low solid content, and a pipe-shaped tube for processing a liquid to be processed having a high solid content. In many cases, a reactor is used.
[0005]
The supercritical water reactor 10 serves as a supply system for supplying a reactant to be subjected to a supercritical water reaction to the reactor 12, and supplies a liquid to be treated containing organic matter to the reactor 12 through a liquid tube 22 to be treated. A treatment liquid pump 24 and an air compressor 28 that feeds air as an oxidant into the reactor 12 through an air feed pipe 26 are provided.
Furthermore, the supercritical water reaction apparatus 10 receives auxiliary fuel made of a hydrophobic organic substance such as petroleum hydrocarbon oil as a heat energy source necessary for maintaining the supercritical water reaction in the reactor 12 as necessary. Auxiliary fuel pipe 30 to be fed into the reactor 12, and an alkaline agent feed pipe to which an alkaline agent that neutralizes chlorine generated from organic substances in the processing liquid by supercritical water reaction in the reactor 12 is fed into the reactor 12. 31 is joined to the liquid pipe 22 to be processed. When the water in the liquid to be treated is insufficient and the supercritical water reaction cannot be maintained, a replenishing water pipe (not shown) for adding make-up water to the liquid pipe 22 to be treated may be connected.
[0006]
The liquid tube 22 to be treated and the air inlet tube 26 are connected to the reactor 12 via a two-fluid nozzle 34.
As shown in FIG. 7, the two-fluid nozzle 34 is configured as a double tube including an inner tube 36 and an outer tube 38, the distal end portion 38 a of the outer tube 38 is reduced in diameter, and the annular opening area at the distal end is upstream. It is rapidly smaller than the annular area. The liquid pipe 22 to be treated is connected to the inner pipe 36 of the two-fluid nozzle 34, and the air inlet pipe 26 is connected to an annular portion 39 including the inner pipe 36 and the outer pipe 38.
[0007]
With the above configuration, the two-fluid nozzle 34 can spray the liquid to be treated from the inner tube 36 into the reactor 12 by the atomizing effect of the air ejected from the tip portion 38 a of the outer tube 38.
In addition, the liquid to be treated is caused to flow through the inner pipe 36 by the two-fluid nozzle 34 and the air is caused to flow through the annular portion 39 at the connecting portion between the two-fluid nozzle 34 and the reactor 12. There is also an effect that the inner tube 36 is insulated from the reactor 12 by the air flowing through the annular portion 39 so that the organic matter in the liquid is not heated and charred (carbonized) by the heat of the reactor 12.
[0008]
In addition, a heat exchanger (not shown) that heat-recovers the process liquid by heat-exchanging the process liquid and the process liquid and raising the temperature of the process liquid to recover the heat is disposed upstream of the cooler 16. 14 or a preheater for preheating the liquid to be treated may be provided in the liquid pipe 22 to be treated upstream of the reactor 12. Further, a supercritical water replenishment water pipe may be connected to the liquid pipe 22 to be treated.
Furthermore, a subcritical water region may be provided in the lower part of the reactor 12, and a mechanism may be provided for causing the inorganic salts generated in the reactor 12 to settle and remove in the subcritical water region.
[0009]
[Problems to be solved by the invention]
However, in a conventional supercritical water reactor using a vessel type reactor as a reactor, a first liquid to be treated containing a water-soluble organic substance as a treatment target and a second liquid containing a hydrophobic organic substance as a treatment target. When the liquids to be treated are simultaneously fed into the reactor through the same liquid pipe to be treated and the two-fluid nozzle, there is a problem that the reaction temperature of the reactor is not stable. For example, the reaction temperature is close to the upper limit temperature in some cases, the reaction temperature is close to the lower limit temperature in some cases, and the progress of the supercritical water reaction becomes extremely unstable, so that the supercritical water reaction can be stably maintained. was difficult.
This is also the case when the first liquid to be treated and the auxiliary fuel mainly composed of a hydrophobic organic substance are simultaneously fed into the reactor through the same liquid pipe and two-fluid nozzle. As in the case of the treatment liquid , there was a problem that the reaction temperature was unstable and fluctuated.
