JP4569884B2

JP4569884B2 - Method and apparatus for treating organic matter in water

Info

Publication number: JP4569884B2
Application number: JP2000182575A
Authority: JP
Inventors: 島泉里小; 口幸男野; 藤信介佐
Original assignee: Nomura Micro Science Co Ltd
Current assignee: Nomura Micro Science Co Ltd
Priority date: 2000-06-19
Filing date: 2000-06-19
Publication date: 2010-10-27
Anticipated expiration: 2020-06-19
Also published as: JP2002001366A

Description

【０００１】
【発明の属する技術分野】
本発明は、水中の有機物処理方法および装置に関し、特に半導体や液晶の製造工程により発生する有機物含有排水に対し、オゾンの使用量を低減させて効率よく酸化処理することが可能な水中の有機物処理方法および処理装置に関する。
【０００２】
【従来の技術】
今日、地球の環境保全の立場から資源の有効利用に関する地球規模の要求が高まり、大量に水を消費していた半導体や液晶工場においても水の再利用を求める動きが高まりつつある。
【０００３】
この半導体や液晶の生産工程では、フォトレジストの剥離等に有機溶剤が多量に使用されている。使用される有機物としては、例えば、ＩＰＡ（イソプロピルアルコール）、ＤＭＳＯ（ジメチルスルホキシド）、ＴＭＡＨ（テトラメチルアンモニウムヒドロキシド）またはアセトンなどがあり、排水中からこれらの有機成分を除去することが必要となる。
【０００４】
有機物を除去する方法としては、活性炭などを用いて直接吸着したり、強力な酸化手段により有機物を分解することがなされている。後者の酸化手段によって分解して生成するＣＯ_２や有機酸はイオン交換樹脂などで除去している。このように有機物が分解されることで、多量に有機物を含んでいた排水を再利用することが可能となっている。
【０００５】
有機物を分解する他の手段としては、紫外線を利用したり、微生物などを利用することが行われている。また、紫外線を利用する場合には、オゾンやＨ_２Ｏ_２など促進剤を併用することがなされている。しかし、微生物による分解処理では、難分解性の有機物の処理が難しく、紫外線を用いた処理では、多量の電気エネルギーを消費する経済的な負担が大きい問題がある。
【０００６】
近年、有機物を分解する新しい手段として、オゾンを利用する方法が注目されている。この場合、オゾンガスに加えて過酸化水素を促進剤として使用することにより、効率のよい有機物の分解が可能となる。過酸化水素の影響により、ヒドロキシルラジカル（ＯＨラジカル）の生成が一段と増し、水中の有機物を効率よく分解することができるためである。
【０００７】
オゾンと過酸化水素を併用した有機物の処理装置は、オゾン発生装置、原料ガス前処理装置、反応槽および排オゾンガス処理装置等からなる。また、反応槽で処理された処理水から反応に使用されなかったオゾンおよび過酸化水素を処理する酸化剤処理装置および有機物が分解して生成するＣＯ_２や有機酸を除去する手段、例えばイオン交換器などを付加している（特開平１１−１１４５８４）。
【０００８】
図６はオゾンガスを用いた従来の有機物処理装置を示し、オゾン発生器５１１と、反応槽５２１と、ガス溶解手段５３１とを備えている。オゾン発生器５１１はそのガスの前処理装置５１０に接続されている。反応槽５２１には被処理水５６１が充填される。ガス溶解手段５３１は被処理水５６１に浸漬されるように反応槽５２１内に設けられており、配管５４１によってオゾン発生器と接続されている。反応槽５２１内には供給配管５７１が接続されており、供給配管５７１を介してＨ２Ｏ２５８１およびｐＨ調整剤５８２が被処理水５６１内に混合される。さらに、反応槽５２１には酸化処理に用いられることなく被処理水５６１から抜き出たオゾンやＨ２Ｏ２を処理する廃ガス処理装置５８４が接続されている。
【０００９】
このような装置では、被処理水５６１にＨ２Ｏ２と、ＮａＯＨなどのｐＨ調整剤とを混合すると共に、オゾン発生器５１１からのオゾンガスをガス溶解手段５３１から噴出させて被処理水５６１を酸化処理する。酸化処理された被処理水５６１中に残留した酸化剤や炭酸ガス、有機酸などの酸化分解生成物等は、活性炭吸着装置、イオン交換器により除去される。
【００１０】
オゾン発生器５１１としては、通常、無声放電によってオゾンを発生させる装置が用いられる。この無声放電では、原料ガス前処理装置５１０で処理された原料ガスをオゾン発生器５１１に通し交流電圧を印加して放電を行うことにより、オゾンを発生させるようになっている。原料ガス前処理装置５１０では、空気を原料とした酸素濃度が８０％以上のガスを発生させる。オゾン発生器５１１では、放電により熱が発生するため冷却装置を併用している。廃ガス処理装置５８４は、廃ガス中に残留しているオゾンを触媒樹脂などによって除去した後、大気中に排出する。
【００１１】
ガス溶解手段５３１は、細孔を通過することにより気体を液中に導入したり、回転する翼により気体を導入する。
【００１２】
また、このような有機物処理装置の反応槽に、液中に気体を溶解させるガス溶解手段の代わりに、気体中に液体を溶解させる充填塔などを用いたものも使われている。
【００１３】
充填塔を用いた反応槽では、多段方式で処理することが可能なため、廃ガスを順次再利用することで、廃ガスのオゾン濃度を限りなく低くすることはできる。ただし、オゾンの利用効率がガス溶解手段よりも悪いため、必要なオゾン量に関しては回転翼式のガス溶解手段と大きな差はない。すなわち、充填塔はオゾンを効率的に吸収することはできるが、吸収されたオゾンを反応に利用することに関して効率的ではなく、逆に、ガス溶解手段は吸収したオゾンを効率的に反応に利用できるにもかかわらず、吸収効率が悪く、廃ガス中に取り逃がしてしまうオゾンの割合が大きく、それぞれ一長一短があり、目的に応じて使用されている。
【００１４】
【発明が解決しようとする課題】
このような従来の有機物処理装置では、反応槽におけるオゾンの利用効率が悪く、多量にオゾンを消費している。このため経済的には好ましくない。また、オゾンは大気汚染物質であるため、その使用量を最小限とすることが望まれている。従来の装置では、反応槽３２内で、反応に消費されなかったオゾンが廃ガス処理装置４０を介して大気中に放出されるため、このような要望にこたえることができない問題がある。
【００１５】
また一方で、近年のＬＳＩやＵＬＳＩの超微細化に伴い、これらの製造に用いられている純水の純度に対する要求も高くなっており、オゾンと過酸化水素を併用した有機物含有水の処理装置においても高い分解率を得ることが求められていた。
【００１６】
このようなガス溶解手段を採用した従来の有機物処理装置を使用して、有機物の酸化分解処理を行う場合、有機物の分解率を高くしようとすればするほど、オゾン必要量は、飛躍的に高くなっている。つまり、ＴＯＣの分解率が低い場合には、オゾン利用効率は比較的高いが、ＴＯＣの分解効率を良くすると、オゾン利用効率が悪くなる傾向がる。
【００１７】
例えば、ＩＰＡの濃度が有機炭素として１０ｐｐｍである被処理水を処理するために必要なオゾン量は、処理水の濃度が有機炭素として２ｐｐｍを目標とすればΔＯ_３／ΔＴＯＣ（ｇ／ｇ）＝１５．０であるが、１ｐｐｍを目標とすればΔＯ_３／ΔＴＯＣ（ｇ／ｇ）＝１８．７に増大していた。
【００１８】
また、従来のガス溶解手段を採用した水中の有機物処理装置において、分解効率を良くするために増大したオゾンの全てが、必ずしも有機物の反応に利用されるわけではなく、その大部分は廃ガスとして残存する。例えば、前述のＩＰＡ濃度が１０ｐｐｍである被処理水を２ｐｐｍにまで除去する場合、オゾン発生器より反応槽に供給されたオゾンの中で、反応に利用されず廃ガス中に残存するオゾンの割合は約２０％であるが、更に、１ｐｐｍにまで除去する場合には、約４０％となる。このことから、分解効率を向上させる場合には却ってオゾンの利用効率の低下を招いている。
【００１９】
そのため、本発明では、分解効率が高く、かつ、必要なオゾン量を最小限にすることのできる、オゾンと過酸化水素を併用した水中の有機物処理方法及び装置を提供することを目的とする。
【課題を解決するための手段】
【００２０】
本発明は上記の目的を達成するため、オゾンと過酸化水素とを併用して被処理水を第１反応槽から第２反応槽に移送しつつ連続的に処理する処理方法であって、
（１）第１反応槽に充填された被処理水に、
過酸化水素を、単位時間当たりの重量比でオゾンの１−３倍量加え、
第２反応槽への配管の出口に於けるｐＨが７〜８になるようにｐＨ調整剤を加え、
酸素濃度が８０％以上の酸素ガスを用いオゾン発生器によって発生させたオゾン含有ガスを、微細気泡にし溶解させて被処理水を酸化処理し、
（２）第１反応槽の液面上に排出されたオゾン含有ガスを、第１反応槽からガス導入手段によって第２反応槽に送り、第２反応槽に収容された被処理水に、微細気泡にし溶解させて被処理水を更に酸化処理し、
（３）第２反応槽の反応槽の後段に、廃ガス処理装置を設け残存するオゾンガスを処理し、吸着器を設け未反応の過酸化水素を除去し、吸着器の後段にイオン交換器を設けて酸化処理で水中の有機物から生成した有機酸を除去することを特徴とする。
【００２１】
また本発明は、オゾンと過酸化水素とを併用して被処理水を第１反応槽から第２反応槽に移送しつつ連続的に連続的に処理する処理方法であって、
（１）第２反応槽に収容された被処理水に、
酸素濃度が８０％以上の酸素ガスを用いオゾン発生器によって発生させたオゾン含有ガスを、微細気泡にし溶解させて被処理水を酸化処理し、
（２）第２反応槽の液面上に排出されたオゾン含有ガスを、第２反応槽からガス導入手段により第１反応槽に送り、第１反応槽に収容された被処理水に、過酸化水素を、単位時間当たりの重量比でオゾンの１−３倍量加え、第２反応槽への配管の出口に於けるｐＨが７〜８になるようにｐＨ調整剤を加え、第２反応槽の液面上に排出されたオゾン含有ガスを、微細気泡にし溶解させて第１反応槽に収容された被処理水に導入して被処理水を更に酸化処理し、
（３）第１反応槽に廃ガス処理装置を設け残存するオゾンガスを処理し、第２反応槽の後段に、吸着器を設け未反応の過酸化水素を除去し、吸着器の後段にイオン交換器を設けて酸化処理で水中の有機物から生成した有機酸を除去することを特徴とする。
【００２２】
また本発明は、酸化処理は、回転する翼によりオゾン含有ガスの微細気泡を発生させることにより行うことが好ましい。
【００２３】
更に本発明の水中の有機物処理装置は、第１反応槽とその下流に連結する第２反応槽とを有し、オゾンと過酸化水素とを併用して被処理水を連続的に処理する水中の有機物処理装置であって、
