JP2004160344A - Method for decomposing halogenated organic compound and decomposition agent - Google Patents
Method for decomposing halogenated organic compound and decomposition agent Download PDFInfo
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Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は、ハロゲン化有機化合物で汚染された固体物質からなる被処理物質中のハロゲン化有機化合物を、安全かつ安価に分解して無害化する分解方法と、そのための分解剤に関する。
【０００２】
【従来の技術】
従来、ごみ焼却場から排出されるダイオキシン類に代表される有害なハロゲン化有機化合物の分解、無害化法としては、次のような方法が提案されている。
【０００３】
▲１▼ 高温度で焼却、酸化分解する方法（「第８回廃棄物学会研究発表会講演論文集」ｐ．６７７−６７９）
▲２▼ 不活性ガス雰囲気中で加熱して脱塩素する方法（「ＯＲＧＡＮＯＨＡＬＯＧＥＮ ＣＯＭＰＯＵＮＤＳ Ｖｏｌ．２７（１９９６）」ｐ．１４７−１５２）
▲３▼ 金属ナトリウムと接触させて還元脱塩素する方法（「第７回廃棄物学会研究発表会講演論文集」ｐ．９５４−９５７）
▲４▼ アミン化合物等の還元性物質と共に加熱して脱塩素する方法（特許第３２８７２９８号）
【０００４】
【特許文献１】
特許第３２８７２９８号
【非特許文献２】
「第８回廃棄物学会研究発表会講演論文集」ｐ．６７７−６７９
【非特許文献３】
「ＯＲＧＡＮＯＨＡＬＯＧＥＮ ＣＯＭＰＯＵＮＤＳ Ｖｏｌ．２７（１９９６）」
ｐ．１４７−１５２
【非特許文献４】
「第７回廃棄物学会研究発表会講演論文集」ｐ．９５４−９５７
【０００５】
【発明が解決しようとする課題】
上記▲１▼の方法では、８００℃以上の高温加熱が必要であり、毒性としては高濃度であっても熱量として不十分なハロゲン化有機化合物で汚染された固体汚染物質では、エネルギー多消費型の処理技術となり、不経済である。
【０００６】
また、▲２▼の方法では、２００〜５５０℃程度の加熱でダイオキシン類を分解しているが、直接燃焼法よりもエネルギー的には有利である。しかしながら、都市ごみの焼却で発生する飛灰のように冷却過程でダイオキシン類が再合成するものもあり、冷却に別途対策を必要とする。また、融点の低い飛灰では、ダイオキシン類の分解反応中にマトリックスの一部が溶融し、安定した反応器の運転が困難となる。
【０００７】
▲３▼の方法では、常温の処理が可能であるが、反応性が高く、危険な金属ナトリウムを使用するため、発火、爆発の危険性が高く、厳重な安全管理が必要となる。
【０００８】
▲４▼の方法は、１００〜３００℃という比較的低温度で処理が可能で、低融点の飛灰に対して有効であり、エネルギー的に▲１▼及び▲２▼の方法に比較して安価な処理方法であるが、混合した薬剤が揮発又は分解して悪臭が発生したり、タール成分が生成したりするため、悪臭やタールに対する後処理が必要となるという問題があった。
【０００９】
このようなことから、より安価で安全にハロゲン化有機化合物を無害化処理できるハロゲン化有機化合物の分解技術が求められているのが現状である。
【００１０】
本発明は上記従来の実情に鑑みてなされたものであって、ダイオキシン類等のハロゲン化有機化合物で汚染された固体物質からなる被処理物質中のハロゲン化有機化合物を、安全かつ安価に分解して無害化する分解方法と、そのための分解剤を提供することを目的とする。
【００１１】
【課題を解決するための手段】
本発明（請求項１）のハロゲン化有機化合物の分解方法は、ハロゲン化有機化合物で汚染された固体物質からなる被処理物質中のハロゲン化有機化合物を分解する方法において、該被処理物質にハロゲン化有機化合物の分解に対して有効な高分子脂肪族炭化水素類を含む薬剤を添加して加熱することを特徴とする。
【００１２】
本発明（請求項２）のハロゲン化有機化合物の分解方法は、ナトリウム及び／又はカリウムを含むアルカリ剤が添加された排ガスから得られた集塵灰以外の、ハロゲン化有機化合物で汚染された固体物質からなる被処理物質中のハロゲン化有機化合物を分解する方法において、該被処理物質に糖類及び／又は有機酸類を含む薬剤を添加して加熱することを特徴とする。
【００１３】
また、本発明のハロゲン化有機化合物の分解剤は、ハロゲン化有機化合物の分解能を有する高分子脂肪族炭化水素類、糖類、又は有機酸類を含むことを特徴とする。
【００１４】
ハロゲン化有機化合物の分解能を有する高分子脂肪族炭化水素類、糖類、又は有機酸類であれば、従来のアミン化合物のように悪臭やタール状物質を殆ど発生させることなく、１００〜４５０℃程度の比較的低温で被処理物質中のハロゲン化有機化合物を安全かつ安価に分解して無害化することができる。
【００１５】
特に、糖類、有機酸類は、従来のアミン化合物では３５０℃以上に温度を上げないと分解効果が十分に得られなかったカルシウム系のアルカリ剤が添加された焼却飛灰にも有効であり、比較的低温の加熱でハロゲン化有機化合物を効率的に分解することができる。
【００１６】
