JP3954227B2 - Method and apparatus for treating organic sewage containing endocrine disrupting substance or carcinogenic substance - Google Patents
Method and apparatus for treating organic sewage containing endocrine disrupting substance or carcinogenic substance Download PDFInfo
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- JP3954227B2 JP3954227B2 JP00948299A JP948299A JP3954227B2 JP 3954227 B2 JP3954227 B2 JP 3954227B2 JP 00948299 A JP00948299 A JP 00948299A JP 948299 A JP948299 A JP 948299A JP 3954227 B2 JP3954227 B2 JP 3954227B2
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Description
【０００１】
【発明の属する技術分野】
本発明は内分泌撹乱物質または発ガン性物質を含有する有機汚水の処理に関するものであり、特に浸出水や工業廃水などのような内分泌撹乱物質または発ガン性物質を含有する有機汚水の処理方法に関するものである。
【０００２】
【従来の技術】
内分泌撹乱化学物質は動物の体内に取り込まれた場合に、本来その生体内で営まれている正常なホルモン作用に影響を与える化学物質をいい、それらの曝露は人や野生動物の内分泌作用を撹乱し、生殖機能障害、悪性腫瘍などを引き起こす可能性があると指摘されている。これら内分泌撹乱物質は極めて低濃度で作用し、特に胎児期など発生段階で深刻な影響を与え、成長後にその影響が発現するなどの可能性が指摘されていることから、生物存続に関わる重大な影響をもたらす可能性も懸念されている。これまでに魚類、は虫類、鳥類などの野生生物において、生殖機能異常、生殖行動異常、雄の雌性化、ふ化能力の低下などと内分泌撹乱物質との関連が指摘されている。さらに人においても精子数の減少、前立腺癌の増加、および子宮内膜症の増加の傾向性と内分泌撹乱物質との関連も指摘されている。動物実験の結果では、いくつかの化学物質によって精巣停留や精子数の減少などの生殖機能障害や子宮内膜症などが引き起こされることが確認されている。発ガン性物質は細胞の癌化を促進することが知られている。
【０００３】
これまでの調査により内分泌撹乱物質および発ガン性物質として疑われるものとしては、ＰＣＢ類、ダイオキシン類、ポリ臭化ビフェニル、ヘキサクロロベンゼン、ペンタクロロフェノール、２，４，５−トリクロロフェノキシ酢酸、２，４−ジクロロフェノキシ酢酸、アミトロール、アトラジン、シマジン、ヘキサクロロシクロヘキサン、エチルパラチオン、カルバリル、クロルデン類、１，２−ジブロモ−３−クロロプロパン、ＤＤＴおよびその代謝物（ＤＤＥ、ＤＤＤ）、ケルセン、アルドリン、エンドリン、ディルドリン、エンドサルファン、ヘプタクロルおよびヘプタクロルエポキシド、マラチオン、メソミル、メトキシクロル、マイレックス、ニトロフェン、トキサフェン、カンフェクロル、有機スズ（トリブチルスズなど）、トリフルラリン、アルキルフェノール類、ビスフェノールＡ、フタル酸ジ（２−エチルヘキシル）、フタル酸ブチルベンジル、フタル酸ジブチル、フタル酸ジシクロヘキシル、フタル酸ジエチル、ベンゾ（ａ）ピレン、カドミウム、鉛、水銀、２，４−ジクロロフェノール、アジピン酸（２−エチルヘキシル）、ベンゾフェノン、４−ニトロトルエン、ジオキサン等が挙げられている。
【０００４】
これらは、それぞれ、難燃剤、殺菌剤、殺虫剤、防汚材、腐食防止剤、熱媒体、防腐剤、除草剤、樹脂の硬化剤、樹脂原料、プラスチック可塑剤、溶媒などとして、または燃焼過程で生成され、物質によって異なるが概ねμｇ／リットル〜ｐｇ／リットルオーダーの濃度で環境水中で検出されている。このような濃度レベルはＣＯＤ、ＴＯＣ等から推測される水中有機物濃度のｍｇ／リットルオーダーに比べて非常に低いものであるが、これらの内分泌撹乱化学物質が、非常に微量な量で上記のような作用を引き起こすことが知られていることから、環境水中あるいは環境に放出される以前の水に含まれる微量の内分泌撹乱化学物質を除去する技術の開発が望まれている。特に埋立地浸出水は、様々な種類の内分泌撹乱物質および発ガン性物質が含まれており、濃度も高い（ダイオキシン類が１００〜５０００ｐｇ／リットル、ビスフェノールＡが１００〜１００００ｎｇ／リットル、１，４−ジオキサンが１０００〜１０００００ｎｇ／リットル）ことから埋立地浸出水中の内分泌撹乱物質および発ガン性物質の処理は急務である。
【０００５】
従来、浸出水などの有機汚水（以下、被処理水とも言う）の主な処理方法としては、有機物除去を主体とした処理法を用いている。主な処理法としては、ＢＯＤ、窒素の除去を目的とした生物処理、色度、ＣＯＤ及びＳＳなどの除去を目的とした凝集沈殿処理、ＳＳなど濁質の除去を目的とした砂ろ過処理がある。さらに、高度処理法としては、活性炭処理を用いることがある。しかし、上記処理法のいずれも、汚水中の微量溶存性の内分泌撹乱物質および発ガン性物質、とりわけ、ダイオキシン、ジオキサン、ビスフェノールＡを分解除去する効果が少なく、放流水中にこれらの物質が残留する場合が多い。さらに内分泌撹乱物質および発ガン性物質の多くが水にはほとんど不溶であり、各処理工程で内分泌撹乱物質または発ガン性物質が減少しても、そのほとんどが処理工程から発生する汚泥中に含まれており、脱水処理後、ケーキ中の内分泌撹乱物質および発ガン性物質含率が高く、系内全体の内分泌撹乱物質および発ガン性物質の分解除去効果があまりないと考えられている。