（１）第１反応槽に、酸素濃度が８０％以上の酸素ガスを用いオゾン含有ガスを発生させるオゾン発生器と連結し、オゾン含有ガスを、第１反応槽に収容された被処理水に、微細気泡を発生させ溶解させる溶解手段と、第１反応槽の液面上に排出されたオゾン含有ガスを、第１反応槽から引き出して第２反応槽に送るガス導入手段と、過酸化水素を、単位時間当たりの重量比でオゾンの１−３倍量加える過酸化水素供給手段と、第２反応槽への配管の出口に於けるｐＨが７〜８になるようにｐＨ調整剤を加えるｐＨ調製手段と、を備え、
（２）第２反応槽に、第１反応槽から引き出されたオゾン含有ガスを、第２反応槽に収容された被処理水に、微細気泡を発生させ溶解させる溶解手段を備え、
（３）第２反応槽の後段に、残存するオゾンガスを処理する廃ガス処理装置と、被処理液中の未反応の過酸化水素を除去する吸着器と、吸着器の後段に連結して設けられ被処理液中の有機物から生成した有機酸を除去するイオン交換器と、を備えることを特徴とする。
【００２４】
また、本発明の、水中の有機物処理装置は、第１反応槽とその下流に連結する第２反応槽とを有し、オゾンと過酸化水素とを併用して被処理水を連続的に処理する水中の有機物処理装置であって、
（１）第２反応槽に、酸素濃度が８０％以上の酸素ガスを用いオゾン含有ガスを発生させるオゾン発生器と連結し、オゾン含有ガスを、第２反応槽に収容された被処理水に、微細気泡を発生させ溶解させる溶解手段と、第２反応槽の液面上に排出されたオゾン含有ガスを、第２反応槽から引き出して第１反応槽に送るガス導入手段と、を備え、
（２）第１反応槽に、第２反応槽から引き出されたオゾン含有ガスを、第１反応槽に収容された被処理水に、微細気泡を発生させ溶解させる溶解手段と、過酸化水素を、単位時間当たりの重量比でオゾンの１−３倍量加える過酸化水素供給手段と、第２反応槽へ配管の出口に於けるｐＨが７〜８になるようにｐＨ調整剤を加えるｐＨ調製手段と、残存するオゾンガスを処理する廃ガス処理装置と、を備え、
（３）第２反応槽の後段に、被処理液中の未反応の過酸化水素を除去する吸着器と、吸着器の後段に連結して設けられ被処理液中の有機物から生成した有機酸を除去するイオン交換器と、を備えることを特徴とする。
【００２５】
溶解手段は、導入されたオゾン含有ガスを回転する翼によって微細気泡を発生させることが好ましい。
【００２６】
【発明の実施の形態】
以下、図面を参照して本発明の実施の形態について詳細に説明する。
【００２７】
図１は本発明における水中の有機物処理装置の第１の実施態様を示す断面図である。有機物処理装置は、主として、オゾン発生器１１と、反応槽１２１、１２２と、溶解手段１３１、１３２と、ガス導入手段１４１、１４２を備えている。
【００２８】
オゾン発生器１１は原料ガス前処理装置１０に接続されている。反応槽１２１には被処理水１６１が充填される。溶解手段１３１は被処理水１６１に浸漬されるように反応槽１２１内に設けられており、オゾン発生器１１からガス導入手段１４１によってオゾン発生器１１と接続されている。これによりオゾン含有ガスが導入される。反応槽１２１には供給配管７１が接続されており、供給配管７１を介してＨ_２Ｏ_２８１およびｐＨ調整剤８２が被処理水１６１に混合される。
【００２９】
反応槽１２１内に入れられた被処理水１６１には、Ｈ_２Ｏ_２８１およびｐＨ調整剤８２が混合され、ガス導入手段１４１から導入されるオゾン混合ガスが溶解手段１３１から微細気泡として噴出されることによって、被処理水１６１中の有機物が酸化処理される。
【００３０】
反応槽１２２は、反応槽１２１から配管７２によって接続されており、反応槽１２１で酸化処理された被処理水１６１が移送され、充填される。溶解手段１３２は被処理水１６２に浸漬されるように反応槽１２２内に設けられている。ガス導入手段１４２は、反応槽１２１の頂部から引き出されており、その先端が溶解手段１３２と連結されている。これにより、ガス導入手段１４２は、反応槽１２１内に残った余剰のオゾン含有ガスを溶解手段１３２に導入するように作用する。
【００３１】
反応槽１２２内に移された被処理水１６２には、ガス導入手段１４２によって導入される反応槽１２１に残余のオゾン含有ガスが、溶解手段１３２から微細気泡として噴出されることによって、被処理水１６２中の有機物が酸化分解処理される。
【００３２】
反応槽１２２の頂部には、反応終了後に残るオゾン混合ガスを排出し、廃ガス処理装置８４に接続される排出管８３が設けられている。
【００３３】
反応槽１２２からは排水管８５が吸着器８６へ接続され、さらに吸着器８６から排水管８７がイオン交換器８８へ接続されている。吸着器８６には、活性炭などの吸着材が充填されている。これにより、反応槽１２２で酸化分解処理された被処理水１６２が排出され、被処理水１６２中に残留したオゾン、Ｈ_２Ｏ_２等が吸着除去される。被処理水１６２は、排水管８７を介してイオン交換器８８へ排出され、イオン交換器８８において、被処理水１６２中の有機酸、微量の炭酸ガスなどの酸化分解生成物が除去される。
【００３４】
また、上記第１の実施態様において、必要に応じて反応槽１２１と反応槽１２２との間に、更に一以上の反応槽を設置し、消費されずに残るオゾンガスの再利用度を高めることもできる。この場合には、反応槽１２１から反応槽１２２に接続され、反応槽１２１で酸化処理された被処理水１６１を移送する配管７２と同様の配管を、追加設置する各反応槽に設ける。また、反応槽１２１の頂部から引き出され、その先端が溶解手段１３２と連結されているガス導入手段１４２と同様のガス導入手段、溶解手段を各反応槽に装備する。更に、追加設置する各反応槽に充填される被処理水及び反応槽１２２に充填される被処理水１６２にＨ_２Ｏ_２８１およびｐＨ調整剤８２を混合する供給配管が各反応槽に接続される。
【００３５】
図２は本発明における水中の有機物処理装置の第２の実施態様を示す断面図であり、第１の実施態様のオゾン混合ガスの流れと反対方向にガス導入手段を設置した処理装置である。
【００３６】
この第２の実施態様における処理装置では、反応槽２２１に供給配管７１が接続されており、供給配管７１を介してＨ_２Ｏ_２８１およびｐＨ調整剤８２が被処理水２６１に混合され、反応槽２２１に充填される。反応槽２２１に設けられた溶解手段２３１には、反応槽２２２の頂部から引き出されたガス導入手段２４２の先端が連結されている。これにより、ガス導入手段２４２は、反応槽２２２内における酸化処理後のオゾン含有ガスを溶解手段２３１に導入し、オゾン混合ガスの微細気泡を発生する。
【００３７】
反応槽２２１内に入れられた被処理水２６１には、Ｈ_２Ｏ_２８１およびｐＨ調整剤８２が混合され、ガス導入手段２４２から導入されるオゾン混合ガスが溶解手段２３１から微細気泡として噴出されることによって、被処理水２６１中の有機物が酸化処理される。また、反応槽２２１の頂部には、反応終了後に残るオゾン混合ガスを排出し、廃ガス処理装置８４に接続される排出管８３が設けられている。
【００３８】
反応槽２２２は、反応槽２２１から配管７２によって接続されており、反応槽２２１で酸化処理された被処理水２６１が移送され、充填される。溶解手段２３２は被処理水２６２に浸漬されるように反応槽２２２内に設けられ、溶解手段２３２には、オゾン発生器１１からガス導入手段２４１によってオゾン発生器１１と接続されている。これによりオゾン含有ガスが溶解手段２３２に導入され、オゾン含有ガスの微細気泡を発生する。
【００３９】
反応槽２２２内に移された被処理水２６２には、ガス導入手段２４１によって導入されるオゾン含有ガスが、溶解手段２３２から微細気泡として噴出されることによって、被処理水２６２中の有機物が酸化分解処理される。
【００４０】
反応槽２２２から吸着器８６へ、また吸着器８６からイオン交換器８８への接続形態は、第１の実施態様と同様であり、反応槽２２２で酸化分解処理された被処理水２６２が排出され、被処理水２６２中に残留したオゾン、Ｈ_２Ｏ_２等が吸着器８６によって吸着除去される。さらに被処理水２６２は、排水管８７を介してイオン交換器８８へ排出され、イオン交換器８８において、被処理水２６２中の有機酸、微量の炭酸ガスなどの酸化分解生成物が除去される。
【００４１】
また、上記第２の実施態様において、反応槽２２１における酸化処理で消費されずにオゾン含有ガスが残余する場合、必要に応じて、更にオゾン含有ガスを再利用する形態に変形することができる。この場合には、反応槽２２１と反応槽２２２の間に更に一以上の反応槽を設置し、反応槽２２２から反応槽２２１の方向へ順次、ガス導入手段２４２と同様のガス導入手段を設ける形態、又は、反応槽２２２の後段に、更に一以上の反応槽を設置し、反応槽２２２から反応槽２２１へのガス導入手段２４２のオゾン含有ガス導入の方向とクロスさせる形態に構成することが可能である。
【００４２】
上記前者の形態に変形した処理装置の場合には、反応槽２２１から反応槽２２２に接続され、反応槽２２１で酸化処理された被処理水２６１を移送する配管７２と同様の配管を、追加設置する各反応槽に設ける。また、反応槽２２２の頂部から引き出され、その先端が溶解手段２３１と連結されているガス導入手段２４２と同様のガス導入手段、溶解手段を各反応槽に装備する。更に、追加設置する各反応槽に充填される被処理水及び反応槽２２２に充填される被処理水２６２にＨ_２Ｏ_２８１およびｐＨ調整剤８２を混合する供給配管が各反応槽に接続される。
【００４３】
上記後者の形態に変形した処理装置の場合には、反応槽２２１で酸化処理された被処理水２６１を移送する配管７２と同様の配管を、追加設置する各反応槽に装備する。また、反応槽２２１の頂部に設置され、廃ガス処理装置８４に接続される排出管８３の代わりに、反応槽２２２の頂部から引き出され、その先端が溶解手段２３１と連結されているガス導入手段２４２と同様のガス導入手段、溶解手段を各反応層に設ける。更に、追加設置する各反応槽に充填される被処理水及び反応槽２２２に充填される被処理水２６２にＨ_２Ｏ_２８１およびｐＨ調整剤８２を混合する供給配管が各反応槽に接続される。
【００４４】
図３は本発明における水中の有機物処理装置の第３の実施態様を示す断面図であり、複数のガス導入手段をそれぞれ分岐及び連結する形態に装備した処理装置である。
【００４５】
この第３の実施態様における有機物処理装置は、主にオゾン発生器１１と、反応槽３２１、３２２、３２３と、溶解手段３３１、３３２、３３３と、ガス導入手段３４１、３４２、３４３、３４４を備えている。反応槽３２１には供給配管７１が接続されており、供給配管７１を介してＨ_２Ｏ_２８１およびｐＨ調整剤８２が被処理水３６１に混合され、反応槽３２１に充填される。溶解手段３３１は被処理水３６１に浸漬されるように反応槽３２１内に設けられており、オゾン発生器１１からガス導入手段３４１によってオゾン発生器１１と接続されている。ガス導入手段３４１は、ガス導入手段３４２へ分岐する分岐部３５１を有する。
【００４６】
反応槽３２１内に入れられた被処理水３６１には、Ｈ_２Ｏ_２８１およびｐＨ調整剤８２が混合され、またガス導入手段３４１から導入されるオゾン混合ガスが溶解手段３３１から微細気泡として噴出されることによって、被処理水３６１中の有機物が酸化処理される。
【００４７】