[0010]
Therefore, an object of the present invention is to provide a supercritical water that maintains a supercritical water reaction at a stable reaction temperature even when a liquid to be treated containing a water-soluble organic substance and a hydrophobic organic substance are simultaneously fed into a reactor. It is to provide a reactor.
[0011]
[Means for Solving the Problems]
In the course of repeated experiments, the present inventor caused the reaction temperature to become unstable when a liquid to be treated containing a water-soluble organic substance and a hydrophobic organic substance were simultaneously fed into the reactor. I found something to do.
In the conventional supercritical water reaction apparatus, the hydrophobic organic substance is covered by the property of the hydrophobic organic substance that is insoluble in water and easily separated from water in the liquid pipe to which the liquid to be processed and the hydrophobic organic substance are sent simultaneously. The process liquid is separated from the process liquid and blocked in the process liquid, and the process liquid and the hydrophobic organic substance block flow into the reactor from the process liquid pipe in a form close to the plug flow. That is, the block is separated into a block having a high organic matter concentration and a block having a low organic matter concentration, and flows into the reactor.
As a result, when a block with a high organic matter concentration flows into the reactor, the supercritical water reaction proceeds rapidly and the reaction temperature rises. On the other hand, it was found that if the block with a low organic matter concentration continues to flow, the reaction temperature decreases due to insufficient heat generation. That is, it has been found that the instability of the reaction temperature is because the organic matter does not flow into the reactor in a state of being dispersed in the liquid to be treated.
[0012]
Therefore, the present inventor has conceived that the liquid to be treated and the auxiliary fuel are separately fed into the reactor, and has completed the present invention . A first means for realizing the present invention uses a three-fluid nozzle in place of the two-fluid nozzle, and disperses the hydrophobic organic substance in the liquid to be treated dispersedly flowing into the supercritical water in the reactor. The organic substance and the liquid to be treated are simultaneously dispersed in supercritical water.
The second means uses two two-fluid nozzles. One of the two-fluid nozzles feeds the liquid to be treated and air, and the other two-fluid nozzle feeds auxiliary fuel and air.
In addition, when air and water or a water-soluble organic substance are supplied to the annular part of the two-fluid nozzle and the hydrophobic organic substance is circulated through the inner tube, the reaction temperature is somewhat stable, but the fluid flowing through the annular part It has been found that the heat insulating effect is poor, and the hydrophobic organic substance flowing through the inner tube is heated, causing charring and clogging the inner tube.
[0013]
In order to achieve the above object, based on the above knowledge, the supercritical water reactor according to the present invention (hereinafter referred to as the first invention) includes a vertical reactor that contains supercritical water, and is mainly composed of water. In addition to the first liquid to be treated that contains substantially water-soluble organic substance and substantially does not contain the hydrophobic organic substance, at least a second liquid to be treated mainly containing the hydrophobic organic substance and at least an auxiliary fuel mainly composed of the hydrophobic organic substance A supercritical water reactor that sends one of them into the reactor and supplies an oxygen-containing gas as an oxidant to the reactor to perform a supercritical water reaction between organic matter and oxygen in the presence of supercritical water Because
First feed availability stage, the second feed-in means for fed into a reactor at least one of the second liquid to be treated and auxiliary fuel fed to the first liquid to be treated to the reactor, and oxygen As a means for feeding the contained gas, a three-fluid nozzle is provided at the reactant inlet of the reactor,
The three-fluid nozzle includes an inner tube, an inner tube into which the inner tube is inserted, and an outer tube into which the inner tube and the inner tube are inserted. It is configured as a triple tube having a second annular portion composed of an intermediate tube and an inner tube, and an inner tube. The outer tube is reduced in diameter at the distal end of the triple tube, and the area of the distal annular opening of the first annular portion Is smaller than the area of the upstream first annular portion,
A gas inlet pipe provided as an oxygen-containing gas inlet means is provided in the first annular portion, and a first inlet pipe provided as the first inlet means is provided in the second annular portion, and the second inlet portion. The second feed pipe provided as a means is connected to the inner pipe, respectively .