最近の内分泌撹乱物質および発ガン性物質の分解処理技術としては、一般的に有機汚濁物質や懸濁物質を除去した処理水に溶存している内分泌撹乱物質および発ガン性物質を紫外線照射による脱塩素化反応及びオゾン注入による酸化反応で分解除去することが知られている。
【０００６】
【発明が解決しようとする課題】
しかし、この方法では内分泌撹乱物質および発ガン性物質の多くは水中に溶存できる濃度が微量であるため、従来の水処理工程を経た処理水中の内分泌撹乱物質および発ガン性物質が少なくなる場合が多く、その処理水に対して、分解除去を行っても、分解除去できる量が限られていた。このため流入内分泌撹乱物質および発ガン性物質のほとんどが処理工程より発生する汚泥に蓄積され、その分解除去が大きな課題となっている。
【０００７】
従って本発明は、従来技術の上記の問題点を解決するために、有機汚水に対し、溶存及び非溶存の内分泌撹乱物質および発ガン性物質を高効率で分解除去し、引き続いて、その他の有機汚濁物質や懸濁物質を除去し、さらに水処理工程から発生する汚泥中の内分泌撹乱物質および発ガン性物質を低濃度にすることで、処理系内全体の内分泌撹乱物質および発ガン性物質を高い除去率で分解除去する方法及び装置を提供しようとするものである。
【０００８】
【課題を解決するための手段】
本発明者らは鋭意検討の結果、下記の処理方法を用いることで処理系内全体の内分泌攪乱物質および発ガン性物質の分解除去率が著しく向上することを見いだした。すなわち本発明は、
（１） 内分泌撹乱物質または発ガン性物質を含有する有機汚水の処理方法であって、被処理水に対し、オゾンと、過酸化水素または紫外線のいずれかとの二つ、あるいは三つを組み合わせて用いる前段の水処理工程により処理し、その処理水をさらに生物処理、凝集処理、濾過処理、活性炭処理の少なくとも一つ、又は二つ以上を組み合わせて行う後段の水処理工程により処理し、前記後段の水処理工程から発生する汚泥に対し、前記前段の水処理工程からの排オゾンガスを導入し、該排オゾンガスで汚泥を処理した後の汚泥処理上澄水を後段の水処理工程の流入部に返送することを特徴とする内分泌撹乱物質または発ガン性物質を含有する有機汚水の処理方法。
（２） 内分泌撹乱物質または発ガン性物質がダイオキシン、ビスフェノールＡ、ジオキサン、またはフタル酸ジ（２−エチルヘキシル）であることを特徴とする前記（１）記載の内分泌撹乱物質または発ガン性物質を含有する有機汚水の処理方法。
（３） 内分泌撹乱物質または発ガン性物質を含有する有機汚水を導入し、オゾンと、過酸化水素または紫外線のいずれかとの二つ、あるいは三つを組み合わせて用いる前段水処理装置、前段水処理装置からの処理水を導入し、さらに生物処理、凝集処理、濾過処理、活性炭処理の少なくとも一つ、又は二つ以上を組み合わせて行う後段水処理装置、前記後段水処理装置から発生した汚泥を貯留する汚泥貯留槽、前記前段水処理装置からの排オゾンガスを前記汚泥貯留槽に導入する経路を設け、前記汚泥貯留槽の上澄水を後段水処理工程の流入部に返送する経路を設けたことを特徴とする内分泌撹乱物質または発ガン性物質を含有する有機汚水の処理装置。
【０００９】
【発明の実施の形態】
本発明によれば、被処理水に対し、予め、オゾン、過酸化水素または紫外線のいずれか一つ、または二つ以上を組み合わせて前段の水処理工程を行うことにより生成したヒドロキシラジカル等が、被処理水中の溶存及び非溶存の内分泌撹乱物質および発ガン性物質を高効率で酸化分解することができる。内分泌撹乱物質および発ガン性物質が酸化分解によって除去された該処理水中の有機物やＳＳ、重金属類については、生物処理等後段の水処理工程を行えば、ほぼ、高度に除去分離することができる。
【００１０】
上記のように被処理水の内分泌撹乱物質および発ガン性物質を予め、前段の水処理工程において酸化分解することから、有機物やＳＳ等が除去される後段の水処理工程から発生する汚泥中には、内分泌撹乱物質および発ガン性物質の残留が少なく、汚泥中の内分泌撹乱物質および発ガン性物質の分解除去を目的とした汚泥処理工程を軽減化することができる。また、内分泌撹乱物質および発ガン性物質の分解処理工程からの排オゾンを該汚泥に注入することによって、排オゾンの処理ができるのみでなく、汚泥の減容や内分泌撹乱物質および発ガン性物質含率の更なる低減も可能である。このため、処理系外への汚泥排出量と内分泌撹乱物質および発ガン性物質含率がともに低減できる。
【００１１】
本発明は、その前段の水処理工程においては、オゾン、過酸化水素あるいは紫外線のいずれか一つ、又は二つ以上を組み合わせた処理を行う。オゾンと過酸化水素あるいは紫外線のいずれか一つを用いて処理することもできるが、オゾンと過酸化水素、オゾンと紫外線、或いは過酸化水素と紫外線との二つの組み合わせで用いた方が良く、これらの三者を組み合わせるとさらに良い効果が得られる。これらを併用する場合には、先にオゾンを作用させた後に過酸化水素を用いるというように順次に用いてもよいが、同時に用いることもできる。
これらの使用量や照射量については、その処理条件等を勘案して定めることができる。
【００１２】
【実施例】
以下、本発明の具体的実施例を図面を用いて詳細に説明するが、本発明はこれに限定されるものではない。