反応槽３２２は、反応槽３２１から配管７２によって接続されており、反応槽３２１で酸化処理された被処理水３６１が移送される。溶解手段３３２は被処理水３６２に浸漬されるように反応槽３２２内に設けられている。ガス導入手段３４２は、ガス導入手段３４１の分岐部３５１に連結し、反応槽３２２に設けられた溶解手段３３２の先端に接続されており、オゾン発生器１１からオゾン含有ガスを導入する。
【００４８】
反応槽３２２内に充填された被処理水３６２には、ガス導入手段３４２によって導入されるオゾン含有ガスが、溶解手段３３２から微細気泡として噴出されることによって、被処理水３６２中の有機物が酸化処理される。
【００４９】
反応槽３２３は、反応槽３２２から配管７３によって接続されており、反応槽３２２で酸化処理された被処理水３６２が移送される。溶解手段３３３は被処理水３６３に浸漬されるように反応槽３２３内に設けられている。溶解手段３３３には、反応槽３２１の頂部からガス導入手段どうしを結合する連結部３５２を有するガス導入手段３４３と、反応槽３２２の頂部からガス導入手段３４３の連結部３５２に結合されたガス導入手段３４４の先端部が接続されている。ガス導入手段３４３と、連結部３５２に連結されたガス導入手段３４４とにより、反応槽３２１において酸化処理後に残るオゾン含有ガスと、反応槽３２２の酸化処理後に残るオゾン含有ガスが混合されて溶解手段３３３に導入される。
【００５０】
反応槽３２３に充填された被処理水３６３には、ガス導入手段３４３及び３４４により導入されるオゾン含有ガスが、溶解手段３３３から微細気泡として噴出されることで、被処理水３６３中の有機物が酸化処理される。反応槽３２３の頂部から酸化分解処理後に残るオゾン含有ガスを排出し、廃ガス処理装置８４に接続される排出管８３が設けられている。
【００５１】
反応槽３２３からは、排水管８５が吸着器８６へ接続され、さらに吸着器８６から排水管８７がイオン交換器８８へ接続されている。これにより、反応槽１２２で酸化分解処理された被処理水１６２が排出され、被処理水１６２中に残留したオゾン、Ｈ_２Ｏ_２等が吸着除去される。被処理水１６２は、排水管８７を介してイオン交換器８８へ排出され、イオン交換器８８において、被処理水１６２中の有機酸、微量の炭酸ガスなどの酸化分解生成物が除去される。
【００５２】
また、上記第３の実施態様の有機物処理装置において、更に１以上の反応槽を追加して設置したり、ガス導入手段どうしを三方バルブ、四方バルブなどのバルブ手段を介して分岐、連結する分岐部、連結部を有する多数のガス導入手段をさらに組合わせて装備する形態に変形することができる。このように変形した処理装置では、多数のガス導入手段を組合わせて設けたそれぞれのガス導入手段における分岐部、連結部のバルブ手段をそれぞれ目的に応じて切換えることによって、各反応槽に備えられた溶解手段毎に多様に混合されたオゾン含有ガスを導入することが可能である。例えば、酸化処理後の複数の反応槽からのオゾン含有ガスを混合し、これにオゾン発生器からのオゾン含有ガスを追加混合したオゾン含有ガスを溶解手段に導入したり、酸化分解反応の途中に、酸化処理後の他の反応槽に残ったオゾン含有ガス又はオゾン発生器からのオゾン含有ガスを追加して溶解手段に導入することもできる。
【００５３】
図４は本発明における水中の有機物処理装置の第４の実施態様を示す断面図であり、複数のガス導入手段と複数の溶解手段を一つの反応槽に装備した処理装置である。
【００５４】
この第４の実施態様の処理装置では、反応槽４２１には、複数の溶解手段４３１及び４３２が設置され、それぞれガス導入手段４４１及び４４２が接続されている。オゾン発生器１１は原料ガス前処理装置１０に接続されており、反応槽４２１には被処理水４６１が充填される。溶解手段４３１は被処理水４６１に浸漬されるように反応槽４２１内に設けられており、オゾン発生器１１からガス導入手段４４１によってオゾン発生器１１と接続されている。これによりオゾン含有ガスが導入される。反応槽４２１には供給配管７１が接続されており、供給配管７１を介してＨ_２Ｏ_２８１およびｐＨ調整剤８２が被処理水４６１に混合される。
【００５５】
反応槽４２１内に入れられた被処理水４６１には、Ｈ_２Ｏ_２８１およびｐＨ調整剤８２が混合され、ガス導入手段４４１から導入されるオゾン混合ガスが溶解手段４３１から微細気泡として噴出されることによって、被処理水４６１中の有機物が酸化処理される。
【００５６】
また反応槽４２１には、溶解手段４３２が被処理水４６１に浸漬されるように設けられている。ガス導入手段４４２は、反応槽４２１の頂部から引き出されており、その先端が溶解手段４３２と連結されている。これにより、ガス導入手段４４２は、反応槽４２１内の被処理水４６１を通過して液面上に排出された余剰のオゾン含有ガスを溶解手段４３２に導入する。
【００５７】
反応槽４２１内の被処理水４６１には、ガス導入手段４４２によって導入される反応槽４２１に残余のオゾン含有ガスが、溶解手段４３２から微細気泡として噴出されることによって、被処理水４６１中の有機物が酸化分解処理される。ここで、溶解手段４３２に導入されるオゾン含有ガスは、溶解手段４３１から微細気泡として噴出され、酸化分解に消費されずに被処理水４６１を通過し反応槽頂部に排出されるオゾン含有ガスに加えて、溶解手段４３２から噴出され、１回以上被処理水４６１を通過したオゾン含有ガスも含まれるため、さらにオゾンの利用効率を高められる。また、溶解手段４３１及び４３２へ、それぞれガス導入手段４４１及び４４２から併行して導入することも可能であり、オゾン濃度、酸化処理速度など目的に応じてコントロールできる。
【００５８】
反応槽４２１の頂部には、反応終了後に残る廃ガスを排出し、廃ガス処理装置８４に接続される排出管８３が設けられている。
【００５９】
反応槽４２１からは排水管８５が吸着器８６へ接続され、さらに吸着器８６から排水管８７がイオン交換器８８へ接続されている。吸着器８６により、反応槽４２１で酸化分解処理された被処理水４６１が排出され、被処理水４６１中に残留したオゾン、Ｈ_２Ｏ_２等が吸着除去される。被処理水４６１は、排水管８７を介してイオン交換器８８へ排出され、イオン交換器８８において、被処理水１６２中の有機酸、微量の炭酸ガスなどの酸化分解生成物が除去される。
【００６０】
各態様の処理装置に共通して設けられる原料ガス前処理装置１０としては、空気を原料とした酸素濃度が８０％以上のガスを発生させることができる装置であればどのような装置であっても良く、オゾン発生器１１としては、無声放電方式、電気分解方式、光化学反応方式、化学反応方式、放射線照射方式、高周波電界方式等の装置があり、いずれの装置も使用可能であるが、冷却装置を備え、交流電圧を印加する無声放電方式のオゾン発生器が好適である。
【００６１】
溶解手段１３１、１３２、２３１、２３２、３３１、３３２、３３３、４３１及び４３２としては、それぞれガス導入手段から導入されるオゾン含有ガスを微細気泡として噴出できるものであれば、どのようなタイプの装置も使用できるが、細孔を有する形式又は回転する翼を有する形式の装置が望ましい。また、溶解手段１３２、２３１、３３３、４３１及び４３２には、特に、回転する翼を有する形式の装置が好適である。細孔を有する形式の装置を用いる場合には、ガス導入手段に、ブロワーなどによる昇圧機を加えて装備する。
【００６２】
吸着器８６には吸着材として活性炭が充填されたカラムからなる装置が良く、イオン交換器８８としては、陽イオン交換体と陰イオン交換体が充填されたカラムからなる装置が使用でき、陽イオン交換樹脂及び強塩基性陰イオン交換樹脂が充填された再生型又は非再生混床型の装置が好適である。廃ガス処理装置８４には、触媒樹脂を備え、廃ガス中のオゾンを分解する形式の装置が望ましい。
【００６３】
以上、本発明の水中の有機物処理装置について、第１〜第４の実施態様を示してそれぞれ変形した装置を含めて説明したが、この他にも本発明の技術範囲内で様々に変形した形態に構成することができる。このように多様な形態に構成される有機物処理装置は、酸化処理を施す被処理水に含まれる有機物の種類、濃度などに応じて、それぞれ適切な形態が選択される。
【００６４】
次に、上記のような有機物処理装置を用いる本発明における水中の有機物処理方法について説明する。
【００６５】
上記第１の実施態様の処理装置による処理方法は、反応槽１２１に入れられた被処理水１６１に、オゾン発生器１１からガス導入手段１４１を介して溶解手段１３１に導入されるオゾン含有ガスを、溶解手段１３１によりオゾン含有ガスの微細気泡として溶解させる酸化処理工程と、反応槽１２１において酸化処理工程を経た後の被処理水１６１を反応槽１２２に配管７２を介して移送した後、反応槽１２１から酸化処理工程で消費されずに残ったオゾン含有ガスをガス導入手段１４２を介して取り出し、溶解手段１３２によって、このオゾン含有ガスの微細気泡を発生させ被処理水１６２に溶解・溶解させる酸化処理工程とを有する。
【００６６】
反応槽１２１に入れられる被処理水１６１には、供給配管７１を介してＨ_２Ｏ_２８１を注入する。注入濃度はΔＨ_２Ｏ_２／ΔＯ_３（ｇ／ｇ）＝１〜３程度が良い。このＨ_２Ｏ_２の注入濃度については、諸条件により決定されるが、Ｈ_２Ｏ_２濃度が低すぎると生成するＯＨラジカルが不足し、高すぎると生成したＯＨラジカルがＨ_２Ｏ_２に攻撃するから効率が悪くなる。なお、Ｈ_２Ｏ_２８１の注入は、必ずしも被処理水１６１が反応槽１２１に入るまでにする必要はなく、反応槽１２１に供給配管７１を介して直接注入しても良い。
【００６７】
また、反応槽１２１に入れられる被処理水１６１には、供給配管７１を介してｐＨ調整剤８２を注入する。ｐＨ調整剤８２には通常ＮａＯＨやＫＯＨなどのアルカリを用いる。これにより、反応槽１２１の配管６２への出口のｐＨを中性または弱アルカリ側にコントロールする。酸性側では、ＯＨラジカルの生成が十分ではなく、高アルカリでは、スカベンジャーである炭酸イオンが悪影響を及ぼす。また、被処理水１６１は、オゾン反応によりそのｐＨが酸性側になるため、反応槽への充填時の他、酸化処理工程の終了後、必要に応じて反応槽１２１に供給配管７１を介してｐＨ調整剤２２を注入し、反応槽１２１出口のｐＨを適切なｐＨにコントロールする。
【００６８】
そして、Ｈ_２Ｏ_２７１の注入量やｐＨのコントロールは、酸化処理工程における有機物の除去性能に微妙に影響するので、必要に応じて、酸化処理工程の終了後、反応槽１２１の被処理水１６１に対して供給配管７１を介して、更に、Ｈ_２Ｏ_２７１及び／又はｐＨ調整剤２２を注入する。これにより、反応槽１２２における後段の酸化処理工程においても適切な処理条件での処理が可能となる。
【００６９】
また、酸化分解される有機物は、物質毎にヒドロキシルラジカルとの反応性が異なり、それぞれ効率的に酸化分解処理を行うためには、被処理水中に含まれる有機物の種類、濃度及び反応の進行状態等によって、各被処理水における至適オゾン濃度、過酸化水素濃度、ｐＨに差異が生じる。酸化処理を施す被処理水に含まれる有機物の種類、濃度に応じて、第１〜第４の実施態様の処理装置並びにそれぞれ変形した形態に構成した処理装置から適切な形態の処理装置を選択して酸化分解処理を行う。