即ち、一般に、ごみ焼却炉から排出される排ガスは、ボイラ、ガス冷却塔を経た後、消石灰、生石灰等のカルシウム系塩化水素除去剤が噴霧され、その後バグフィルタ等の集塵機で除塵された後、煙突から大気に放出される。このように、排ガス中の塩化水素を消石灰、生石灰等のカルシウム系塩化水素除去剤で処理している焼却施設から排出される飛灰中には、消石灰等のカルシウム系のアルカリ剤と塩化水素との反応生成物である塩化カルシウムが含有されている。しかし、飛灰中の塩化カルシウムは、官能基としてアミン基を有するアミン化合物や水酸基を有する多価アルコールを強固に吸着する性質がある。そのため、ダイオキシン類の分解を目的としてカルシウム系アルカリ剤を含有した飛灰にアミン化合物や多価アルコール類を添加した場合、塩化カルシウムに吸着されてしまう。そのため、飛灰内部に存在するダイオキシン類への拡散が阻害を受けるため、塩化カルシウムを含む飛灰にアミン化合物や多価アルコール類を添加して加熱を行っても、充分なダイオキシン類の分解効果は得られない。ただし、酸性ガスの吸着剤としてナトリウム系やカリウム系のアルカリ剤として噴霧された排ガスから集塵された飛灰では、生成物である塩化ナトリウムや塩化カリウムにアミン化合物や多価アルコール類を吸着する作用がないため、これらはダイオキシン類分解剤として有効に作用する。
【００１７】
一方、糖類や有機酸類は、塩化カルシウムを含む飛灰に対しても、有効に作用することを発見した。特に有機酸塩類のうち、ギ酸ナトリウムは塩化カルシウムの影響を実質的に全く受けないため、塩化カルシウムを含む飛灰のダイオキシン類分解剤として最適である。なお、底質を対象とした場合には、薬剤を添加せずに加熱すると、底質にもともと含まれている有機物に起因する焦げ臭い強い臭気を生じるが、本発明の分解剤を添加すると、焦げ臭い臭いを活性炭のように吸着、吸収、又は分解するため、反応中の臭気発生を低減、消失することができる。
特にグルコースは臭いを抑える効果が強く、底質の場合は好適である。
【００１８】
なお、本発明に係る分解剤により処理した処理物質中のハロゲン化有機化合物の挙動を追跡すると、例えばダイオキシン類の場合、反応開始当初は、まず、８塩素置換体であるＯＣＤＤ（８塩素化ジベンゾパラジオキシン）又はＯＣＤＦ（８塩素化ジベンゾフラン）が減少し、途中、低塩素置換体は増加傾向を示す。更に、反応を継続すると、逐次、低塩素化ダイオキシン類の減少が進んでいく。このことから、本発明によるハロゲン化有機化合物の分解反応は、逐次脱ハロゲン化反応であると推定される。
【００１９】
本発明において、高分子脂肪族炭化水素類としては、ポリエチレン及び／又はポリプロピレンが好ましい。また、糖類としては、グルコース、フルクトース、ガラクトース、スクロース、マルトース、ラクトース、セロビオース、澱粉及びセルロースよりなる群から選ばれる１種又は２種以上が、有機酸類としては、クエン酸、エリソルビン酸、グルコン酸、ギ酸及びこれらの有機酸の塩類よりなる群から選ばれる１種又は２種以上が好適である。
【００２０】
被処理物質の加熱には、反応器を用いることができ、この場合、被処理物質を反応器に供給する前工程で、或いは反応器内で、粉体状又は顆粒状の分解剤を被処理物質に添加混合することができる。反応器としては、不活性ガスを積極的に供給する機能を必要としない間接加熱型の連続式又は回分式の反応器を用いることが好ましい。
【００２１】
本発明の分解剤の添加率は、被処理物質に対して有効成分量として０．１〜２０重量％であることが好ましく、加熱温度は１００〜４５０℃であることが好ましい。
【００２２】
なお、被処理物質が重金属を含む場合には、更に重金属類溶出防止剤を添加して、その溶出を防止することが好ましく、この場合、リン酸化合物を主成分とする重金属類溶出防止剤を本発明の分解剤と同時に、或いは本発明の分解剤と事前に混合して、被処理物質に添加して加熱することが好ましい。
【００２３】
【発明の実施の形態】
以下に本発明のハロゲン化有機化合物の分解方法及び分解剤の実施の形態について詳細に説明する。
【００２４】
まず、本発明のハロゲン化有機化合物の分解剤について説明する。
【００２５】
本発明のハロゲン化有機化合物の分解剤は、
ハロゲン化有機化合物の分解能を有する高分子脂肪族炭化水素
糖類
或いは
有機酸類
を含むものである。なお、本発明のハロゲン化有機化合物の分解剤は、高分子脂肪族炭化水素、糖類及び有機酸類のうちの１種のみを含むものに限らず、２種以上を含むものであっても良い。即ち、高分子脂肪族炭化水素と糖類及び／又は有機酸類を含むものであっても良く、糖類及び有機酸類を含むものであっても良い。また、高分子脂肪族炭化水素、糖類、有機酸類の各々についても、それぞれ２種以上を含んでいても良い。
【００２６】
本発明において、高分子脂肪族炭化水素としては、ポリエチレン、ポリプロピレン、ポリスチレン等が挙げられるが、これらのうち、加熱反応中に悪臭の発生がないことから、ポリエチレン及び／又はポリプロピレンを用いることが好ましい。
【００２７】
糖類としては、グルコース、フルクトース、ガラクトースなどの単糖類、スクロース、マルトース、ラクトース、セロビオースなどの二糖類、澱粉、セルロースなどの多糖類が挙げられる。また、サポニンなどの配糖体、リグニンなどの高分子電解質も有効である。
【００２８】
有機酸類としては、クエン酸、エリソルピン酸、ギ酸、グルコースが酸化されたグルコン酸、或いはこれらの塩、例えばナトリウム塩、カリウム塩、カルシウム塩等が挙げられる。
【００２９】
本発明のハロゲン化有機化合物の分解剤は、これら高分子脂肪族炭化水素、糖類、有機酸類の他、他のハロゲン化有機化合物分解薬剤を含んでいても良い。また、後述の重金属溶出防止剤を含むものであっても良い。
【００３０】
本発明のハロゲン化有機化合物の分解剤は、後述の本発明の方法に従って、ハロゲン化有機化合物で汚染された固体物質からなる被処理物質に添加される他、次のようにして、ごみ焼却炉におけるダイオキシン類の発生防止にも有効に使用することができる。
【００３１】
即ち、ごみ焼却炉の焼却飛灰はダイオキシン類の合成触媒として知られているが、排ガス配管内や集塵機内に堆積した飛灰や、濾過式集塵器の濾布の織目に入り込んで払い落とされずに残る飛灰は、ダイオキシン類が合成しやすい温度環境で長時間滞留することになり、ダイオキシン類含有量が増加するだけでなく、集塵機内に滞留することで排ガス中で増加したダイオキシン類が再び脱離、揮散して煙突でのダイオキシン類濃度を増加させることがある。