図１は本発明による処理法の一例をフローシートで示した。
図１に示すように、被処理水１に過酸化水素注入管から過酸化水素３を注入するとともに、ＡＯＰ分解処理工程４に導入し、オゾン注入管よりオゾン２を注入し、紫外線照射ランプ５との接触反応で被処理水中の内分泌攪乱物質または発ガン性物質が酸化力の強いヒドロキシラジカルによって酸化分解される。ただし、本明細書でＡＯＰ（アドバンスド オキシデーション プロセス）分解処理とは、紫外線、オゾン、過酸化水素等の非塩素系酸化剤を用いる酸化分解処理のことを示す。
ＡＯＰ分解処理により得たＡＯＰ分解処理水６は、後段処理、すなわち生物処理工程８、凝集沈殿処理工程９、砂ろ過処理工程１０、そして活性炭処理工程１１を通って前記処理水中の有機物やＳＳ、重金属類の除去が行われる。活性炭処理工程１１から得られる処理水は放流水１２として系外へ排出できる。なお、砂ろ過処理工程１０の逆洗排水１５については、凝集沈殿処理工程９の流入部に返送し、ＳＳ等の分離除去を行う。
【００１３】
一方、生物処理工程８より発生する生物処理汚泥１３と凝集沈殿処理工程９より発生する凝集沈殿処理汚泥１４を汚泥貯留槽１７に集め、該汚泥貯留槽１７に前記ＡＯＰ分解工程４より排出する排オゾン７を導入することで、排オゾン７が汚泥の分解及び内分泌撹乱物質および発ガン性物質の酸化分解に消費される。汚泥分解処理した後の汚泥分解処理上澄水１６が生物処理工程８の流入部に返送されれば、汚泥分解とともに溶出した有機物がその後の処理によって除去可能である。汚泥貯留槽１７の残留汚泥は内分泌撹乱物質および発ガン性物質の含有が少ないことから、排出汚泥１８として系外へ排出される。
上記の処理フロー中、内分泌撹乱物質および発ガン性物質分解除去後の後段処理とした生物処理工程８、凝集沈殿処理工程９、砂ろ過処理工程１０、活性炭処理工程１１はＡＯＰ分解処理水６に対する有機物及びＳＳ除去の一例であり、ＡＯＰ分解処理水６の性状によって、凝集沈殿処理工程９を先に設けてもよい。また、組み合わせとして、生物処理＋ろ過処理＋活性炭処理、生物処理＋凝集沈殿ろ過処理＋活性炭処理、などが挙げられる。生物処理工程８としては、接触酸化法、回転円板法、標準活性汚泥法などのいずれでもよい。凝集処理及びろ過処理としては、凝集膜ろ過、凝集沈殿と砂ろ過のいずれでもよい。さらに、汚泥貯留槽１７のかわりに、あるいは汚泥貯留槽１７の後にあるいは汚泥分解槽を設け、該汚泥分解槽に排オゾン７を導入することも可能である。
上記図１に示すようにして得られた各処理工程の水質を表１、排オゾン７による汚泥分解前後の水質を表２に示す。ＡＯＰ分解処理工程４の処理条件を表３に示す。
【００１４】
【表１】
表１に示すように、総ダイオキシンが１５００ｐｇ／リットル、ダイオキシンＴＥＱが２５ｐｇ／リットル、ジオキサンが７５００ｎｇ／リットル、ビスフェノールＡが６００ｎｇ／リットルである被処理水に対し、過酸化水素の添加率を１０ｍｇ／リットル、オゾン注入率を１００ｍｇ／リットル、紫外線照射量０．５Ｗ・ｈｒ／リットル、滞留時間２０分の処理条件で分解反応を行った結果、該処理水の総ダイオキシンとダイオキシンＴＥＱがともに約１０分の１以下に低下し、それぞれ、１５０ｐｇ／リットルと２．０ｐｇ／リットルとなった。また、ジオキサン及びビスフェノールＡもそれぞれ１５００ｎｇ／リットルと８０ｎｇ／リットルに低減した。この結果、該ＡＯＰ分解反応によって流入ダイオキシンのほぼ９０％、ジオキサンの８０％、ビスフェノールＡの８７％が除去できた。なお、表１において、ＴＥＱは２，３，７，８−ＴＣＤＤ毒性等価換算濃度を示す。
【００１６】
なお、内分泌撹乱物質および発ガン性物質以外の代表的な汚濁物に関しては、被処理水中の色度６００度、ＣＯＤ ２００ｍｇ／リットル、ＢＯＤ １５０ｍｇ／リットル、ＳＳ １００ｍｇ／リットルが、ＡＯＰ分解処理後の処理水では色度３００度、ＣＯＤ １５０ｍｇ／リットル、ＢＯＤ １７０ｍｇ／リットル、ＳＳ ８０ｍｇ／リットルとなり、有機汚濁物の大部分が残留しているが、後段処理工程の生物処理、凝集沈殿処理、砂ろ過処理、活性炭処理を得た放流水は色度１０度、ＣＯＤ １０ｍｇ／リットル、ＢＯＤ、ＳＳともに１ｍｇ／リットル以下となった。また、有機物やＳＳが高度に除去されたことにともない、放流水中の総ダイオキシン、ダイオキシンＴＥＱ、ビスフェノールＡとも検出限界以下となり、ジオキサンも５００ｎｇ／リットルに低下した。
【００１７】
【表２】
表２に示すように、生物処理及び凝集沈殿処理からの混合汚泥中総ダイオキシンは０．７９ｎｇ／ｇであり、ジオキサンが０．５０μｇ／ｇ、ビスフェノールＡが０．６６μｇ／ｇとなり、通常ＡＯＰ分解処理を行わない処理工程からの汚泥と比べるとほぼ１０分の１以下となっている。さらに上記の汚泥に対し、排オゾン２０ｍｇ／リットルを導入し、滞留時間約３時間を得た後では、汚泥のＳＳが排オゾン導入前の１５０００ｍｇ／リットルから１３０００ｍｇ／リットルに低下し、約１３％の減容となった。また、総ダイオキシン及びダイオキシンＴＥＱがオゾン導入前では、それぞれ１２０００ｐｇ／リットル、２００ｐｇ／リットルであるのに対し、オゾン処理後はそれぞれ３０００ｐｇ／リットル、５０ｐｇ／リットルに低下した。ＳＳ中総ダイオキシンも０．２２ｎｇ／ｇに低下した。汚泥のジオキサン及びビスフェノールＡも処理前の９０００ｎｇ／リットルと１００００ｎｇ／リットルからそれぞれ５０００ｎｇ／リットルと４０００ｎｇ／リットルに低下した。汚泥中内分泌撹乱物質および発ガン性物質の分解効果も得られた。なお、汚泥ろ液の有機物濃度が排オゾン導入後、やや高くなった。これらを生物処理流入部に返送すれば、十分処理可能である。ろ液中のダイオキシン、ジオキサン、ビスフェノールＡも排オゾン導入後、若干の増加となったが、総量としては、わずかであり、水処理工程で十分除去でき、放流水の水質にまったく影響が認められなかった。