[0015]
An oxygen-containing gas, a first liquid to be treated, and, at least one of the auxiliary fuel and the second liquid to be treated was fed separately to the three-fluid nozzle, by Atomaijin grayed I by the oxygen-containing gas, The second liquid to be treated and the auxiliary fuel can be uniformly dispersed in the supercritical water or the first liquid to be treated that is dispersed in the supercritical water.
In addition, a gas inlet pipe for feeding an oxygen-containing gas is provided in a first annular portion including an outer pipe and an inner pipe, and a first inlet pipe for feeding a first liquid to be treated is an inner pipe and an inner pipe. A second feed pipe for feeding at least one of the second liquid to be treated and the auxiliary fuel is connected to the inner pipe, respectively. Due to the heat insulating effect of the oxygen-containing gas flowing through the second gas, charring of the second liquid to be treated or auxiliary fuel flowing through the inner pipe can be prevented.
[0016]
In a preferred embodiment of the first invention , a heat insulating layer is provided along the outer peripheral surface or the inner peripheral surface of the inner tube. Due to the heat insulating effect of the heat insulating layer, heat conduction to the hydrophobic organic substance flowing through the inner pipe can be prevented, and charring of the hydrophobic organic substance can be more effectively prevented. In addition, the heat insulation layer should just be a material layer with low heat conductivity, for example, can use layers, such as an air layer and a ceramic which has many closed cells, and permiculite.
[0017]
The supercritical water reactor according to the present invention (hereinafter referred to as the second invention) includes a vertical reactor containing supercritical water, mainly containing water and water-soluble organic matter, and substantially containing hydrophobic organic matter. In addition to the first liquid to be treated not contained in the second liquid to be treated, which contains at least one of the second liquid to be treated mainly containing the hydrophobic organic substance and the auxiliary fuel mainly composed of the hydrophobic organic substance, and A supercritical water reactor that supplies an oxygen-containing gas as an oxidant to a reactor and performs a supercritical water reaction between an organic substance and oxygen in the presence of supercritical water,
First feeding means for feeding the first liquid to be treated into the reactor, second feeding means for feeding at least one of the second liquid to be treated and auxiliary fuel into the reactor, and oxygen As a means for feeding the contained gas, two two-fluid nozzles are provided at the reactant inlet of the reactor,
Each of the two two-fluid nozzles is a double tube including an inner tube and an outer tube into which the inner tube is inserted, an annular portion including the outer tube and the inner tube as a flow path, and an inner tube. The outer tube is reduced in diameter at the tip of the double tube, the area of the tip annular opening of the annular part is smaller than the area of the upstream annular part,
The first feeding pipe provided as the first feeding means is the inner pipe of one of the two fluid nozzles, and the second feeding pipe provided as the second feeding means is the other of the two fluid nozzles. Two branch pipes connected to the inner pipe and branched from the gas feed pipe provided as a means for feeding the oxygen-containing gas are respectively connected to the annular portion of one of the two fluid nozzles and the other two pipes. It is characterized in that it is connected to the annular portion of the fluid nozzle.
[0018]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, embodiments of the present invention will be described specifically and in detail with reference to the accompanying drawings.
Embodiment 1
This embodiment is an example of an embodiment of the supercritical water reactor according to the first invention, and FIG. 1 is a flow sheet showing the configuration of the supercritical water reactor of this embodiment, FIG. ) Is a vertical partial sectional view showing the structure of a three-fluid nozzle used in this embodiment, and FIG. 2B is a transverse sectional view taken along line II in FIG. 2A. 1 that are the same as those in FIG. 6 are given the same reference numerals, and descriptions thereof are omitted.
The supercritical water reactor 40 of the present embodiment uses a three-fluid nozzle instead of the two-fluid nozzle, and the configuration of the reactor and the outflow system after the reactor, except for the changes associated with the use of the three-fluid nozzle. Has the same configuration as the conventional supercritical water reactor described above.