【００３２】
そこで、この排ガス中に本発明のハロゲン化有機化合物の分解剤を添加して、排ガス流中で混合し、飛灰に付着、又は飛灰と混合した形で堆積させることにより、飛灰上で合成されたダイオキシン類の分解する効果、及び飛灰上でのダイオキシン類の合成を抑制する効果を得ることができる。
【００３３】
特に、焼却炉の始動運転時や停止運転時は、不完全燃焼によりダイオキシン類及びその前駆体が多量に発生し、このため、ダイオキシン類が多量に付着した飛灰も発生するため、始動運転時、停止運転時に本発明の分解剤を添加することは特に効果的である。
【００３４】
本発明のハロゲン化有機化合物の分解方法は、このような本発明の分解剤を用いて、ハロゲン化有機化合物で汚染された固体物質からなる被処理物質中のハロゲン化有機化合物を分解して、無害化する方法である。
【００３５】
本発明においては、被処理物質に対して前述の高分子脂肪族炭化水素、或いは糖類及び／又は有機酸類を添加混合して加熱することにより、被処理物質中のハロゲン化有機化合物を分解するが、高分子脂肪族炭化水素と共に糖類及び／又は有機酸類を併用しても良い。
【００３６】
被処理物質に対するこれらの分解剤の添加量は、用いる薬剤の種類や、被処理物質中のハロゲン化有機化合物含有量に応じて適宜決定されるが、通常の場合、被処理物質に対して有効成分量として０．１〜２０重量％、特に０．５〜１５重量％、とりわけ１〜１０重量％とするのが好ましい。
【００３７】
被処理物質をハロゲン化有機化合物の分解剤と共に加熱するには、加熱反応器を用い、被処理物質と分解剤とを反応器に投入すれば良い。この場合、分解剤は粉体状又は顆粒状の固体のまま被処理物質に添加することができ、被処理物質を反応器に投入する前工程で添加混合しても良く、また、反応器に添加して被処理物質に混合しても良い。
【００３８】
加熱雰囲気は空気雰囲気でも良く、必ずしも不活性ガスで置換する必要は無い。従って、反応器に不活性ガスを積極的に供給する機能は不要である。加熱方法は特に限定しないが、分解剤が作用する前に反応器内で酸化燃焼することがないよう、間接加熱式の反応器を用いることが好ましい。また、必須要件ではないが、反応器内への空気の吸い込みは抑制されることが好ましい。
【００３９】
用いる反応器は、連続式であっても回分式であっても構わないが、分解剤と被処理物質との均一な接触を実現するために、撹拌機能を有する反応器の利用が望ましい。例えば、連続式では間接加熱式の回転式キルンや、複数の撹拌用パドルを有するパドルドライヤーに類似の反応器などを用いることができ、また、回分反応器としては撹拌機能を有したオートクレーブ或いはこれに類似の反応器などを用いることができるが、何らこれらに限定されるものではない。
【００４０】
加熱温度は１００〜４５０℃、特に１００〜４００℃、とりわけ１５０〜４００℃とすることが好ましい。加熱温度が１００℃未満では十分な分解効果を得ることができず、４５０℃を超える高温加熱はコスト面、設備面で不利である。加熱時間は加熱温度や処理量によっても異なるが、３分以上であれば良く、通常５〜６０分程度である。
【００４１】
本発明において、処理対象となる被処理物質は特に限定されないが、ダイオキシン類等のハロゲン化有機化合物を含有する焼却飛灰、焼却灰土壌、河川／湖沼／港湾の底質、灰ピットのスラッジ、耐火レンガや金属片等の焼却炉の解体残渣、排ガス配管内の堆積物や濾過式集塵器の濾布といった焼却炉のメンテナンス時に発生する廃棄物等が挙げられる。
【００４２】
なお、被処理物が都市ごみ焼却炉の飛灰等のように、重金属類を含有するものである場合には、重金属溶出防止剤を併用して重金属の溶出防止処理も行ってこれを無害化することが好ましい。
【００４３】
重金属溶出防止剤としては、有機系、無機系の各種のものがあるが、キレート化合物等の有機系重金属溶出防止剤では、加熱処理時に分解して損失するため、これを避けるためにハロゲン化有機化合物の加熱分解処理後に、ハロゲン化有機化合物の分解剤とは別に添加混練する操作が必要となる。これに対して、無機系の重金属溶出防止剤であれば、加熱により分解するおそれがないため、ハロゲン化有機化合物の加熱分解処理時に、ハロゲン化有機化合物の分解剤と共に被処理物質に添加混合することができ、この場合にはハロゲン化有機化合物の分解剤と予め所定の割合で混合して被処理物質に添加することもでき、処理効率の面で有利である。
【００４４】
無機系重金属溶出防止剤としては、例えば次のようなものが挙げられるが、これらのうち、特にリン酸化合物が重金属を長期に安定に固定化できるので好ましい。
【００４５】
正リン酸（オルソリン酸）、ポリリン酸、メタリン酸、次リン酸、亜リン酸、次亜リン酸、ピロリン酸、過リン酸、第一リン酸ソーダ、第二リン酸ソーダ、第三リン酸ソーダ、第一リン酸カリウム、第二リン酸カリウム、第三リン酸カリウム、第一リン酸カルシウム、第二リン酸カルシウム、第一リン酸マグネシウム、第二リン酸マグネシウム、第一リン酸アンモニウム、第二リン酸アンモニウム、過燐酸石灰、トリポリリン酸ナトリウム、トリポリリン酸カリウム、ヘキサメタリン酸ナトリウム、ヘキサメタリン酸カリウム、ピロリン酸ナトリウム、ピロリン酸カリウム、亜リン酸ナトリウム、亜リン酸カリウム、次亜リン酸ナトリウム、次亜リン酸カリウム等のリン酸化合物。
【００４６】
焼き石膏、ポルトランドセメント、早強セメント、ジェットセメント、高炉セメント、アルミナセメント等のセメント類。
【００４７】
各種活性白土、合成珪酸、天然珪酸加工物等の無機吸着剤。
【００４８】
汎用の珪酸ソーダ、珪酸カリウム等の水溶性珪酸塩等の水ガラス。
【００４９】
これらの重金属溶出防止剤の添加量は用いる薬剤の種類や被処理物質の性状により異なるが、通常の場合、都市ごみ焼却炉の飛灰等の重金属含有被処理物質に対して有効成分量として０．１〜５０重量％、特に１〜２０重量％とするのが好ましい。
【００５０】