【００７０】
このような本発明の有機物処理方法および処理装置によれば、１回以上被処理水を通過して被処理水の液面上に排出され、反応に消費されず余剰となったオゾンが、ガス導入手段を介して他の反応槽又は同一反応槽の溶解手段へ送られ、酸化分解されずに被処理水に残存する有機物の酸化分解に再利用することができるため、オゾンの利用効率の改善と、有機物の分解効率の向上とを両立して達成する。また、被処理水に含まれる有機物の種類、濃度に応じた適切な形態の処理装置を選択して酸化分解処理を行うことができるため、多様な有機物を含む被処理水について適応可能である。
【００７１】
以下に、本発明につき、実施例を示して具体的に説明するが、これによって本発明が限定されるものではない。
【００７２】
【実施例】
図１に示す処理装置を用い、次の条件で被処理水を処理した。被処理水としては、総有機炭素（ＴＯＣ）として１０ｐｐｍを含有したＩＰＡを用いた。なお、図に示された処理装置の内、吸着器については、本来の設置目的はオゾン、過酸化水素を除去するためであるが、吸着器に充填されている活性炭には、有機物除去能力もありオゾンの酸化処理能力を評価するに際しての影響を考慮し、本実施例においては使用しなかった。
【００７３】
上記ＩＰＡの処理流量を０．５ｍ^３／ｈ、オゾン含有ガス中のオゾン濃度を１２０ｇ／ｍ^３、オゾンと併用する過酸化水素の添加量２０ｐｐｍとし、ＮａＯＨによって反応槽出口のｐＨを７．０〜８．０に調整した。
【００７４】
図５は、この実施例に対する比較例の処理装置を示し、図１と同一な要素は同一の符号を付してある。図５の処理装置では、図１の処理装置におけるガス導入手段１４１に、分岐管１５１を接続してある。このような接続を行うことにより、オゾン発生器１１からのオゾン含有ガスをガス導入手段１４１を通じて反応槽１２１の溶解手段１３１に供給すると共に、分岐管１５１を介して反応槽１２２の溶解手段１３２にも供給するようになっている。この比較例では、オゾン含有ガスを溶解手段１３１及び溶解手段１３２のそれぞれに１：１の比率で導入した。また、反応槽１２１及び反応槽１２２からの廃ガスは、再利用せずに直接、廃ガス処理装置８４に通した。その他の条件は実施例と同様である。また、図６に示す従来の処理装置においても、実施例及び比較例と同様な条件で処理を行った。
【００７５】
実施例、比較例および従来例のそれぞれの処理結果を表１、表２に示す。
【００７６】
【表１】
【００７７】
【表２】
【００７８】
表１から明らかなように、本発明の実施例では、比較例や従来例に比べ、高い除去性能が得られている。また、比較例では、従来例とほとんど除去性能は変わっていない。表２は、被処理水のＴＯＣ濃度が、炭素として１０ｐｐｍ含有するＩＰＡを処理した場合、被処理水のＴＯＣ濃度が１または０．５ｐｐｍに達するために必要なオゾン量を示している。指標として、△Ｏ_３／△ＴＯＣ（ｇ／ｇ）を用いた。表２から明らかなように、本発明の実施例では、必要なオゾン量が大きく低減できた。また、比較例においては、必要オゾン量は従来例とほとんど変わらなかった。
【００７９】
【発明の効果】
以上説明したように、本発明によれば、分解効率が高く、しかも必要なオゾン量を最小限とすることができる有機物処理が可能となる。
【００８０】
【図面の簡単な説明】
【図１】本発明における処理装置の第１の実施態様を示す断面図である。
【図２】本発明における処理装置の第２の実施態様を示す断面図である。
【図３】本発明における処理装置の第３の実施態様を示す断面図である。
【図４】本発明における処理装置の第４の実施態様を示す断面図である。
【図５】比較例の処理装置の断面図である。
【図６】従来の処理装置の断面図である。
【００８１】
【符号の説明】
１１オゾン発生器
１２１、１２２反応槽
１３１、１３２溶解手段
１４１、１４２ガス導入手段
２２１、２２２反応槽
２３１、２３２溶解手段
２４１、２４２ガス導入手段
３２１、３２２、３２３反応槽
３３１、３３２、３３３溶解手段
３４１、３４２、３４３、３４４ガス導入手段
４２１、４２２反応槽
４３１、４３２溶解手段
４４１、４４２ガス導入手段[0001]
BACKGROUND OF THE INVENTION
TECHNICAL FIELD The present invention relates to a method and apparatus for treating organic matter in water, and in particular, treatment of organic matter in water that can efficiently oxidize organic matter-containing wastewater generated by semiconductor and liquid crystal manufacturing processes by reducing the amount of ozone used. The present invention relates to a method and a processing apparatus.
[0002]
[Prior art]
Today, global demands for effective use of resources are increasing from the standpoint of environmental conservation of the earth, and movements for water reuse are also increasing in semiconductor and liquid crystal factories that have consumed large amounts of water.
[0003]
In this semiconductor and liquid crystal production process, a large amount of an organic solvent is used for stripping the photoresist. Examples of organic substances used include IPA (isopropyl alcohol), DMSO (dimethyl sulfoxide), TMAH (tetramethylammonium hydroxide), and acetone. It is necessary to remove these organic components from the waste water. .
[0004]
As a method for removing the organic matter, direct adsorption using activated carbon or the like, or decomposition of the organic matter by a powerful oxidizing means is performed. CO produced by decomposition by the latter oxidation means₂And organic acids are removed with ion exchange resins. As the organic matter is decomposed in this way, wastewater containing a large amount of the organic matter can be reused.
[0005]
As other means for decomposing organic substances, ultraviolet rays or microorganisms are used. When using ultraviolet rays, ozone and H₂O₂It is made to use an accelerator together. However, the decomposition treatment with microorganisms makes it difficult to treat organic substances that are hardly decomposable, and the treatment using ultraviolet rays has a problem that the economic burden of consuming a large amount of electric energy is large.
[0006]
In recent years, a method using ozone has attracted attention as a new means for decomposing organic substances. In this case, by using hydrogen peroxide as an accelerator in addition to ozone gas, it is possible to efficiently decompose organic substances. This is because the generation of hydroxyl radicals (OH radicals) is further increased by the influence of hydrogen peroxide, and organic substances in water can be efficiently decomposed.
[0007]
An organic treatment apparatus using ozone and hydrogen peroxide in combination includes an ozone generator, a raw material gas pretreatment apparatus, a reaction tank, and an exhaust ozone gas treatment apparatus. Moreover, the oxidizing agent processing apparatus which processes ozone and hydrogen peroxide which were not used for reaction from the processing water processed by the reaction tank, and CO which decomposes | disassembles and produces | generates organic substance₂And means for removing organic acids, such as an ion exchanger (Japanese Patent Laid-Open No. 11-114584).