[0019]
Supercritical water reactor 40, as shown in FIG. 1, mainly comprises water and a water-soluble organic material, the first to fed the first liquid to be treated does not contain a hydrophobic organic material substantially into the reactor 12 A first liquid to be treated 44 that feeds the first liquid to be treated into the reactor 12 through the inflow pipe 42 and the first inflow pipe 42, and an auxiliary fuel made of a hydrophobic organic substance as the reactor 12. And a second inlet pipe 46 for feeding into the pipe. The alkaline agent feed pipe 31 is connected to the first feed pipe 42.
The first inlet pipe 42, the second inlet pipe 46, and the air inlet pipe 26 are connected to the reactor 12 through a three-fluid nozzle 50.
[0020]
As shown in FIG. 2 , the three-fluid nozzle 50 used in the reactor of the present embodiment includes an inner tube 52, an inner tube 54 into which the inner tube 52 is inserted, and an inner tube 52 and an inner tube 54 inserted therein. The first annular portion 58 defined by the inner tube 54 and the outer tube 56, and the first annular portion 58 defined by the inner tube 52 and the inner tube 54 as flow paths. Two annular portions 60 and three flow paths of the inner tube 52 are provided.
The outer tube 56 has a reduced diameter at the distal end 62 of the triple tube, and the first annular portion 58 has an area of the annular opening at the distal end smaller than that of the upstream annular flow path.
The first annular part 58 is connected to the air inlet pipe 26, the second annular part 60 is connected to the first inlet pipe 42, and the inner pipe 52 is connected to the second inlet pipe 46.
[0021]
With the above configuration, in the present embodiment, the auxiliary fuel flowing out from the inner pipe 52 is atomized by the air flowing out from the first annular portion 58 in the reactor 12 and dispersed in supercritical water, or the first It flows out from the two annular portions 60 and is dispersed in the first liquid to be treated which is also atomized by air and dispersed in the supercritical water.
Therefore, the auxiliary fuel is sufficiently dispersed and introduced into the reactor 12, so that the reaction temperature does not fluctuate unlike the conventional supercritical water reactor. That is, since the organic substance can be introduced at a constant organic substance concentration, the reaction temperature does not vary.
[0022]
An experimental apparatus having the same configuration as that of the supercritical water reactor 40 of the present embodiment is manufactured, and using A heavy oil as an auxiliary fuel, a supercritical water reaction treatment is performed on a liquid to be treated having a low organic concentration, and the reaction of the reactor When the temperature was measured, the fluctuation range of the reaction temperature was 5 ° C. as shown by the graph (1) in FIG.
On the other hand, an experimental apparatus having the same configuration as that of the above-described conventional supercritical water reactor 10 is manufactured, and similarly, using A heavy oil as an auxiliary fuel, a supercritical water reaction process is performed on a liquid to be treated having a low organic concentration. When the reaction temperature of the reactor was measured, the fluctuation range of the reaction temperature reached 30 ° C. as shown by the graph (2) in FIG.
Also from this experiment, it can be evaluated that the supercritical water reactor 40 of the present embodiment is effective in suppressing fluctuations in the reaction temperature.
[0023]
In this embodiment, the auxiliary fuel is fed into the reactor 12 as a hydrophobic organic substance. However, the second liquid to be treated mainly containing the hydrophobic organic substance in addition to the auxiliary fuel is sent through the second inlet pipe 46. It may be sent to the three-fluid nozzle 50, or a second liquid to be treated mainly containing a hydrophobic organic substance may be sent instead of the auxiliary fuel.
[0024]
Embodiment 2
This embodiment is a modification of the first embodiment. FIG. 4A is a vertical partial sectional view showing the structure of a three-fluid nozzle used in this embodiment, and FIG. It is a cross-sectional view in line II-II of (a). Of the components shown in FIG. 4, the same components as those in FIG.
The supercritical water reactor of the present embodiment is the same as the configuration of Embodiment 1 except that the configuration of the three-fluid nozzle is different, and the three-fluid nozzle 70 of the present embodiment is shown in FIG. As described above, the configuration is the same as that of the three-fluid nozzle 50 of Embodiment 1 except that the outer peripheral surface of the inner tube 52 is provided with a heat insulating layer 72 made of permiculite.