なお、被処理物質中に、アルカリ成分が多量に含まれる場合は、予め汎用の酸を加えて中和することで、これらの重金属溶出防止剤の添加量を低く抑えることもできる。
【００５１】
【実施例】
以下に実施例及び比較例を挙げて本発明をより具体的に説明する。
【００５２】
実施例１〜１２
被処理物質として、ナトリウム系及びカリウム系アルカリ剤が添加されず、カルシウム系のアルカリ剤も含まず、ダイオキシン類を７２９ｎｇ／ｇ含有するごみ焼却炉の飛灰を用い、加熱反応器としては撹拌機付の三ッ口フラスコをマントルヒータで加熱する間接加熱型の回分式反応器を用いて、処理を行った。
【００５３】
被処理物質に、表１に示す分解剤（いずれも粉末）を５重量％添加して均一に混合した後、反応器に投入し、空気雰囲気にて３００℃で１０分間加熱処理した。その後、処理物を自然放冷した後、処理物のダイオキシン類含有量を測定し、結果を表１に示した。また、測定結果からダイオキシン類の分解率を算出し、結果を表１に示した。
【００５４】
比較例１
分解剤を添加しなかったこと以外は実施例１と同様に処理を行い、結果を表１に示した。
【００５５】
【表１】
表１から明らかなように、何も添加しないで３００℃に加熱した場合（比較例１）には、ごみ焼却炉の飛灰に含有されるダイオキシン類前駆物質から飛灰の触媒作用によりダイオキシン類が生成し、逆に処理物のダイオキシン類含有量が増加した。一方、本発明に従って、各種の高分子脂肪族炭化水素、糖類、又は有機酸類を添加して加熱した場合（実施例１〜１２）には、３００℃という低温度でも高効率でダイオキシン類を分解することができた。
【００５７】
実施例１３，１４
実施例１で処理したものと同様の焼却炉飛灰に塩化カルシウムの粉末を２０重量％添加混合した模擬試料を調製し、これにＤ−グルコース粉末（実施例１３）又はギ酸ナトリウム（実施例１４）を重量比で５％添加し、実施例１と同様に加熱処理し、ダイオキシン類の分解率を調べた。
【００５８】
結果を塩化カルシウムを添加しない実施例４，１２と各々比較すると、表２に示す如く、同等のダイオキシン類分解率が得られた。
【００５９】
【表２】
実施例１５〜２２
港湾から採取した底質を事前にメッシュ２ｍｍのふるいを用い、ふるい下を採取し、８０℃で乾燥させて試料とした。この試料中のダイオキシン類濃度は１０５０ｎｇ／ｇであった。４０ｇの底質にグルコースを２ｇ（乾燥底質重量に対し５重量％）添加、混合したものを１０分間、２５０℃で加熱した。自然放冷後の処理物についてダイオキシン類濃度を測定し、分解率を求めた（実施例１５）。
【００６１】
同様にして、実施例１６から実施例２０は、分解剤として高分子脂肪族炭化水素、糖類、有機酸類をそれぞれ５重量％加えて、実施例１５と同じ操作を行った。
【００６２】
また、実施例１５のときと加熱温度を変え、実施例２１では加熱温度を１５０℃、実施例２２では加熱温度を３５０℃にして、同様の操作を行い、これらの結果を表３に示した。
【００６３】
比較例２〜４
薬剤を加えないこと以外は、実施例１５と同様に処理を行った結果を比較例２として表３に示した。また、加熱温度を１５０℃にした場合と３５０℃にした場合の結果を、それぞれ比較例３，４として表３に示した。
【００６４】
なお、表３には、反応時の臭気の強さを併記した。
【００６５】
【表３】
表３の比較例２から分かるように、何も添加しないで２５０℃に加熱した場合にはダイオキシン類の分解率は４３％であり、十分な分解率を得ることはできなかった。また、加熱中の臭気がひどく、かなり焦げ臭いにおいが充満していた。
【００６７】
一方、分解剤を添加した実施例１５〜２０では、８０％を超える高い分解率が確認でき、分解剤による分解効果が発揮されていることが分かる。このとき臭気は、殆ど認められなかった。
【００６８】
次に、加熱温度を３５０℃とした比較例３をみると、９０％を超える高い分解率が得られたが、装置周辺は非常に焦げ臭いにおいが充満し、この方法で処理を行うには、十分な装置気密化対策と排ガスの脱臭設備が不可欠であった。
【００６９】
一方、実施例２１に示すように、グルコースを５％添加して３５０℃で加熱した場合には、高い分解率が得られるとともに、臭気も殆ど認められず、極めて簡便な操作で安全に底質に含まれるダイオキシン類を無害化処理できることが明らかである。
【００７０】
また、実施例２２に示すように、１５０℃でも６０％の分解率が得られており、高い分解率を必要としない場合には、極めて低い温度で無害化処理を行うことができ、経済的な処理といえる。
【００７１】
【発明の効果】
以上詳述した通り、本発明のハロゲン化有機化合物の分解方法及び分解剤によれば、ダイオキシン類等のハロゲン化有機化合物で汚染された固体物質からなる被処理物質中のハロゲン化有機化合物を、安全かつ安価に分解して無害化することができる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a decomposition method for decomposing a halogenated organic compound in a substance to be treated, which is a solid substance contaminated with the halogenated organic compound, safely and inexpensively, and a decomposing agent therefor.
[0002]
[Prior art]
Conventionally, the following methods have been proposed as methods for decomposing and detoxifying harmful halogenated organic compounds represented by dioxins discharged from waste incineration plants.