【００１９】
【表３】
【発明の効果】
実施例に示すように、本発明によれば、内分泌撹乱物質および発ガン性物質を含有する有機性汚水に対し、先ず、オゾン、過酸化水素あるいは紫外線のいずれか一つ、又は二つ以上を組み合わせて用いる前段の処理を行うことにより、被処理水中の溶存及び非溶存内分泌撹乱物質および発ガン性物質を９０％前後の高効率で酸化分解することができる。内分泌撹乱物質および発ガン性物質分解処理を得た被処理水はその後の生物処理と凝集処理及びろ過処理、活性炭処理を組み合わせた後段の処理を行えば、被処理水の有機物やＳＳまたは重金属類等他の汚濁物は、高度に除去分離することができる。また、内分泌撹乱物質および発ガン性物質分解処理後に残留した微量の内分泌撹乱物質および発ガン性物質も前記水処理工程によってほぼ完全に除去することができることから、良質な放流水が得られる。
【００２１】
上記のように被処理水中の内分泌撹乱物質および発ガン性物質を先ず酸化分解することによって除去できたことから、有機物やＳＳ等の除去となる後段の水処理工程から発生する汚泥中に内分泌撹乱物質および発ガン性物質の残留が少なく、固形物単位当たりの内分泌撹乱物質および発ガン性物質含有量が先に該物質の分解処理を行わなかった処理工程の汚泥と比べると約１０分の１以下となる。そのまま、排出しても環境への負荷が大きく低減できる。さらに内分泌撹乱物質および発ガン性物質分解処理工程からの排オゾンを該汚泥に導入することによって、排オゾンの処理ができるのみでなく、汚泥の減容や内分泌撹乱物質および発ガン性物質含率の更なる低減も可能となった。このため、処理系外への汚泥排出量と内分泌撹乱物質および発ガン性物質総量がともに少なくなる。
【図面の簡単な説明】
【図１】本発明の有機汚水の処理方法の実施形態の１例を示すフロー図
【符号の説明】
１ 被処理水
２ オゾン
３ 過酸化水素
４ ＡＯＰ分解処理工程
５ 紫外線照射ランプ
６ ＡＯＰ分解処理水
７ 排オゾン
８ 生物処理工程
９ 凝集沈殿処理工程
１０ 砂ろ過処理工程
１１ 活性炭処理工程
１２ 放流水
１３ 生物処理汚泥
１４ 凝集沈殿処理汚泥
１５ 逆洗排水
１６ 汚泥分解処理上澄水
１７ 汚泥貯留槽
１８ 排出汚泥[0001]
BACKGROUND OF THE INVENTION
The present invention relates to treatment of organic sewage containing endocrine disrupting substances or carcinogenic substances, and more particularly to a method for treating organic sewage containing endocrine disrupting substances or carcinogenic substances such as leachate and industrial wastewater. Is.
[0002]
[Prior art]
Endocrine disrupting chemicals are chemicals that, when taken into the body of an animal, affect the normal hormonal actions that are normally carried out in the body, and their exposure disrupts the endocrine action of humans and wild animals. However, it has been pointed out that it may cause reproductive dysfunction and malignant tumors. These endocrine disrupting substances act at extremely low concentrations, and have been pointed out that they may have serious effects at the developmental stage, especially in the fetal period, and the effects may be manifested after growth. There is also concern about the potential for impact. So far, in wildlife such as fish, reptiles, and birds, abnormalities in reproductive function, reproductive behavior, male feminization, decreased hatching ability, and the like have been pointed out and related to endocrine disruptors. Furthermore, it has been pointed out that in humans, the tendency of decreased sperm count, increased prostate cancer, and increased endometriosis is associated with endocrine disruptors. The results of animal experiments have confirmed that some chemical substances cause reproductive dysfunction such as testicular retention and decreased sperm count, and endometriosis. It is known that carcinogens promote cell carcinogenesis.