[0008]
Figure6Indicates a conventional organic matter processing apparatus using ozone gas, and includes an ozone generator 511, a reaction tank 521, and a gas dissolving means 531. The ozone generator 511 is connected to the gas pretreatment device 510. The reaction tank 521 is filled with water to be treated 561. The gas dissolving means 531 is provided in the reaction tank 521 so as to be immersed in the water to be treated 561, and is connected to an ozone generator through a pipe 541. A supply pipe 571 is connected to the reaction tank 521, and H 2 O 2581 and a pH adjuster 582 are mixed into the water to be treated 561 through the supply pipe 571. Further, a waste gas treatment device 584 for treating ozone and H 2 O 2 extracted from the water to be treated 561 without being used for the oxidation treatment is connected to the reaction tank 521.
[0009]
In such an apparatus, H2O2 and a pH adjusting agent such as NaOH are mixed with the water to be treated 561, and ozone gas from the ozone generator 511 is jetted from the gas dissolving means 531 to oxidize the water to be treated 561. . Oxidizing agents, carbon dioxide gas, oxidative decomposition products such as organic acids, etc. remaining in the treated water 561 subjected to oxidation treatment are removed by an activated carbon adsorption device and an ion exchanger.
[0010]
As the ozone generator 511, a device that generates ozone by silent discharge is usually used. In the silent discharge, ozone is generated by discharging the source gas processed by the source gas pretreatment device 510 through an ozone generator 511 and applying an AC voltage. The source gas pretreatment device 510 generates a gas having an oxygen concentration of 80% or more using air as a source material. In the ozone generator 511, since heat is generated by discharge, a cooling device is used in combination. The waste gas treatment device 584 removes ozone remaining in the waste gas with a catalyst resin or the like, and then discharges it into the atmosphere.
[0011]
The gas dissolving means 531 introduces gas into the liquid by passing through the pores, or introduces gas by rotating blades.
[0012]
In addition, instead of a gas dissolving means for dissolving a gas in the liquid, a reactor using a packed tower for dissolving the liquid in the gas is used in the reaction tank of such an organic substance processing apparatus.
[0013]
Since a reaction tank using a packed tower can be processed in a multistage manner, the ozone concentration of the waste gas can be lowered as much as possible by sequentially reusing the waste gas. However, since the utilization efficiency of ozone is worse than that of the gas dissolving means, the required amount of ozone is not significantly different from that of the rotary blade type gas dissolving means. In other words, the packed tower can efficiently absorb ozone, but it is not efficient in using the absorbed ozone in the reaction. Conversely, the gas dissolving means efficiently uses the absorbed ozone in the reaction. Despite being able to do so, the absorption efficiency is low, and the proportion of ozone that escapes into the waste gas is large. Each has its advantages and disadvantages, and is used according to its purpose.
[0014]
[Problems to be solved by the invention]
In such a conventional organic matter processing apparatus, the utilization efficiency of ozone in the reaction tank is poor and a large amount of ozone is consumed. For this reason, it is not preferable economically. In addition, since ozone is an air pollutant, it is desired to minimize the amount used. In the conventional apparatus, ozone that has not been consumed in the reaction is released into the atmosphere through the waste gas treatment apparatus 40 in the reaction tank 32, and thus there is a problem that such a request cannot be met.
[0015]
On the other hand, with the recent miniaturization of LSIs and ULSIs, the demand for the purity of pure water used in these productions has also increased, and an organic substance-containing water treatment apparatus using ozone and hydrogen peroxide in combination. Also, a high decomposition rate has been demanded.
[0016]
In the case of performing oxidative decomposition treatment of an organic substance using a conventional organic substance processing apparatus employing such a gas dissolving means, the higher the decomposition rate of the organic substance, the higher the ozone requirement becomes. It has become. That is, when the decomposition rate of TOC is low, the ozone utilization efficiency is relatively high, but when the decomposition efficiency of TOC is improved, the ozone utilization efficiency tends to deteriorate.
[0017]
For example, the amount of ozone required for treating the water to be treated having an IPA concentration of 10 ppm as organic carbon is ΔO if the concentration of the treated water is 2 ppm as organic carbon.₃/ ΔTOC (g / g) = 15.0, but if 1 ppm is targeted, ΔO₃/ ΔTOC (g / g) = 18.7.
[0018]
In addition, in an underwater organic matter treatment apparatus employing conventional gas dissolution means, not all of the ozone increased to improve the decomposition efficiency is necessarily utilized for the reaction of organic matter, most of which is used as waste gas. Remains. For example, when removing the water to be treated having an IPA concentration of 10 ppm up to 2 ppm, the proportion of ozone remaining in the waste gas that is not used for the reaction in the ozone supplied to the reaction tank from the ozone generator Is about 20%, but when it is further removed to 1 ppm, it is about 40%. For this reason, when the decomposition efficiency is improved, the utilization efficiency of ozone is reduced.
[0019]
Therefore, an object of the present invention is to provide a method and apparatus for treating organic substances in water using ozone and hydrogen peroxide in combination, which has high decomposition efficiency and can minimize the amount of ozone required.
[Means for Solving the Problems]
[0020]
In order to achieve the above object, the present invention provides water to be treated using ozone and hydrogen peroxide in combination.Continuously from the first reactor to the second reactorProcessing method to processBecause,
(1) To the treated water filled in the first reaction tank,
  Hydrogen peroxide is added 1-3 times the amount of ozone by weight per unit time,
  Add a pH adjuster so that the pH at the outlet of the piping to the second reactor is 7-8,
  Ozone-containing gas generated by an ozone generator using oxygen gas having an oxygen concentration of 80% or more is dissolved in fine bubbles to oxidize the water to be treated,
(2) The ozone-containing gas discharged on the liquid level of the first reaction tank is sent from the first reaction tank to the second reaction tank by the gas introduction means, and finely added to the water to be treated accommodated in the second reaction tank. The water to be treated is further oxidized by dissolving it in bubbles,
(3) A waste gas treatment device is provided at the rear stage of the reaction tank of the second reaction tank to treat the remaining ozone gas, an adsorber is provided to remove unreacted hydrogen peroxide, and an ion exchanger is provided at the rear stage of the adsorber. It is provided to remove an organic acid generated from an organic substance in water by an oxidation treatment.
[0021]
Further, the present invention is a treatment method for continuously treating the water to be treated while transferring ozone and hydrogen peroxide from the first reaction tank to the second reaction tank,
(1) To treated water stored in the second reaction tank,
Ozone-containing gas generated by an ozone generator using oxygen gas having an oxygen concentration of 80% or more is dissolved in fine bubbles to oxidize the water to be treated,
(2) The ozone-containing gas discharged on the liquid level of the second reaction tank is sent from the second reaction tank to the first reaction tank by the gas introduction means, and is added to the treated water stored in the first reaction tank. Hydrogen oxide is added in an amount of 1-3 times the amount of ozone by weight per unit time, and a pH adjuster is added so that the pH at the outlet of the pipe to the second reaction tank is 7-8. The ozone-containing gas discharged on the liquid level of the tank is dissolved into fine bubbles and introduced into the water to be treated contained in the first reaction tank to further oxidize the water to be treated.
(3) A waste gas treatment device is installed in the first reaction tank to treat the remaining ozone gas, and an unreacted hydrogen peroxide is removed after the second reaction tank, and ion exchange is performed after the adsorber. A vessel is provided to remove organic acids generated from organic substances in water by oxidation treatment.
[0022]
In the present invention, the oxidation treatment is preferably performed by generating fine bubbles of ozone-containing gas with a rotating blade.
[0023]
Furthermore, the underwater organic substance treatment apparatus of the present invention has a first reaction tank and a second reaction tank connected downstream thereof, and is an underwater that continuously treats water to be treated using ozone and hydrogen peroxide together. An organic matter processing apparatus,
(1) The first reaction tank is connected to an ozone generator that generates an ozone-containing gas using oxygen gas having an oxygen concentration of 80% or more, and the ozone-containing gas is supplied to the water to be treated contained in the first reaction tank. A dissolving means for generating and dissolving fine bubbles, a gas introducing means for drawing out the ozone-containing gas discharged on the liquid surface of the first reaction tank from the first reaction tank and sending it to the second reaction tank, hydrogen peroxide A hydrogen peroxide supply means for adding 1 to 3 times the amount of ozone in a weight ratio per unit time, and a pH adjuster so that the pH at the outlet of the pipe to the second reaction tank is 7-8 pH adjusting means,
(2) The second reaction tank is provided with a dissolving means for generating and dissolving fine bubbles in the water to be treated contained in the second reaction tank, the ozone-containing gas drawn from the first reaction tank,
(3) A waste gas treatment device for treating the remaining ozone gas, an adsorber for removing unreacted hydrogen peroxide in the liquid to be treated, and a post stage of the adsorber are provided at the subsequent stage of the second reaction tank. And an ion exchanger for removing an organic acid generated from an organic substance in the liquid to be treated.
[0024]
Moreover, the underwater organic substance processing apparatus of this invention has a 1st reaction tank and the 2nd reaction tank connected downstream from it, and processes a to-be-processed water continuously using ozone and hydrogen peroxide together. An underwater organic matter processing device,
(1) The second reaction tank is connected to an ozone generator that generates an ozone-containing gas using oxygen gas having an oxygen concentration of 80% or more, and the ozone-containing gas is added to the water to be treated contained in the second reaction tank. A dissolving means for generating and dissolving fine bubbles, and a gas introducing means for drawing out the ozone-containing gas discharged on the liquid surface of the second reaction tank from the second reaction tank and sending it to the first reaction tank,
(2) In the first reaction tank, the ozone-containing gas drawn from the second reaction tank is dissolved in water to be treated contained in the first reaction tank to generate fine bubbles and dissolved in hydrogen peroxide; , Hydrogen peroxide supply means for adding 1-3 times the amount of ozone by weight per unit time, and pH adjustment to add pH adjuster to the second reaction tank so that the pH at the outlet of the pipe is 7-8 Means and a waste gas treatment device for treating the remaining ozone gas,
(3) An adsorber that removes unreacted hydrogen peroxide in the liquid to be treated in the latter stage of the second reaction tank, and an organic acid that is connected to the latter stage of the adsorber and is generated from organic substances in the liquid to be treated. And an ion exchanger for removing water.