[0003]
(1) Method of incineration and oxidative decomposition at high temperature ("Proceedings of the 8th Annual Conference of the Society of Waste Management Research," pp. 677-679)
{Circle around (2)} Method of dechlorination by heating in an inert gas atmosphere (“ORGANOHALOGEN COMPOUNDS Vol. 27 (1996)” p. 147-152)
(3) Method of reducing and dechlorinating by contacting with metallic sodium ("Proceedings of the 7th Waste Management Research Conference" p.954-957)
{Circle around (4)} A method of dechlorination by heating with a reducing substance such as an amine compound (Japanese Patent No. 3287298)
[0004]
[Patent Document 1]
Patent No. 3287298 [Non-Patent Document 2]
"Proceedings of the 8th Waste Management Research Conference" p. 677-679
[Non-Patent Document 3]
"ORGANOHALOGEN COMPOUNDS Vol. 27 (1996)"
p. 147-152
[Non-patent document 4]
Proceedings of the 7th Waste Management Research Conference, p. 954-957
[0005]
[Problems to be solved by the invention]
In the above method (1), heating at a high temperature of 800 ° C. or more is necessary. For a solid pollutant contaminated with a halogenated organic compound having an insufficient calorie even at a high concentration, an energy-consuming type is used. Processing technology, which is uneconomical.
[0006]
In the method (2), dioxins are decomposed by heating at about 200 to 550 ° C., which is more energy-efficient than the direct combustion method. However, some dioxins are re-synthesized during the cooling process, such as fly ash generated from the incineration of municipal solid waste, requiring additional measures for cooling. In the case of fly ash having a low melting point, a part of the matrix is melted during the decomposition reaction of dioxins, and stable operation of the reactor becomes difficult.
[0007]
In the method (3), treatment at normal temperature is possible, but since it is highly reactive and uses dangerous metal sodium, there is a high risk of ignition and explosion, and strict safety management is required.
[0008]
The method (4) can be processed at a relatively low temperature of 100 to 300 ° C., is effective for fly ash having a low melting point, and is energetically compared with the methods (1) and (2). Although it is an inexpensive treatment method, there is a problem that a bad treatment is required for the bad smell and tar because the mixed chemicals volatilize or decompose to generate a bad smell or generate a tar component.
[0009]
Under these circumstances, there is a current need for a technique for decomposing halogenated organic compounds that can safely and inexpensively detoxify halogenated organic compounds.
[0010]
The present invention has been made in view of the above-described conventional circumstances, and can safely and inexpensively decompose a halogenated organic compound in a substance to be treated consisting of a solid substance contaminated with a halogenated organic compound such as dioxins. It is an object of the present invention to provide a decomposing method for detoxifying and decomposing agent.
[0011]
[Means for Solving the Problems]
The method for decomposing a halogenated organic compound according to the present invention (claim 1) is a method for decomposing a halogenated organic compound in a substance to be treated consisting of a solid substance contaminated with the halogenated organic compound. Characterized by adding a chemical containing a high molecular weight aliphatic hydrocarbon effective for decomposing a fluorinated organic compound and heating.
[0012]
In the method for decomposing a halogenated organic compound according to the present invention (claim 2), a solid contaminated with a halogenated organic compound other than dust ash obtained from an exhaust gas to which an alkali agent containing sodium and / or potassium has been added. A method for decomposing a halogenated organic compound in a substance to be treated comprising a substance, wherein a substance containing a saccharide and / or an organic acid is added to the substance to be treated and heated.
[0013]
The halogenated organic compound decomposer of the present invention is characterized by containing a high molecular weight aliphatic hydrocarbon, saccharide, or organic acid having the resolution of the halogenated organic compound.
[0014]
If it is a high molecular weight aliphatic hydrocarbon, saccharide, or organic acid having the resolution of a halogenated organic compound, almost no foul odor or tar-like substance is generated unlike conventional amine compounds, the temperature is about 100 to 450 ° C. The halogenated organic compound in the substance to be treated can be safely and inexpensively decomposed and made harmless at a relatively low temperature.
[0015]
In particular, saccharides and organic acids are also effective for incinerated fly ash to which a calcium-based alkali agent was added, in which a conventional amine compound could not obtain a sufficient decomposition effect unless the temperature was raised to 350 ° C. or higher. Halogenated organic compounds can be decomposed efficiently by heating at a relatively low temperature.
[0016]
That is, generally, the exhaust gas discharged from the refuse incinerator, after passing through a boiler and a gas cooling tower, is sprayed with a calcium-based hydrogen chloride remover such as slaked lime and quicklime, and is then dust-removed by a dust collector such as a bag filter. Released into the atmosphere from the chimney. Thus, fly ash discharged from an incineration facility that treats hydrogen chloride in flue gas with calcium-based hydrogen chloride remover such as slaked lime and quick lime contains calcium-based alkaline agent such as slaked lime and hydrogen chloride. Contains calcium chloride which is a reaction product of However, calcium chloride in fly ash has a property of strongly adsorbing an amine compound having an amine group as a functional group or a polyhydric alcohol having a hydroxyl group. Therefore, when an amine compound or a polyhydric alcohol is added to fly ash containing a calcium-based alkali agent for the purpose of decomposing dioxins, the fly ash is adsorbed on calcium chloride. Therefore, the diffusion of dioxins inside the fly ash is hindered, so even if an amine compound or polyhydric alcohol is added to the fly ash containing calcium chloride and heating is performed, a sufficient dioxin decomposition effect is obtained. Cannot be obtained. However, fly ash collected from exhaust gas sprayed as sodium-based or potassium-based alkaline agent as an adsorbent for acidic gas adsorbs amine compounds and polyhydric alcohols to the product sodium chloride and potassium chloride. Since they have no effect, they effectively act as dioxin decomposers.
[0017]
On the other hand, it has been found that sugars and organic acids effectively act on fly ash containing calcium chloride. In particular, among organic acid salts, sodium formate is practically completely unaffected by calcium chloride, and is therefore optimal as a dioxin decomposer for fly ash containing calcium chloride. In addition, when the sediment is targeted, when heated without adding a chemical, a strong odor due to the organic matter originally contained in the sediment is generated, but when the decomposing agent of the present invention is added, the odor becomes strong. Since the odor is adsorbed, absorbed or decomposed like activated carbon, odor generation during the reaction can be reduced or eliminated.