[0003]
Suspected as endocrine disrupting substances and carcinogenic substances according to the investigations so far, PCBs, dioxins, polybrominated biphenyls, hexachlorobenzene, pentachlorophenol, 2,4,5-trichlorophenoxyacetic acid, 2, 4-dichlorophenoxyacetic acid, amitrol, atrazine, simazine, hexachlorocyclohexane, ethyl parathion, carbaryl, chlordens, 1,2-dibromo-3-chloropropane, DDT and its metabolites (DDE, DDD), quercene, aldrin, endrin, Dieldrin, endosulfan, heptachlor and heptachlor epoxide, malathion, mesomil, methoxychlor, myrex, nitrophene, toxaphene, camfechlor, organotin (such as tributyltin), Rifluralin, alkylphenols, bisphenol A, di (2-ethylhexyl) phthalate, butylbenzyl phthalate, dibutyl phthalate, dicyclohexyl phthalate, diethyl phthalate, benzo (a) pyrene, cadmium, lead, mercury, 2,4- Examples include dichlorophenol, adipic acid (2-ethylhexyl), benzophenone, 4-nitrotoluene, dioxane and the like.
[0004]
These are flame retardants, bactericides, insecticides, antifouling materials, corrosion inhibitors, heat media, preservatives, herbicides, resin curing agents, resin raw materials, plastic plasticizers, solvents, etc., respectively, or in the combustion process Although it varies depending on the substance, it is detected in environmental water at a concentration of the order of μg / liter to pg / liter. Such concentration levels are very low compared to the organic substance concentration in the mg / liter order of water estimated from COD, TOC, etc., but these endocrine disrupting chemicals are in very small amounts as described above. Therefore, it is desired to develop a technique for removing a small amount of endocrine disrupting chemical contained in environmental water or water before being released into the environment. In particular, landfill leachate contains various types of endocrine disrupting substances and carcinogenic substances and has high concentrations (100 to 5000 pg / liter for dioxins, 100 to 10,000 ng / liter for bisphenol A, 1,4 -Since dioxane is 1000 to 100,000 ng / liter), it is urgent to treat endocrine disrupting substances and carcinogenic substances in landfill leachate.