[0025]
The melting means preferably generates fine bubbles by means of a blade that rotates the introduced ozone-containing gas.
[0026]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.
[0027]
FIG. 1 is a cross-sectional view showing a first embodiment of an underwater organic matter processing apparatus in the present invention. The organic matter processing apparatus mainly includes an ozone generator 11, reaction vessels 121 and 122, dissolution means 131 and 132, and gas introduction means 141 and 142.
[0028]
The ozone generator 11 is connected to the raw material gas pretreatment device 10. The reaction tank 121 is filled with water to be treated 161. The dissolving means 131 is provided in the reaction tank 121 so as to be immersed in the water to be treated 161, and is connected to the ozone generator 11 from the ozone generator 11 by the gas introducing means 141. Thereby, ozone-containing gas is introduced. A supply pipe 71 is connected to the reaction tank 121, and H is supplied through the supply pipe 71.₂O₂81 and the pH adjuster 82 are mixed with the water to be treated 161.
[0029]
To-be-treated water 161 put in the reaction tank 121 contains H₂O₂81 and the pH adjusting agent 82 are mixed, and the ozone mixed gas introduced from the gas introduction unit 141 is ejected as fine bubbles from the dissolution unit 131, whereby the organic matter in the water to be treated 161 is oxidized.
[0030]
The reaction tank 122 is connected from the reaction tank 121 by a pipe 72, and the water to be treated 161 oxidized in the reaction tank 121 is transferred and filled. The dissolution means 132 is provided in the reaction tank 122 so as to be immersed in the water to be treated 162. The gas introduction unit 142 is drawn from the top of the reaction tank 121, and its tip is connected to the dissolution unit 132. As a result, the gas introduction unit 142 acts to introduce the surplus ozone-containing gas remaining in the reaction tank 121 into the dissolution unit 132.
[0031]
In the water to be treated 162 transferred into the reaction tank 122, the remaining ozone-containing gas is ejected as fine bubbles from the dissolving means 132 into the reaction tank 121 introduced by the gas introduction means 142. The organic matter in 162 is subjected to oxidative decomposition treatment.
[0032]
At the top of the reaction tank 122, there is provided a discharge pipe 83 that discharges the ozone mixed gas remaining after the completion of the reaction and is connected to the waste gas treatment device 84.
[0033]
A drain pipe 85 is connected to the adsorber 86 from the reaction tank 122, and a drain pipe 87 is connected to the ion exchanger 88 from the adsorber 86. The adsorber 86 is filled with an adsorbent such as activated carbon. As a result, the water to be treated 162 subjected to the oxidative decomposition treatment in the reaction tank 122 is discharged, and ozone remaining in the water to be treated 162, H₂O₂Etc. are removed by adsorption. The treated water 162 is discharged to the ion exchanger 88 through the drain pipe 87, and the oxidative decomposition products such as the organic acid and the trace amount of carbon dioxide in the treated water 162 are removed in the ion exchanger 88.
[0034]
In the first embodiment, if necessary, one or more reaction tanks may be further provided between the reaction tank 121 and the reaction tank 122 to increase the degree of reuse of ozone gas that remains without being consumed. it can. In this case, a pipe similar to the pipe 72 that is connected from the reaction tank 121 to the reaction tank 122 and that transfers the water to be treated 161 oxidized in the reaction tank 121 is provided in each additional reaction tank. Further, each reaction tank is equipped with gas introduction means and dissolution means similar to the gas introduction means 142 drawn from the top of the reaction tank 121 and connected at the tip thereof to the dissolution means 132. Further, the water to be treated filled in each additional reaction tank and the water to be treated 162 filled in the reaction tank 122 are H.₂O₂A supply pipe for mixing 81 and the pH adjusting agent 82 is connected to each reaction tank.
[0035]
FIG. 2 is a cross-sectional view showing a second embodiment of the underwater organic matter processing apparatus in the present invention, which is a processing apparatus in which gas introducing means is installed in the direction opposite to the flow of the ozone mixed gas of the first embodiment.
[0036]
In the processing apparatus according to the second embodiment, a supply pipe 71 is connected to the reaction tank 221, and H is supplied via the supply pipe 71.₂O₂81 and the pH adjusting agent 82 are mixed with the water to be treated 261 and filled into the reaction tank 221. The tip of the gas introducing means 242 drawn from the top of the reaction tank 222 is connected to the dissolving means 231 provided in the reaction tank 221. Thereby, the gas introduction means 242 introduces the ozone-containing gas after the oxidation treatment in the reaction tank 222 to the dissolution means 231 and generates fine bubbles of the ozone mixed gas.
[0037]
The treated water 261 placed in the reaction tank 221 contains H₂O₂81 and the pH adjusting agent 82 are mixed, and the ozone mixed gas introduced from the gas introduction unit 242 is ejected from the dissolution unit 231 as fine bubbles, whereby the organic matter in the water to be treated 261 is oxidized. In addition, an exhaust pipe 83 is provided at the top of the reaction tank 221 to discharge the ozone mixed gas remaining after the completion of the reaction and to be connected to the waste gas treatment device 84.
[0038]
The reaction tank 222 is connected from the reaction tank 221 by a pipe 72, and the water to be treated 261 oxidized in the reaction tank 221 is transferred and filled. The dissolving means 232 is provided in the reaction tank 222 so as to be immersed in the water to be treated 262, and the dissolving means 232 is connected to the ozone generator 11 from the ozone generator 11 by the gas introducing means 241. As a result, the ozone-containing gas is introduced into the melting means 232 and fine bubbles of the ozone-containing gas are generated.
[0039]
The ozone-containing gas introduced by the gas introduction unit 241 is ejected from the dissolution unit 232 as fine bubbles into the water to be treated 262 transferred into the reaction tank 222, so that the organic matter in the water to be treated 262 is oxidized. Disassembled.
[0040]
The connection form from the reaction tank 222 to the adsorber 86 and from the adsorber 86 to the ion exchanger 88 is the same as in the first embodiment, and the water to be treated 262 that has been subjected to the oxidative decomposition treatment in the reaction tank 222 is discharged. , Ozone remaining in treated water 262, H₂O₂Etc. are adsorbed and removed by the adsorber 86. Further, the water to be treated 262 is discharged to the ion exchanger 88 through the drain pipe 87, and in the ion exchanger 88, oxidative decomposition products such as organic acids and trace amounts of carbon dioxide in the water to be treated 262 are removed. .
[0041]
Moreover, in the said 2nd embodiment, when ozone containing gas remains without being consumed by the oxidation process in the reaction tank 221, it can deform | transform into the form which recycles ozone containing gas as needed. In this case, one or more reaction vessels are further provided between the reaction vessel 221 and the reaction vessel 222, and a gas introduction unit similar to the gas introduction unit 242 is sequentially provided from the reaction vessel 222 toward the reaction vessel 221. Alternatively, one or more reaction tanks may be further installed in the subsequent stage of the reaction tank 222 and may be configured to cross the direction of ozone-containing gas introduction of the gas introduction means 242 from the reaction tank 222 to the reaction tank 221. It is.
[0042]
In the case of the processing apparatus modified to the former form, an additional pipe similar to the pipe 72 that is connected from the reaction tank 221 to the reaction tank 222 and that transfers the water to be treated 261 oxidized in the reaction tank 221 is additionally installed. Provided in each reaction tank. In addition, each reaction tank is equipped with gas introduction means and dissolution means similar to the gas introduction means 242 that is drawn out from the top of the reaction tank 222 and whose tip is connected to the dissolution means 231. Further, the water to be treated filled in each additional reaction tank and the water to be treated 262 filled in the reaction tank 222 are H.₂O₂A supply pipe for mixing 81 and the pH adjusting agent 82 is connected to each reaction tank.
[0043]
In the case of the processing apparatus modified in the latter form, each reaction tank to be additionally installed is equipped with a pipe similar to the pipe 72 for transferring the water to be treated 261 oxidized in the reaction tank 221. In addition, instead of the discharge pipe 83 installed at the top of the reaction tank 221 and connected to the waste gas treatment device 84, a gas introduction means drawn from the top of the reaction tank 222 and connected at the tip thereof to the dissolution means 231. The same gas introduction means and dissolution means as those of 242 are provided in each reaction layer. Further, the water to be treated filled in each additional reaction tank and the water to be treated 262 filled in the reaction tank 222 are H.₂O₂A supply pipe for mixing 81 and the pH adjusting agent 82 is connected to each reaction tank.
[0044]
FIG. 3 is a cross-sectional view showing a third embodiment of the underwater organic matter treatment apparatus in the present invention, which is a treatment apparatus equipped with a plurality of gas introduction means in a branched and connected form.
[0045]
The organic matter processing apparatus in the third embodiment mainly includes an ozone generator 11, reaction vessels 321, 322, 323, dissolution means 331, 332, 333, and gas introduction means 341, 342, 343, 344. ing. A supply pipe 71 is connected to the reaction tank 321, and H is supplied through the supply pipe 71.₂O₂81 and the pH adjusting agent 82 are mixed with the water to be treated 361 and filled into the reaction tank 321. The dissolving means 331 is provided in the reaction tank 321 so as to be immersed in the water to be treated 361, and is connected to the ozone generator 11 from the ozone generator 11 by the gas introducing means 341. The gas introduction unit 341 includes a branching portion 351 that branches to the gas introduction unit 342.
[0046]
The treated water 361 placed in the reaction tank 321 contains H₂O₂81 and the pH adjuster 82 are mixed, and the ozone mixed gas introduced from the gas introduction unit 341 is ejected as fine bubbles from the dissolution unit 331, whereby the organic matter in the water to be treated 361 is oxidized.
[0047]
The reaction tank 322 is connected from the reaction tank 321 by a pipe 72, and the water to be treated 361 oxidized in the reaction tank 321 is transferred. The dissolving means 332 is provided in the reaction tank 322 so as to be immersed in the water to be treated 362. The gas introduction unit 342 is connected to the branch portion 351 of the gas introduction unit 341 and connected to the tip of the dissolution unit 332 provided in the reaction tank 322, and introduces an ozone-containing gas from the ozone generator 11.
[0048]
In the water to be treated 362 filled in the reaction tank 322, the ozone-containing gas introduced by the gas introduction unit 342 is ejected as fine bubbles from the dissolving unit 332, so that the organic matter in the water to be treated 362 is oxidized. It is processed.