In particular, glucose has a strong effect of suppressing odor, and is suitable for bottom sediment.
[0018]
Incidentally, when the behavior of the halogenated organic compound in the treated substance treated with the decomposing agent according to the present invention is traced, for example, in the case of dioxins, at the beginning of the reaction, OCDD (octachlorinated dibenzo), Paradioxin) or OCDF (octachlorinated dibenzofuran) decreases, and on the way, the low-chlorine substituted product shows an increasing tendency. Further, when the reaction is continued, the reduction of the low-chlorinated dioxins gradually progresses. From this, it is presumed that the decomposition reaction of the halogenated organic compound according to the present invention is a sequential dehalogenation reaction.
[0019]
In the present invention, polyethylene and / or polypropylene are preferable as the high molecular weight aliphatic hydrocarbons. The saccharides include one or more selected from the group consisting of glucose, fructose, galactose, sucrose, maltose, lactose, cellobiose, starch and cellulose, and the organic acids include citric acid, erythorbic acid, and gluconic acid. One or more selected from the group consisting of, formic acid and salts of these organic acids are preferred.
[0020]
A reactor can be used for heating the substance to be treated. In this case, a powdery or granular decomposing agent is treated in a step before supplying the substance to the reactor or in the reactor. It can be added to and mixed with the substance. As the reactor, it is preferable to use an indirect heating type continuous or batch reactor which does not require a function of positively supplying an inert gas.
[0021]
The rate of addition of the decomposing agent of the present invention is preferably 0.1 to 20% by weight as an active ingredient based on the substance to be treated, and the heating temperature is preferably 100 to 450 ° C.
[0022]
When the substance to be treated contains a heavy metal, it is preferable to further add a heavy metal elution inhibitor to prevent the elution thereof. In this case, the heavy metal elution inhibitor mainly containing a phosphoric acid compound is used. It is preferable to add the decomposing agent of the present invention simultaneously with the decomposing agent of the present invention or to mix the same with the decomposing agent of the present invention in advance, add to the substance to be treated, and heat.
[0023]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, embodiments of the method for decomposing a halogenated organic compound and the decomposer of the present invention will be described in detail.
[0024]
First, the decomposing agent for a halogenated organic compound of the present invention will be described.
[0025]
The decomposer for the halogenated organic compound of the present invention,
It contains high molecular weight aliphatic hydrocarbon sugars or organic acids having the resolution of halogenated organic compounds. In addition, the decomposer of the halogenated organic compound of the present invention is not limited to the one containing only one kind of the high molecular weight aliphatic hydrocarbon, the saccharide and the organic acid, and may be the one containing two or more kinds. That is, it may contain a high-molecular aliphatic hydrocarbon and a saccharide and / or an organic acid, or may contain a saccharide and an organic acid. In addition, each of the high molecular weight aliphatic hydrocarbons, sugars, and organic acids may contain two or more kinds.
[0026]
In the present invention, examples of the high-molecular aliphatic hydrocarbon include polyethylene, polypropylene, and polystyrene. Of these, it is preferable to use polyethylene and / or polypropylene, since no malodor is generated during the heating reaction. .
[0027]
Examples of the saccharide include monosaccharides such as glucose, fructose, and galactose; disaccharides such as sucrose, maltose, lactose, and cellobiose; and polysaccharides such as starch and cellulose. Glycosides such as saponin and polymer electrolytes such as lignin are also effective.
[0028]
Examples of the organic acids include citric acid, erythorbic acid, formic acid, gluconic acid obtained by oxidizing glucose, and salts thereof such as sodium salt, potassium salt, and calcium salt.
[0029]
The decomposing agent for a halogenated organic compound of the present invention may contain other halogenated organic compound decomposing agents in addition to these high molecular weight aliphatic hydrocarbons, sugars and organic acids. Further, it may contain a heavy metal elution inhibitor described below.
[0030]
The decomposing agent for a halogenated organic compound of the present invention is added to a substance to be treated consisting of a solid substance contaminated with a halogenated organic compound according to the method of the present invention described below. It can also be used effectively to prevent the generation of dioxins in the above.
[0031]
In other words, incineration fly ash from refuse incinerators is known as a catalyst for synthesizing dioxins, but fly ash accumulated in exhaust gas pipes and dust collectors, and enters into the cloth of filter cloth of filtration type dust collectors and is removed. Fly ash that remains without being dropped will stay for a long time in a temperature environment where dioxins are easy to synthesize, and not only will the dioxin content increase, but also dioxins that have increased in the exhaust gas due to stagnation in the dust collector May desorb and evaporate again, increasing the concentration of dioxins in the chimney.
[0032]
Therefore, the decomposing agent of the halogenated organic compound of the present invention is added to the exhaust gas, mixed in the exhaust gas stream, adhered to the fly ash, or deposited in a form mixed with the fly ash. The effect of decomposing the synthesized dioxins and the effect of suppressing the synthesis of dioxins on fly ash can be obtained.
[0033]
In particular, during start-up and shutdown operations of the incinerator, incomplete combustion generates a large amount of dioxins and their precursors, and this also generates fly ash with a large amount of dioxins attached. It is particularly effective to add the decomposing agent of the present invention during the stop operation.
[0034]
The method for decomposing a halogenated organic compound of the present invention uses such a decomposer of the present invention to decompose a halogenated organic compound in a substance to be treated consisting of a solid substance contaminated with the halogenated organic compound, It is a way to make it harmless.
[0035]
In the present invention, the halogenated organic compound in the substance to be treated is decomposed by adding the above-mentioned high molecular weight aliphatic hydrocarbon or the saccharide and / or the organic acid to the substance to be treated and heating the mixture. In addition, saccharides and / or organic acids may be used in combination with the high molecular weight aliphatic hydrocarbon.