[0005]
Conventionally, as a main treatment method for organic sewage such as leachate (hereinafter also referred to as water to be treated), a treatment method mainly using organic matter removal is used. The main treatment methods include biological treatment for the purpose of removing BOD and nitrogen, flocculation and precipitation treatment for the purpose of removing chromaticity, COD and SS, and sand filtration for the purpose of removing turbidity such as SS. is there. Furthermore, activated carbon treatment may be used as an advanced treatment method. However, any of the above treatment methods has little effect of decomposing and removing trace-dissolved endocrine disrupting substances and carcinogenic substances, particularly dioxin, dioxane and bisphenol A in wastewater, and these substances remain in the discharged water. There are many cases. Furthermore, most endocrine disrupting substances and carcinogenic substances are almost insoluble in water, and even if endocrine disrupting substances or carcinogenic substances decrease in each treatment process, most of them are contained in the sludge generated from the treatment process. It is considered that after dehydration, the content of endocrine disrupting substances and carcinogenic substances in the cake is high, and the endocrine disrupting substances and carcinogenic substances in the whole system are not so much decomposed and removed.
As a recent technology for decomposing endocrine disrupting substances and carcinogenic substances, in general, endocrine disrupting substances and carcinogenic substances dissolved in treated water from which organic pollutants and suspended substances have been removed are removed by UV irradiation. It is known to decompose and remove by an oxidation reaction by chlorination reaction and ozone injection.
[0006]
[Problems to be solved by the invention]
However, in this method, the concentration of many endocrine disrupting substances and carcinogenic substances that can be dissolved in water is very small, so there may be a decrease in the amount of endocrine disrupting substances and carcinogenic substances in the treated water that has undergone the conventional water treatment process. In many cases, even if the treated water is decomposed and removed, the amount that can be decomposed and removed is limited. For this reason, most of the inflow endocrine disrupting substances and carcinogenic substances are accumulated in the sludge generated from the treatment process, and the decomposition and removal thereof is a big problem.
[0007]
Therefore, in order to solve the above-mentioned problems of the prior art, the present invention decomposes and removes dissolved and non-dissolved endocrine disrupting substances and carcinogenic substances from organic wastewater with high efficiency, and subsequently other organic substances. By removing pollutants and suspended substances, and reducing the concentration of endocrine disrupting substances and carcinogenic substances in the sludge generated from the water treatment process, the endocrine disrupting substances and carcinogenic substances in the entire treatment system can be reduced. It is an object of the present invention to provide a method and apparatus for decomposing and removing at a high removal rate.
[0008]
[Means for Solving the Problems]
As a result of intensive studies, the present inventors have found that the degradation removal rate of endocrine disrupting substances and carcinogenic substances in the entire processing system is remarkably improved by using the following processing method. That is, the present invention
(1) A method for treating organic sewage containing an endocrine disrupting substance or a carcinogenic substance, wherein the water to be treated is a combination of ozone and either hydrogen peroxide or ultraviolet light, or a combination of three. Treated by the water treatment step in the former stage to be used, and treat the treated water in a subsequent water treatment step in which at least one of biological treatment, coagulation treatment, filtration treatment, activated carbon treatment or a combination of two or more thereof is performed , The sludge generated from the previous water treatment process is introduced with the waste ozone gas from the previous water treatment process, and the sludge treated supernatant after the sludge is treated with the waste ozone gas is returned to the inflow part of the subsequent water treatment process. A method for treating organic sewage containing an endocrine disrupting substance or a carcinogenic substance.
(2) The endocrine disrupting substance or carcinogenic substance according to (1) above, wherein the endocrine disrupting substance or carcinogenic substance is dioxin, bisphenol A, dioxane, or di (2-ethylhexyl) phthalate. Treatment method of organic wastewater contained.
(3) Pre-stage water treatment apparatus, pre-stage water treatment using organic wastewater containing endocrine disrupting substances or carcinogenic substances, and using ozone in combination with two or three of hydrogen peroxide or ultraviolet rays The treated water from the apparatus is introduced, and further, at least one of biological treatment, agglomeration treatment, filtration treatment, activated carbon treatment, or a combination of two or more thereof, a subsequent water treatment device, and sludge generated from the latter water treatment device is stored. A sludge storage tank, a path for introducing exhaust ozone gas from the front-stage water treatment device into the sludge storage tank, and a path for returning the supernatant water of the sludge storage tank to the inflow portion of the rear-stage water treatment process. An apparatus for treating organic sewage containing a characteristic endocrine disrupting substance or carcinogenic substance.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
According to the present invention, with respect to the water to be treated, hydroxy radicals generated by performing the previous water treatment step in advance by combining any one of ozone, hydrogen peroxide or ultraviolet light, or two or more, Dissolved and non-dissolved endocrine disrupting substances and carcinogenic substances in the treated water can be oxidatively decomposed with high efficiency. Organic substances, SS, and heavy metals in the treated water from which endocrine disrupting substances and carcinogenic substances have been removed by oxidative decomposition can be removed and separated to a high degree by performing a subsequent water treatment step such as biological treatment. .