[0025]
The heat insulating layer 72 is provided, and the heat insulating effect prevents heat conduction to the hydrophobic organic substance flowing through the inner tube 52, thereby preventing the hydrophobic organic substance from being charred more effectively. The heat insulating layer 72 may be provided on the inner peripheral surface of the inner tube 52.
[0026]
Embodiment 3
This embodiment is an example of an embodiment of a supercritical water reactor according to the second invention. FIG. 5 is a flow sheet showing the configuration of the supercritical water reactor according to this embodiment.
As shown in FIG. 5, the supercritical water reactor 80 of the present embodiment example uses the two two-fluid nozzles 82 and 84 in place of the three-fluid nozzle, and the supercritical water reactor of the first embodiment example. The same configuration as the water reactor 40 is provided.
The supercritical water reactor 80 according to this embodiment includes two two-fluid nozzles 82 and 84 having the same configuration as the two-fluid nozzle 34 shown in FIG. 7 described above at the reactant inlet of the reactor 12. The first inlet pipe 42 is connected to the inner pipe of one of the two fluid nozzles 82, the second inlet pipe 46 is connected to the inner pipe of the other two fluid nozzle 84, and the air inlet pipe 26. The two branch pipes 86 and 88 branched from the two are connected to the annular portion of one two-fluid nozzle 82 and the annular portion of the other two-fluid nozzle 84, respectively.
As a result, the first liquid to be treated and the auxiliary fuel can be separately dispersed and introduced into the reactor 12, so that the organic substance is introduced at a constant organic substance concentration and reacted as in the first embodiment. The temperature stabilizes.
[0027]
【The invention's effect】
According to the present invention, the first feeding means for feeding the first liquid to be treated into the reactor, and the second for feeding at least one of the second liquid to be treated and the auxiliary fuel into the reactor. The organic substance can be introduced at a constant organic substance concentration, and the reaction temperature can be stabilized.
That is, a three-fluid nozzle is provided at the inlet to the reactor, and a gas inlet pipe for feeding an oxygen-containing gas is provided in the first annular portion consisting of an outer pipe and an intermediate pipe, and a water-soluble organic substance as a main component. A first feed pipe for feeding one liquid to be treated into a second annular portion composed of an intermediate pipe and an inner pipe, and a second feed pipe for feeding a hydrophobic organic substance into an inner pipe, By connecting and dispersing the hydrophobic organic substance in the supercritical water or the first liquid to be treated, the supercritical water reaction can be continued at a stable reaction temperature.
Further, the same effect can be obtained by two two-fluid nozzles instead of the three-fluid nozzle.
[Brief description of the drawings]
FIG. 1 is a flow sheet showing a configuration of a supercritical water reactor according to Embodiment 1;
2A is a vertical partial cross-sectional view showing the structure of a three-fluid nozzle used in Embodiment 1, and FIG. 2B is a cross-sectional view taken along line II in FIG. 2A. It is.
FIG. 3 is a graph showing fluctuations in reaction temperature.
4 (a) is a vertical partial sectional view showing the structure of a three-fluid nozzle used in Embodiment 2, and FIG. 4 (b) is a transverse sectional view taken along line II-II in FIG. 4 (a). It is.
FIG. 5 is a flow sheet showing a configuration of a supercritical water reactor according to Embodiment 3;
FIG. 6 is a flow sheet showing the configuration of a conventional supercritical water reactor.
FIG. 7 (a) is a vertical partial sectional view showing the structure of a two-fluid nozzle used in a conventional supercritical water reactor, and FIG. 7 (b) is a view taken along line III-III in FIG. 7 (a). It is a cross-sectional view.