[0036]
The amount of these decomposing agents to be added to the substance to be treated is appropriately determined depending on the type of the chemical used and the content of the halogenated organic compound in the substance to be treated. The component amount is preferably 0.1 to 20% by weight, particularly 0.5 to 15% by weight, particularly preferably 1 to 10% by weight.
[0037]
In order to heat the substance to be treated together with the decomposing agent for the halogenated organic compound, a substance to be treated and the decomposing agent may be charged into the reactor using a heating reactor. In this case, the decomposing agent can be added to the substance to be treated as a powdery or granular solid, and may be added and mixed in a step prior to charging the substance to be treated into the reactor. It may be added and mixed with the substance to be treated.
[0038]
The heating atmosphere may be an air atmosphere, and does not necessarily need to be replaced with an inert gas. Therefore, the function of positively supplying an inert gas to the reactor is unnecessary. The heating method is not particularly limited, but it is preferable to use an indirect heating type reactor so as not to oxidize and burn in the reactor before the decomposing agent acts. Although not an essential requirement, it is preferable that the intake of air into the reactor be suppressed.
[0039]
The reactor used may be a continuous type or a batch type, but it is desirable to use a reactor having a stirring function in order to achieve uniform contact between the decomposing agent and the substance to be treated. For example, in the continuous type, a rotary kiln of an indirect heating type, a reactor similar to a paddle dryer having a plurality of stirring paddles, or the like can be used, and a batch reactor has an autoclave or a stirrer having a stirring function. Can be used, but the present invention is not limited thereto.
[0040]
The heating temperature is preferably 100 to 450 ° C, particularly preferably 100 to 400 ° C, particularly preferably 150 to 400 ° C. If the heating temperature is lower than 100 ° C., a sufficient decomposition effect cannot be obtained, and high-temperature heating exceeding 450 ° C. is disadvantageous in terms of cost and equipment. The heating time varies depending on the heating temperature and the treatment amount, but may be 3 minutes or more, and is usually about 5 to 60 minutes.
[0041]
In the present invention, the substance to be treated is not particularly limited, but includes incinerated fly ash containing incinerated organic compounds such as dioxins, incinerated ash soil, river / lake / port sediment, ash pit sludge, Examples include wastes generated during maintenance of the incinerator, such as remnants of incinerators such as refractory bricks and metal fragments, deposits in exhaust gas pipes, and filter cloths of filter dust collectors.
[0042]
If the material to be treated contains heavy metals, such as fly ash from a municipal solid waste incinerator, a heavy metal dissolution inhibitor is used in combination to prevent the dissolution of heavy metals and detoxify it. Is preferred.
[0043]
As the heavy metal elution preventive, there are various types of organic and inorganic ones. However, organic heavy metal elution preventives such as chelate compounds are decomposed and lost at the time of heat treatment. After the thermal decomposition treatment of the compound, an operation of adding and kneading separately from the decomposer for the halogenated organic compound is required. On the other hand, if it is an inorganic heavy metal elution inhibitor, since there is no risk of decomposition by heating, it is added to the substance to be treated together with the decomposer of the halogenated organic compound during the heat decomposition treatment of the halogenated organic compound. In this case, it can be mixed with a decomposer for the halogenated organic compound in a predetermined ratio in advance and added to the substance to be treated, which is advantageous in terms of treatment efficiency.
[0044]
Examples of the inorganic heavy metal elution inhibitor include the following. Among them, a phosphoric acid compound is particularly preferable because a heavy metal can be stably immobilized for a long period of time.
[0045]
Orthophosphoric acid, orthophosphoric acid, polyphosphoric acid, metaphosphoric acid, hypophosphoric acid, phosphorous acid, hypophosphorous acid, pyrophosphoric acid, perphosphoric acid, sodium phosphate monobasic, sodium phosphate dibasic, tertiary phosphoric acid Soda, monobasic potassium phosphate, dibasic potassium phosphate, tribasic potassium phosphate, monobasic calcium phosphate, dibasic calcium phosphate, monobasic magnesium phosphate, dibasic magnesium phosphate, monobasic ammonium phosphate, dibasic phosphoric acid Ammonium, lime superphosphate, sodium tripolyphosphate, potassium tripolyphosphate, sodium hexametaphosphate, potassium hexametaphosphate, sodium pyrophosphate, potassium pyrophosphate, sodium phosphite, potassium phosphite, sodium hypophosphite, hypophosphorous acid Phosphoric acid compounds such as potassium.
[0046]
Cement such as plaster of Paris, Portland cement, early-strength cement, jet cement, blast furnace cement, alumina cement.
[0047]
Inorganic adsorbents for various types of activated clay, synthetic silicic acid, and natural silicic acid products.
[0048]
Water glass such as water-soluble silicates such as general-purpose sodium silicate and potassium silicate.
[0049]
The amount of the heavy metal elution inhibitor added varies depending on the type of chemical used and the properties of the substance to be treated, but usually, the amount of the active ingredient is 0 as an effective amount with respect to the substance to be treated containing heavy metals such as fly ash of a municipal solid waste incinerator. It is preferably from 1 to 50% by weight, especially from 1 to 20% by weight.
[0050]
When a large amount of an alkali component is contained in the substance to be treated, the amount of the heavy metal elution inhibitor added can be reduced by adding a general-purpose acid in advance to neutralize the substance.
[0051]
【Example】
Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples.
[0052]
Examples 1 to 12
As a substance to be treated, fly ash from a refuse incinerator containing no dioxins and 729 ng / g containing no sodium-based or potassium-based alkali agent, no calcium-based alkali agent, and a stirrer as a heating reactor is used. The treatment was performed using an indirect heating batch reactor in which the attached three-necked flask was heated by a mantle heater.
[0053]
After 5% by weight of a decomposing agent (all powders) shown in Table 1 was added to the substance to be treated and mixed uniformly, the mixture was charged into a reactor and heated at 300 ° C. for 10 minutes in an air atmosphere. Thereafter, the treated product was allowed to cool naturally, and then the content of dioxins in the treated product was measured. The results are shown in Table 1. In addition, the decomposition rate of dioxins was calculated from the measurement results, and the results are shown in Table 1.
[0054]
Comparative Example 1
The treatment was performed in the same manner as in Example 1 except that the decomposing agent was not added, and the results are shown in Table 1.