[0010]
As described above, the endocrine disrupting substances and carcinogenic substances in the water to be treated are oxidatively decomposed in the preceding water treatment process, so that in the sludge generated from the subsequent water treatment process in which organic substances and SS are removed. Can reduce the sludge treatment process for the purpose of decomposing and removing the endocrine disrupting substances and carcinogenic substances in the sludge with little residual of the endocrine disrupting substances and carcinogenic substances. In addition, by injecting waste ozone from the endocrine disrupting substance and carcinogenic substance decomposition treatment process into the sludge, not only waste ozone can be treated, but also sludge volume reduction, endocrine disrupting substances and carcinogenic substances. The content can be further reduced. For this reason, both sludge discharge amount out of the treatment system and the content of endocrine disrupting substances and carcinogenic substances can be reduced.
[0011]
In the present invention, in the preceding water treatment step, treatment is performed by combining any one of ozone, hydrogen peroxide, and ultraviolet rays, or a combination of two or more. It can be treated with any one of ozone and hydrogen peroxide or ultraviolet light, but it is better to use ozone and hydrogen peroxide, ozone and ultraviolet light, or hydrogen peroxide and ultraviolet light in combination. A better effect can be obtained by combining these three elements. When these are used in combination, they may be used sequentially, such as using hydrogen peroxide after first applying ozone, but can also be used simultaneously.
These usage amounts and irradiation amounts can be determined in consideration of the processing conditions and the like.
[0012]
【Example】
Hereinafter, specific examples of the present invention will be described in detail with reference to the drawings, but the present invention is not limited thereto.
FIG. 1 is a flow sheet showing an example of the processing method according to the present invention.
As shown in FIG. 1, hydrogen peroxide 3 is injected into the water to be treated 1 from a hydrogen peroxide injection tube, introduced into the AOP decomposition treatment step 4,
The AOP decomposition treated water 6 obtained by the AOP decomposition treatment is subjected to post-treatment, that is,
[0013]
On the other hand, the biological treatment sludge 13 generated from the
In the above processing flow, the
The water quality of each treatment step obtained as shown in FIG. 1 is shown in Table 1, and the water quality before and after sludge decomposition by exhaust ozone 7 is shown in Table 2. Table 3 shows the processing conditions of the AOP decomposition processing step 4.
[0014]
[Table 1]
As shown in Table 1, with respect to the water to be treated having a total dioxin of 1500 pg / liter, dioxin TEQ of 25 pg / liter, dioxane of 7500 ng / liter, and bisphenol A of 600 ng / liter, the addition rate of hydrogen peroxide is 10 mg / liter. Liters, ozone injection rate 100 mg / liter, ultraviolet irradiation amount 0.5 W · hr / liter, and a decomposition reaction under the treatment time of 20 minutes. As a result, the total dioxin and dioxin TEQ of the treated water are both about 10 minutes. To 1 pg / liter and 150 pg / liter, respectively. Dioxane and bisphenol A were also reduced to 1500 ng / liter and 80 ng / liter, respectively. As a result, approximately 90% of the inflow dioxin, 80% of dioxane, and 87% of bisphenol A could be removed by the AOP decomposition reaction. In Table 1, TEQ indicates 2,3,7,8-TCDD toxicity equivalent equivalent concentration.
[0016]
For typical pollutants other than endocrine disrupting substances and carcinogenic substances, chromaticity of 600 degrees, COD of 200 mg / liter, BOD of 150 mg / liter, and SS of 100 mg / liter in treated water are those after AOP decomposition treatment. In treated water, chromaticity is 300 degrees, COD is 150 mg / liter, BOD is 170 mg / liter, and SS is 80 mg / liter, and most of organic pollutants remain, but biological treatment, coagulation sedimentation treatment, sand filtration in the latter stage treatment process Discharged water obtained by treatment and activated carbon treatment had a chromaticity of 10 degrees, COD of 10 mg / liter, BOD, and SS were both 1 mg / liter or less. In addition, with the high removal of organic matter and SS, total dioxin, dioxin TEQ and bisphenol A in the effluent water were below the detection limit, and dioxane was also reduced to 500 ng / liter.
[0017]
[Table 2]
As shown in Table 2, the total dioxin in the mixed sludge from biological treatment and coagulation sedimentation treatment is 0.79 ng / g, dioxane is 0.50 μg / g, bisphenol A is 0.66 μg / g, and usually AOP decomposition Compared with the sludge from the process which does not process, it is about 1/10 or less. Furthermore, after introducing 20 mg / liter of waste ozone into the above sludge and obtaining a residence time of about 3 hours, the SS of sludge decreases from 15000 mg / liter before the introduction of waste ozone to 13000 mg / liter, about 13%. The volume was reduced. The total dioxin and dioxin TEQ were 12,000 pg / liter and 200 pg / liter, respectively, before the introduction of ozone, but decreased to 3000 pg / liter and 50 pg / liter, respectively, after the ozone treatment. The total dioxin in SS also decreased to 0.22 ng / g. Sludge dioxane and bisphenol A were also decreased from 9000 ng / liter and 10,000 ng / liter before treatment to 5000 ng / liter and 4000 ng / liter, respectively. Degradation effects of endocrine disrupting substances and carcinogenic substances in sludge were also obtained. In addition, the organic substance density | concentration of sludge filtrate became a little high after exhaust ozone introduction. If these are returned to the biological treatment inflow section, they can be processed sufficiently. Dioxins, dioxane, and bisphenol A in the filtrate also increased slightly after the introduction of waste ozone, but the total amount was slight and could be removed sufficiently in the water treatment process, and the quality of the discharged water was completely affected. There wasn't.