[0049]
The reaction tank 323 is connected from the reaction tank 322 by a pipe 73, and the water to be treated 362 oxidized in the reaction tank 322 is transferred. The dissolving means 333 is provided in the reaction tank 323 so as to be immersed in the water to be treated 363. The melting means 333 includes a gas introduction means 343 having a connecting portion 352 that connects the gas introduction means from the top of the reaction vessel 321, and a gas introduction connected to the connection portion 352 of the gas introduction means 343 from the top of the reaction vessel 322. The tip of the means 344 is connected. By means of the gas introduction means 343 and the gas introduction means 344 connected to the connecting part 352, the ozone-containing gas remaining after the oxidation treatment in the reaction tank 321 and the ozone-containing gas remaining after the oxidation treatment of the reaction tank 322 are mixed and dissolved. 333.
[0050]
In the water to be treated 363 filled in the reaction tank 323, the ozone-containing gas introduced by the gas introducing means 343 and 344 is ejected as fine bubbles from the dissolving means 333, so that organic substances in the water to be treated 363 are discharged. Oxidized. An exhaust pipe 83 that exhausts the ozone-containing gas remaining after the oxidative decomposition treatment from the top of the reaction vessel 323 and is connected to the waste gas treatment device 84 is provided.
[0051]
From the reaction tank 323, a drain pipe 85 is connected to an adsorber 86, and further, a drain pipe 87 is connected from the adsorber 86 to an ion exchanger 88. As a result, the water to be treated 162 subjected to the oxidative decomposition treatment in the reaction tank 122 is discharged, and ozone remaining in the water to be treated 162, H₂O₂Etc. are removed by adsorption. The treated water 162 is discharged to the ion exchanger 88 through the drain pipe 87, and the oxidative decomposition products such as the organic acid and the trace amount of carbon dioxide in the treated water 162 are removed in the ion exchanger 88.
[0052]
Further, in the organic matter treatment apparatus of the third embodiment, one or more reaction vessels are additionally installed, or the gas introduction means are branched and connected via valve means such as a three-way valve and a four-way valve. It is possible to change to a form in which a large number of gas introducing means having a portion and a connecting portion are further combined and equipped. In the processing apparatus modified in this way, each reaction vessel is provided with a switching unit according to the purpose by switching the branch means and the valve means of the connecting part in each gas introduction means provided in combination with a large number of gas introduction means. It is possible to introduce ozone-containing gas mixed in various ways for each dissolving means. For example, ozone-containing gas from a plurality of reaction tanks after oxidation treatment is mixed, and ozone-containing gas obtained by additionally mixing ozone-containing gas from an ozone generator is introduced into the dissolving means, or during the oxidative decomposition reaction The ozone-containing gas remaining in the other reaction tank after the oxidation treatment or the ozone-containing gas from the ozone generator can be additionally introduced into the melting means.
[0053]
FIG. 4 is a sectional view showing a fourth embodiment of the underwater organic matter processing apparatus in the present invention, which is a processing apparatus equipped with a plurality of gas introducing means and a plurality of dissolving means in one reaction tank.
[0054]
In the processing apparatus of the fourth embodiment, a plurality of dissolution means 431 and 432 are installed in a reaction tank 421, and gas introduction means 441 and 442 are connected to the reaction tank 421, respectively. The ozone generator 11 is connected to the raw material gas pretreatment device 10, and the reaction tank 421 is filled with water to be treated 461. The dissolution means 431 is provided in the reaction tank 421 so as to be immersed in the water to be treated 461, and is connected to the ozone generator 11 from the ozone generator 11 by the gas introduction means 441. Thereby, ozone-containing gas is introduced. A supply pipe 71 is connected to the reaction tank 421, and H is supplied through the supply pipe 71.₂O₂81 and the pH adjuster 82 are mixed with the water to be treated 461.
[0055]
The treated water 461 placed in the reaction tank 421 has H₂O₂81 and the pH adjusting agent 82 are mixed, and the ozone mixed gas introduced from the gas introduction unit 441 is ejected as fine bubbles from the dissolution unit 431, whereby the organic matter in the water to be treated 461 is oxidized.
[0056]
In the reaction tank 421, a dissolving means 432 is provided so as to be immersed in the water to be treated 461. The gas introduction unit 442 is drawn from the top of the reaction tank 421 and the tip thereof is connected to the dissolution unit 432. As a result, the gas introduction unit 442 introduces the surplus ozone-containing gas that has passed through the water to be treated 461 in the reaction tank 421 and discharged onto the liquid surface into the dissolution unit 432.
[0057]
In the water to be treated 461 in the reaction tank 421, the remaining ozone-containing gas is ejected as fine bubbles from the dissolving means 432 into the reaction tank 421 introduced by the gas introduction means 442, so that the water in the water to be treated 461 Organic matter is oxidatively decomposed. Here, the ozone-containing gas introduced into the dissolution means 432 is ejected as fine bubbles from the dissolution means 431, passes through the water to be treated 461 without being consumed for oxidative decomposition, and is discharged into the top of the reaction tank. In addition, since the ozone-containing gas ejected from the dissolving means 432 and passed through the water to be treated 461 at least once is included, the utilization efficiency of ozone can be further increased. Moreover, it is also possible to introduce into the dissolution means 431 and 432 from the gas introduction means 441 and 442, respectively, and it can be controlled according to the purpose such as ozone concentration and oxidation treatment speed.
[0058]
At the top of the reaction tank 421, a discharge pipe 83 that discharges the waste gas remaining after the reaction and is connected to the waste gas treatment device 84 is provided.
[0059]
A drain pipe 85 is connected to the adsorber 86 from the reaction tank 421, and a drain pipe 87 is connected to the ion exchanger 88 from the adsorber 86. The water to be treated 461 that has been subjected to the oxidative decomposition treatment in the reaction tank 421 is discharged by the adsorber 86, and ozone remaining in the water to be treated 461, H₂O₂Etc. are removed by adsorption. The treated water 461 is discharged to the ion exchanger 88 through the drain pipe 87, and the oxidative decomposition products such as the organic acid and the small amount of carbon dioxide in the treated water 162 are removed in the ion exchanger 88.
[0060]
The raw material gas pretreatment device 10 provided in common for the treatment devices of each aspect is any device as long as it can generate a gas having an oxygen concentration of 80% or more using air as a raw material. The ozone generator 11 may be a silent discharge method, an electrolysis method, a photochemical reaction method, a chemical reaction method, a radiation irradiation method, a high-frequency electric field method, or the like, and any device can be used. A silent discharge type ozone generator that includes an apparatus and applies an AC voltage is suitable.
[0061]
As the melting means 131, 132, 231, 232, 331, 332, 333, 431 and 432, any type of apparatus can be used as long as the ozone-containing gas introduced from the gas introduction means can be ejected as fine bubbles. Although devices can be used, devices of the type with pores or with rotating wings are desirable. The melting means 132, 231, 333, 431 and 432 are particularly preferably devices of the type having rotating wings. In the case of using a device of a type having pores, a gas booster such as a blower is added to the gas introduction means.
[0062]
The adsorber 86 may be an apparatus composed of a column filled with activated carbon as an adsorbent, and the ion exchanger 88 may be an apparatus composed of a column filled with a cation exchanger and an anion exchanger. A regenerative type or non-regenerative mixed bed type apparatus filled with an exchange resin and a strongly basic anion exchange resin is suitable. The waste gas treatment device 84 is preferably a device of a type that includes a catalyst resin and decomposes ozone in the waste gas.
[0063]
As described above, the underwater organic matter treatment apparatus of the present invention has been described including the apparatuses modified by showing the first to fourth embodiments, but various modifications are also possible within the technical scope of the present invention. Can be configured. Thus, the organic substance processing apparatus comprised in various forms selects an appropriate form according to the kind, density | concentration, etc. of the organic substance contained in the to-be-processed water which performs an oxidation process, respectively.
[0064]
Next, the method for treating organic matter in water in the present invention using the organic matter treating apparatus as described above will be described.
[0065]
In the treatment method by the treatment apparatus of the first embodiment, the ozone-containing gas introduced into the dissolving means 131 from the ozone generator 11 through the gas introduction means 141 is added to the water to be treated 161 put in the reaction tank 121. Then, the oxidation treatment step of dissolving the ozone-containing gas as fine bubbles by the dissolving means 131, and the water to be treated 161 after passing through the oxidation treatment step in the reaction tank 121 are transferred to the reaction tank 122 via the pipe 72, and then the reaction tank The ozone-containing gas remaining without being consumed in the oxidation treatment step 121 is taken out from the gas introduction means 142 through the gas introduction means 142, and the dissolving means 132 generates fine bubbles of the ozone-containing gas to dissolve and dissolve in the water to be treated 162. Processing steps.
[0066]
To-be-treated water 161 put into the reaction tank 121 is supplied to the H₂O₂81 is injected. Injection concentration is ΔH₂O₂/ ΔO₃(G / g) = 1 to 3 is preferable. This H₂O₂The injection concentration of H is determined by various conditions.₂O₂If the concentration is too low, the generated OH radicals are insufficient. If the concentration is too high, the generated OH radicals are H.₂O₂Because it attacks, it becomes inefficient. H₂O₂The injection of 81 is not necessarily performed until the water to be treated 161 enters the reaction tank 121, and may be directly injected into the reaction tank 121 via the supply pipe 71.
[0067]
Further, the pH adjusting agent 82 is injected into the water to be treated 161 put in the reaction tank 121 through the supply pipe 71. As the pH adjuster 82, an alkali such as NaOH or KOH is usually used. Thereby, the pH at the outlet to the pipe 62 of the reaction tank 121 is controlled to the neutral or weak alkali side. On the acidic side, OH radicals are not sufficiently generated, and in high alkali, the scavenger carbonate ion has an adverse effect. In addition, since the pH of the water to be treated 161 becomes acidic due to the ozone reaction, in addition to when filling the reaction tank, and after the completion of the oxidation treatment process, the reaction water 121 is supplied to the reaction tank 121 via the supply pipe 71 as necessary. The pH adjusting agent 22 is injected, and the pH at the outlet of the reaction tank 121 is controlled to an appropriate pH.