[0055]
[Table 1]
As is clear from Table 1, when heated to 300 ° C. without any addition (Comparative Example 1), dioxins were catalyzed by fly ash from dioxin precursors contained in fly ash of a refuse incinerator. Was generated, and conversely, the dioxin content of the treated product increased. On the other hand, according to the present invention, when various polymer aliphatic hydrocarbons, sugars, or organic acids are added and heated (Examples 1 to 12), dioxins are decomposed with high efficiency even at a low temperature of 300 ° C. We were able to.
[0057]
Examples 13 and 14
A simulated sample was prepared by adding and mixing 20% by weight of calcium chloride powder to the same incinerator fly ash as that treated in Example 1 and adding it to D-glucose powder (Example 13) or sodium formate (Example 14). ) Was added in a weight ratio of 5%, and heat treatment was performed in the same manner as in Example 1 to examine the decomposition rate of dioxins.
[0058]
When the results were compared with those of Examples 4 and 12 in which calcium chloride was not added, as shown in Table 2, the same dioxin decomposition rates were obtained.
[0059]
[Table 2]
Examples 15 to 22
The sediment collected from the harbor was used in advance by using a sieve having a mesh of 2 mm, and the bottom of the sieve was collected and dried at 80 ° C. to obtain a sample. The dioxin concentration in this sample was 1,050 ng / g. 2 g of glucose (5% by weight based on the weight of the dried sediment) was added to 40 g of the sediment, and the mixture was heated at 250 ° C. for 10 minutes. The concentration of dioxins in the treated product after natural cooling was measured, and the decomposition rate was determined (Example 15).
[0061]
Similarly, in Examples 16 to 20, the same operation as in Example 15 was performed, except that 5% by weight of each of a polymer aliphatic hydrocarbon, a saccharide, and an organic acid was added as a decomposing agent.
[0062]
Further, the heating temperature was changed from that of Example 15, the heating temperature was set to 150 ° C. in Example 21, and the heating temperature was changed to 350 ° C. in Example 22, and the results are shown in Table 3. .
[0063]
Comparative Examples 2 to 4
The results obtained by performing the same treatment as in Example 15 except that no drug was added are shown in Table 3 as Comparative Example 2. Table 3 shows the results when the heating temperature was 150 ° C. and when the heating temperature was 350 ° C. as Comparative Examples 3 and 4, respectively.
[0064]
Table 3 also shows the odor intensity during the reaction.
[0065]
[Table 3]
As can be seen from Comparative Example 2 in Table 3, when heated to 250 ° C. without any addition, the decomposition rate of dioxins was 43%, and a sufficient decomposition rate could not be obtained. Further, the odor during the heating was severe and the burnt smell was full.
[0067]
On the other hand, in Examples 15 to 20 to which the decomposing agent was added, a high decomposition rate exceeding 80% was confirmed, and it can be seen that the decomposition effect by the decomposing agent was exhibited. At this time, almost no odor was recognized.
[0068]
Next, according to Comparative Example 3 in which the heating temperature was 350 ° C., a high decomposition rate exceeding 90% was obtained, but the periphery of the apparatus was filled with a very burnt smell. Sufficient airtightness measures and exhaust gas deodorization equipment were indispensable.
[0069]
On the other hand, as shown in Example 21, when 5% glucose was added and heated at 350 ° C., a high decomposition rate was obtained, almost no odor was recognized, and sediment was safely obtained by an extremely simple operation. It is clear that the dioxins contained in can be detoxified.
[0070]
In addition, as shown in Example 22, a decomposition rate of 60% was obtained even at 150 ° C, and when a high decomposition rate was not required, the detoxification treatment could be performed at an extremely low temperature, which was economical. It can be said that processing is.
[0071]
【The invention's effect】
As described in detail above, according to the method for decomposing a halogenated organic compound and the decomposing agent of the present invention, a halogenated organic compound in a substance to be treated consisting of a solid substance contaminated with a halogenated organic compound such as dioxins, It can be decomposed safely and inexpensively to make it harmless.
Claims (16)
該被処理物質にハロゲン化有機化合物の分解に対して有効な高分子脂肪族炭化水素類を含む薬剤を添加して加熱することを特徴とするハロゲン化有機化合物の分解方法。In a method for decomposing a halogenated organic compound in a substance to be treated consisting of a solid substance contaminated with the halogenated organic compound,
A method for decomposing a halogenated organic compound, comprising adding a drug containing a high molecular weight aliphatic hydrocarbon effective for decomposing a halogenated organic compound to the substance to be treated and heating the resultant.
該被処理物質に糖類及び／又は有機酸類を含む薬剤を添加して加熱することを特徴とするハロゲン化有機化合物の無害化処理方法。A method for decomposing a halogenated organic compound in a substance to be treated, which is a solid substance contaminated with a halogenated organic compound, other than dust ash obtained from an exhaust gas to which an alkali agent containing sodium and / or potassium has been added, ,
A method for detoxifying a halogenated organic compound, which comprises heating a substance containing a saccharide and / or an organic acid to the substance to be treated.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007175671A (en) * | 2005-12-28 | 2007-07-12 | Oji Paper Co Ltd | Separation method of lead from combustion ash |
| WO2012029433A1 (en) * | 2010-08-30 | 2012-03-08 | 国立大学法人 東京大学 | Processing material and processing method |
| JP2018044064A (en) * | 2016-09-14 | 2018-03-22 | 株式会社ジーエルプラン | Agent for reducing pcb and heavy metals |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007175671A (en) * | 2005-12-28 | 2007-07-12 | Oji Paper Co Ltd | Separation method of lead from combustion ash |
| JP4600276B2 (en) * | 2005-12-28 | 2010-12-15 | 王子製紙株式会社 | Method for desorbing lead from combustion ash |
| WO2012029433A1 (en) * | 2010-08-30 | 2012-03-08 | 国立大学法人 東京大学 | Processing material and processing method |
| JP2018044064A (en) * | 2016-09-14 | 2018-03-22 | 株式会社ジーエルプラン | Agent for reducing pcb and heavy metals |
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