[0019]
[Table 3]
【The invention's effect】
As shown in the examples, according to the present invention, organic wastewater containing an endocrine disrupting substance and a carcinogenic substance is first subjected to any one or more of ozone, hydrogen peroxide, and ultraviolet rays. By performing the pre-treatment used in combination, dissolved and non-dissolved endocrine disrupting substances and carcinogenic substances in the water to be treated can be oxidatively decomposed with a high efficiency of around 90%. The treated water obtained from the endocrine disrupting substance and carcinogenic substance decomposition treatment is treated with organic matter, SS, or heavy metals in the treated water after the subsequent biological treatment, coagulation treatment, filtration treatment, and activated carbon treatment. Such other contaminants can be highly removed and separated. Further, since the endocrine disrupting substances and carcinogenic substances remaining after the decomposition treatment of the endocrine disrupting substances and carcinogenic substances can be almost completely removed by the water treatment step, high-quality discharged water can be obtained.
[0021]
Since endocrine disrupting substances and carcinogenic substances in the water to be treated can be removed by oxidative decomposition as described above, endocrine disrupting is caused in the sludge generated from the subsequent water treatment process for removing organic substances and SS. There is little residue of substances and carcinogenic substances, and the content of endocrine disrupting substances and carcinogenic substances per solid unit is about 1/10 compared to sludge in the treatment process in which the substance was not previously decomposed. It becomes as follows. Even if discharged as it is, the load on the environment can be greatly reduced. Furthermore, by introducing waste ozone from the endocrine disrupting substance and carcinogenic substance decomposition treatment process into the sludge, not only can waste ozone be treated, but also the volume of sludge can be reduced and the content of endocrine disrupting substances and carcinogenic substances Further reduction of the amount is possible. For this reason, both the sludge discharge amount outside the treatment system and the total amount of endocrine disrupting substances and carcinogenic substances are reduced.
[Brief description of the drawings]
FIG. 1 is a flowchart showing an example of an embodiment of a method for treating organic sewage according to the present invention.
1 Water to be treated 2 Ozone 3 Hydrogen peroxide 4 AOP
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| JP00948299A JP3954227B2 (en) | 1999-01-18 | 1999-01-18 | Method and apparatus for treating organic sewage containing endocrine disrupting substance or carcinogenic substance |
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|---|---|---|---|
| JP00948299A JP3954227B2 (en) | 1999-01-18 | 1999-01-18 | Method and apparatus for treating organic sewage containing endocrine disrupting substance or carcinogenic substance |
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| JP2000202493A JP2000202493A (en) | 2000-07-25 |
| JP2000202493A5 JP2000202493A5 (en) | 2004-10-28 |
| JP3954227B2 true JP3954227B2 (en) | 2007-08-08 |
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Cited By (1)
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| CN105439378A (en) * | 2015-12-07 | 2016-03-30 | 江苏博大环保股份有限公司 | Novel advanced oxidation coupling deep biochemical treatment wastewater system |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP3795268B2 (en) * | 1999-08-17 | 2006-07-12 | アタカ工業株式会社 | Method and apparatus for treating wastewater containing organochlorine compounds |
| JP2006000854A (en) * | 2000-09-21 | 2006-01-05 | Ebara Corp | Method and apparatus for treating wastewater containing dioxins |
| CN1323956C (en) * | 2004-12-01 | 2007-07-04 | 南京大学 | Combined effluent treating process of photooxidizing Fenton's reaction, flocculation and microbial degradation |
| CN103922524B (en) * | 2014-05-14 | 2015-03-11 | 山东盛阳集团有限公司 | Advanced treatment method for coking wastewater |
| US11420085B2 (en) | 2017-12-08 | 2022-08-23 | Oshkosh Corporation | Ozone cleaning system |
| US10792613B1 (en) | 2019-03-11 | 2020-10-06 | Oshkosh Corporation | Cleaning device |
| KR20210055839A (en) * | 2019-11-07 | 2021-05-18 | 한국수자원공사 | a livestock excretion wastewater treatment method using both the oxidation and the coagulating process and the livestock excretion wastewater treatment system |
| CN111606464A (en) * | 2020-06-09 | 2020-09-01 | 闫娟 | High COD phenol-containing sewage treatment method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105439378A (en) * | 2015-12-07 | 2016-03-30 | 江苏博大环保股份有限公司 | Novel advanced oxidation coupling deep biochemical treatment wastewater system |
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