[0068]
And H₂O₂The control of the injection amount and pH of 71 slightly affects the organic substance removal performance in the oxidation treatment step. Therefore, if necessary, after the oxidation treatment step is completed, supply piping to the water to be treated 161 in the reaction tank 121 is provided. 71 and further through H₂O₂71 and / or pH adjuster 22 is injected. Thereby, it is possible to perform processing under appropriate processing conditions even in the subsequent oxidation processing step in the reaction tank 122.
[0069]
In addition, organic substances that are oxidatively decomposed have different reactivity with hydroxyl radicals for each substance, and in order to perform oxidative decomposition treatment efficiently, the type, concentration, and progress of the reaction of organic substances contained in the water to be treated Etc. cause differences in the optimum ozone concentration, hydrogen peroxide concentration, and pH in each treated water. Depending on the type and concentration of the organic matter contained in the water to be oxidized, a processing device of an appropriate form is selected from the processing devices of the first to fourth embodiments and the processing devices each configured in a modified form. To oxidatively decompose.
[0070]
According to such an organic matter processing method and processing apparatus of the present invention, ozone that has passed through the water to be processed at least once and is discharged onto the liquid surface of the water to be processed and is not consumed in the reaction, Improved efficiency of ozone utilization because it can be reused for oxidative decomposition of organic substances remaining in the water to be treated without being oxidatively decomposed by being sent to other reaction tanks or dissolving means in the same reaction tank via the introduction means And improving the decomposition efficiency of organic matter. In addition, since the oxidative decomposition treatment can be performed by selecting a treatment device in an appropriate form according to the type and concentration of the organic matter contained in the treated water, it can be applied to the treated water containing various organic matter.
[0071]
Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited thereto.
[0072]
【Example】
The treated water was treated under the following conditions using the treatment apparatus shown in FIG. As the water to be treated, IPA containing 10 ppm as total organic carbon (TOC) was used. Of the treatment devices shown in the figure, the adsorber is originally intended to remove ozone and hydrogen peroxide, but the activated carbon packed in the adsorber also has an organic matter removal ability. In consideration of the influence in evaluating the oxidation treatment ability of ozone, it was not used in this example.
[0073]
The processing flow rate of the above IPA is 0.5m³/ H, ozone concentration in ozone-containing gas is 120 g / m³The amount of hydrogen peroxide used in combination with ozone was 20 ppm, and the pH at the reaction vessel outlet was adjusted to 7.0 to 8.0 with NaOH.
[0074]
Figure5These show the processing apparatus of the comparative example with respect to this Example, and the same code | symbol is attached | subjected to the element same as FIG. Figure5In this processing apparatus, a branch pipe 151 is connected to the gas introducing means 141 in the processing apparatus of FIG. By making such a connection, the ozone-containing gas from the ozone generator 11 is supplied to the melting means 131 of the reaction tank 121 through the gas introduction means 141, and to the melting means 132 of the reaction tank 122 through the branch pipe 151. Also comes to supply. In this comparative example, ozone-containing gas was introduced into the melting means 131 and the melting means 132 in a ratio of 1: 1. Further, the waste gas from the reaction tank 121 and the reaction tank 122 was directly passed to the waste gas treatment device 84 without being reused. Other conditions are the same as in the example. Also figure6In the conventional processing apparatus shown in FIG. 1, the processing was performed under the same conditions as in the examples and comparative examples.
[0075]
Tables 1 and 2 show the processing results of Examples, Comparative Examples, and Conventional Examples.
[0076]
[Table 1]
[0077]
[Table 2]
[0078]
As is apparent from Table 1, in the examples of the present invention, higher removal performance is obtained as compared with the comparative examples and the conventional examples. In the comparative example, the removal performance is almost the same as that of the conventional example. Table 2 shows the amount of ozone necessary for the TOC concentration of the water to be treated to reach 1 or 0.5 ppm when the IPA containing 10 ppm of carbon as the TOC concentration of the water to be treated is treated. △ O as an indicator₃/ ΔTOC (g / g) was used. As is apparent from Table 2, in the examples of the present invention, the required ozone amount could be greatly reduced. Further, in the comparative example, the required ozone amount was almost the same as the conventional example.
[0079]
【The invention's effect】
As described above, according to the present invention, it is possible to perform organic matter treatment with high decomposition efficiency and capable of minimizing the necessary amount of ozone.
[0080]
[Brief description of the drawings]
FIG. 1 is a cross-sectional view showing a first embodiment of a processing apparatus according to the present invention.
FIG. 2 is a cross-sectional view showing a second embodiment of the processing apparatus according to the present invention.
FIG. 3 is a cross-sectional view showing a third embodiment of the processing apparatus according to the present invention.
FIG. 4 is a cross-sectional view showing a fourth embodiment of the processing apparatus in the present invention.
FIG. 5 is a cross-sectional view of a processing apparatus of a comparative example.
FIG. 6 is a cross-sectional view of a conventional processing apparatus.
[0081]
[Explanation of symbols]
11 Ozone generator
121, 122 reactor
131, 132 dissolution means
141, 142 Gas introduction means
221 and 222 reaction tank
231,232 Dissolution means
241,242 Gas introduction means
321, 322, 323 reaction tank
331, 332, 333 dissolution means
341, 342, 343, 344 Gas introduction means
421, 422 reactor
431, 432 dissolution means
441, 442 Gas introduction means

Claims

A treatment method in which ozone and hydrogen peroxide are used together to continuously treat water to be treated while being transferred from the first reaction tank to the second reaction tank ,
( 1) To the water to be treated filled in the first reaction tank,
Hydrogen peroxide is added 1-3 times the amount of ozone by weight per unit time,
Add pH adjuster to the second reaction tank so that the pH at the outlet of the pipe is 7-8,
The oxygen concentration is generated by an ozone generator with more than 80% of the oxygen gas containing ozone gas, dissolved into fine bubbles by oxidizing the water to be treated,
(2) The ozone-containing gas discharged onto the liquid level of the first reaction tank is sent from the first reaction tank to the second reaction tank by the gas introduction means, and is treated water stored in the second reaction tank. In addition, the water to be treated is further oxidized by dissolving it into fine bubbles,
(3) A waste gas treatment device is provided downstream of the second reaction tank to remove residual ozone gas, an adsorber is provided to remove unreacted hydrogen peroxide, and an ion exchanger is provided downstream of the adsorber. And removing the organic acid produced from the organic matter in the water by the oxidation treatment .

A treatment method in which ozone and hydrogen peroxide are used in combination to continuously treat water to be treated while being transferred from the first reaction tank to the second reaction tank,
(1) To treated water stored in the second reaction tank,
Ozone-containing gas generated by an ozone generator using oxygen gas having an oxygen concentration of 80% or more is dissolved into fine bubbles to oxidize the water to be treated,
(2) The ozone-containing gas discharged onto the liquid level of the second reaction tank is sent from the second reaction tank to the first reaction tank by gas introduction means,
Hydrogen peroxide is added to the water to be treated contained in the first reaction tank in an amount 1 to 3 times the amount of ozone per unit time, and the pH at the outlet of the pipe to the second reaction tank is 7 to 7. Add pH adjuster to 8
The ozone-containing gas discharged on the liquid surface of the second reaction tank is dissolved into fine bubbles and introduced into the water to be treated contained in the first reaction tank to further oxidize the water to be treated.
(3) A waste gas treatment device is provided in the first reaction tank to treat the remaining ozone gas, and an unreacted hydrogen peroxide is removed by providing an adsorber at a subsequent stage of the second reaction tank. A method for treating an organic substance in water, wherein an organic acid generated from the organic substance in water by the oxidation treatment is removed by providing an ion exchanger.

The method for treating organic matter in water according to claim 1 or 2 , wherein the oxidation treatment is performed by generating fine bubbles of ozone-containing gas with a rotating blade.

An underwater organic matter treatment apparatus that has a first reaction tank and a second reaction tank connected downstream thereof, and continuously treats water to be treated by using ozone and hydrogen peroxide together.
(1) In the first reaction tank,
It is connected to an ozone generator that generates an ozone-containing gas using oxygen gas with an oxygen concentration of 80% or more, and the ozone-containing gas is dissolved to generate fine bubbles in the water to be treated contained in the first reaction tank. Means,
Gas introduction means for drawing out the ozone-containing gas discharged on the liquid surface of the first reaction tank from the first reaction tank and sending it to the second reaction tank;
A hydrogen peroxide supply means for adding hydrogen peroxide in an amount of 1-3 times ozone by weight per unit time;
PH adjusting means for adding a pH adjusting agent so that the pH at the outlet of the pipe to the second reaction tank is 7-8,
(2) The second reaction tank is provided with a dissolving means for generating and dissolving fine bubbles in the water to be treated contained in the second reaction tank, the ozone-containing gas drawn from the first reaction tank,
(3) Connected to the rear stage of the second reaction tank, a waste gas treatment apparatus for treating the remaining ozone gas, an adsorber for removing unreacted hydrogen peroxide in the liquid to be treated, and a rear stage of the adsorber And an ion exchanger that removes an organic acid generated from the organic matter in the liquid to be treated.

An underwater organic matter treatment apparatus that has a first reaction tank and a second reaction tank connected downstream thereof, and continuously treats water to be treated by using ozone and hydrogen peroxide together.
(1) The second reaction tank is connected to an ozone generator that generates an ozone-containing gas using an oxygen gas having an oxygen concentration of 80% or more, and the ozone-containing gas is treated water accommodated in the second reaction tank. A dissolving means for generating and dissolving fine bubbles, and a gas introducing means for drawing the ozone-containing gas discharged onto the liquid surface of the second reaction tank from the second reaction tank and sending it to the first reaction tank; With
(2) Dissolving means for generating fine bubbles in the first reaction tank and dissolving the ozone-containing gas drawn from the second reaction tank in the water to be treated accommodated in the first reaction tank;
A hydrogen peroxide supply means for adding hydrogen peroxide in an amount of 1-3 times ozone by weight per unit time;
PH adjusting means for adding a pH adjusting agent so that the pH at the outlet of the pipe is 7-8 to the second reaction tank;
A waste gas treatment device for treating the remaining ozone gas,
(3) An adsorber that removes unreacted hydrogen peroxide in the liquid to be treated is connected to the rear stage of the second reaction tank, and an organic substance in the liquid to be processed that is connected to the rear stage of the adsorber. An underwater organic matter treatment apparatus comprising: an ion exchanger that removes the produced organic acid.

6. The apparatus for treating organic matter in water according to claim 4 or 5 , wherein the dissolving means generates fine bubbles by a blade rotating the introduced ozone-containing gas.