[Explanation of symbols]
DESCRIPTION OF SYMBOLS 10 Conventional supercritical water reactor 12 Vertical pressure-resistant sealed reactor 14 Process liquid pipe 16 Cooler 18 Pressure control valve 20 Gas-liquid separator 22 Process liquid pipe 24 Process liquid pump 26 Air inlet pipe 28 Air compressor 30 the auxiliary fuel conduit 31 alkali agent fed tube
3 4 Two-fluid nozzle 36 Inner tube 38 Outer tube 38a Outer tube tip 39 Annular portion 40 Supercritical water reactor 42 of Embodiment 1 First inlet tube 44 First liquid pump 46 Second Inlet tube 50 Three-fluid nozzle 52 Inner tube 54 Middle tube 56 Outer tube 58 First annular portion 60 Second annular portion 70 Three-fluid nozzle 72 used in the supercritical water reactor of Embodiment 2 Heat insulation layer 80 Embodiment 3 Supercritical water reactors 82 and 84 Two-fluid nozzles 86 and 88 Branch pipe

Claims

A vertical reactor containing supercritical water, which mainly contains water and a water-soluble organic substance, and contains a second organic substance mainly containing a hydrophobic organic substance in addition to the first liquid to be treated substantially free of the hydrophobic organic substance. At least one of a liquid to be treated and an auxiliary fuel mainly composed of a hydrophobic organic substance is fed into the reactor, and an oxygen-containing gas as an oxidant is supplied to the reactor, and the organic substance is present in the presence of supercritical water. A supercritical water reaction apparatus for performing a supercritical water reaction between oxygen and oxygen,
First feed availability stage, the second feed-in means for fed into a reactor at least one of the second liquid to be treated and auxiliary fuel fed to the first liquid to be treated to the reactor, and oxygen As a means for feeding the contained gas, a three-fluid nozzle is provided at the reactant inlet of the reactor,
The three-fluid nozzle includes an inner tube, an inner tube into which the inner tube is inserted, and an outer tube into which the inner tube and the inner tube are inserted. It is configured as a triple tube having a second annular portion composed of an intermediate tube and an inner tube, and an inner tube. The outer tube is reduced in diameter at the distal end of the triple tube, and the area of the distal annular opening of the first annular portion Is smaller than the area of the upstream first annular portion,
A gas inlet pipe provided as an oxygen-containing gas inlet means is provided in the first annular portion, and a first inlet pipe provided as the first inlet means is provided in the second annular portion, and the second inlet portion. A supercritical water reactor , wherein the second feeding pipes provided as means are connected to the inner pipe, respectively .

The supercritical water reactor according to claim 1 , wherein a heat insulating layer is provided along an outer peripheral surface or an inner peripheral surface of the inner tube.

A vertical reactor containing supercritical water, which mainly contains water and a water-soluble organic substance, and contains a second organic substance mainly containing a hydrophobic organic substance in addition to the first liquid to be treated substantially free of the hydrophobic organic substance. At least one of a liquid to be treated and an auxiliary fuel mainly composed of a hydrophobic organic substance is fed into the reactor, and an oxygen-containing gas as an oxidant is supplied to the reactor, and the organic substance is present in the presence of supercritical water. A supercritical water reaction apparatus for performing a supercritical water reaction between oxygen and oxygen,
First feeding means for feeding the first liquid to be treated into the reactor, second feeding means for feeding at least one of the second liquid to be treated and auxiliary fuel into the reactor, and oxygen As a means for feeding the contained gas, two two-fluid nozzles are provided at the reactant inlet of the reactor,
Each of the two two-fluid nozzles is a double tube including an inner tube and an outer tube into which the inner tube is inserted, an annular portion including the outer tube and the inner tube as a flow path, and an inner tube. The outer tube is reduced in diameter at the tip of the double tube, the area of the tip annular opening of the annular part is smaller than the area of the upstream annular part,
The first feeding pipe provided as the first feeding means is the inner pipe of one of the two fluid nozzles, and the second feeding pipe provided as the second feeding means is the other of the two fluid nozzles. Two branch pipes connected to the inner pipe and branched from the gas feed pipe provided as a means for feeding the oxygen-containing gas are respectively connected to the annular portion of one of the two fluid nozzles and the other two pipes. supercritical water reactor characterized in that connected to the annular portion of the fluid nozzle.