JP3658602B2 - Method and apparatus for decomposing a hardly decomposable substance - Google Patents

Description

である。
【００４７】
被分解物がＲ１２，即ちフロンＣＦＣ−１２の場合には、溶媒としての水のみを加えて反応させることにより、下記（１）式の加水分解が進行する。
ＣＣｌ_２Ｆ_２＋２Ｈ_２Ｏ → ＣＯ_２＋２ＨＣｌ＋２ＨＦ………………（１）
【００４８】
上記（１）式の反応時に活性化エネルギー注入機構３３を駆動すると、熱電子（ｅ⁻）がフロンＣＦＣ−１２の分子や原子に衝突して分子イオンや解離を伴うラジカル及びラジカルイオンができる。

【００４９】
これらの分子イオンやラジカル及びラジカルイオンは高エネルギーで励起された状態であり、反応性に富む粒子であるため、励起された状態の分子や原子が過剰なエネルギーを放出して最も安定な状態、即ち結合エネルギーが最も低くなるようにー方向反応が進行し分解される。そして反応時間が経過してほぼ完全に分解処理され、次段のシャワリング塔１７内に送り込まれる。
【００５０】
フロンＣＦＣ−２２の加水分解は、下記の（３）〜（５）式により行われる。
ＣＨＣｌＦ_２＋２Ｈ_２Ｏ → ＣＯ_２＋ＨＣｌ＋２ＨＦ＋Ｈ_２………（３）
ＣＨＣｌＦ_２＋Ｈ_２Ｏ → ＨＣｌ＋２ＨＦ＋ＣＯ……………………（４）
４ＣＨＣｌＦ_２＋６Ｈ_２Ｏ → ３ＣＯ_２＋８ＨＦ＋４ＨＣｌ＋ＣＨ_４………（５）
（３）（４）（５）式によれば、Ｈ_２ガス，ＣＯガス，ＣＨ_４ガスという有害もしくは可燃性ガスが生成する問題がある。そこで水とともに空気もしくは酸素を加えて加水酸化分解を行わせると下記の（６）式が進行する。
ＣＨＣｌＦ_２＋２Ｈ_２Ｏ＋Ｏ_２ → ２ＣＯ_２＋２ＨＣｌ＋４ＨＦ……（６）
従って一酸化炭素ＣＯは
２ＣＯ＋Ｏ_２＝２ＣＯ_２
となり、水素ガスＨ_２は
２Ｈ_２＋Ｏ_２＝２Ｈ_２Ｏ
となり、メタンガスＣＨ_４は
ＣＨ_４＋３Ｏ_２＝ＣＯ_２＋２Ｈ_２Ｏ
となる。従って有害もしくは可燃性ガスは二酸化炭素として無害化されるか水分に変換され、（６）式で示す結果に帰結する。
【００５１】
フロンＣＦＣ−１３４ａの加水分解は、下記の（７）〜（９）式により行われる。
Ｃ_２Ｈ_２Ｆ_４＋２Ｈ_２Ｏ → ４ＨＦ＋２ＣＯ＋２Ｈ_２…………………（７）
Ｃ_２Ｈ_２Ｆ_４＋４Ｈ_２Ｏ → ４ＨＦ＋２ＣＯ_２＋３Ｈ_２………………（８）
Ｃ_２Ｈ_２Ｆ_４＋３Ｈ_２Ｏ → ４ＨＦ＋ＣＯ＋２Ｈ_２＋ＣＯ_２…………（９）
（７）（８）（９）式の場合でもＨ_２ガス，ＣＯガスという有害もしくは可燃性ガスが生成するが、水とともに空気もしくは酸素を加えて反応させることによって前記（６）式が進行し、加水酸化分解が行われる。
【００５２】
フロンＣＦＣ−１４１ｂの加水分解は、下記の（１０）〜（１１）式により行われる。
Ｃ_２Ｈ_３Ｃｌ_２Ｆ＋２Ｈ_２Ｏ → ２ＣＯ＋ＨＦ＋２ＨＣｌ＋２Ｈ_２……（１０）
Ｃ_２Ｈ_３Ｃｌ_２Ｆ＋４Ｈ_２Ｏ → ２ＣＯ_２＋ＨＦ＋２ＨＣｌ＋４Ｈ_２……（１１）
（１０）（１１）式は一酸化炭素，Ｈ_２ガスが生成するため不適である。そこで水とともに空気もしくは酸素を加えて反応させると下記の（１２）（１３）式が進行し、加水酸化分解が行われる。

この場合、水、酸素を加えると（１２）（１３）式のようにＣＯ，Ｈ_２が発生して不適である。この場合、酸素だけを加えた酸化分解の場合には下記の（１４）（１５）式が進行する。
Ｃ_２Ｈ_３Ｃｌ_２Ｆ＋２Ｏ_２ → ２ＣＯ_２＋２ＨＣｌ＋ＨＦ…………（１４）
Ｃ_２Ｈ_３Ｃｌ_２Ｆ＋Ｏ_２ → ２ＣＯ＋２ＨＣｌ＋ＨＦ ……………（１５）
この場合にも（１５）式に示されるようにＣＯガスが生成されるが、実際には酸素過剰の状態で（１４）式が優先して起きるため、酸素が十分に過剰な雰囲気を作り、どの過程の分解が起きても最終的には（１４）式になるようにすることが可能となる。酸素だけを加えた場合には酸化分解が進行するが、予期できない副生成物ができることがあるため、水を適量添加することによって生じる過熱蒸気の存在が重要となる。従って分解方法としては加水酸化分解が最適である。
【００５３】
被分解処理物としてフロンガスを用いた場合には下記の生成物が確認された。先ず気体はＣＯ_２，ＨＣｌ，ＨＦであり、冷却後は水にＨＣｌ，ＨＦは溶けて強酸となる。
【００５４】
下記の（１６）式に示したように、フロンの濃度に応じて苛性ソーダＮａＯＨを加えて炭酸ガスを重炭酸ソーダＮａＨＣＯ_３とし、（１７）式のように苛性ソーダと塩酸の反応で食塩ＮａＣｌを生成して、更に（１８）式のように苛性ソーダとフッ酸の反応でフッ化ナトリウムＮａＦを生成して対処する場合もある。液化後の強酸性液をＮａＯＨで中和する場合、（１７）（１８）式が、また、必ずＣＯ_２が発生するので（１６）式も起きて炭酸ガスを放出しない方法も可能となる。
ＮａＯＨ＋ＣＯ_２ → ＮａＨＣＯ_３ …………………………（１６）
ＮａＯＨ＋ＨＣｌ → ＮａＣｌ＋Ｈ_２Ｏ………………………（１７）
ＮａＯＨ＋ＨＦ → ＮａＦ＋Ｈ_２Ｏ…………………………（１８）
【００５５】
以上説明した実施形態は、流体状或は気体状の被分解処理物を分解処理するためのものであり、環境汚染物質としてフロンガスの外にクロロベンゼン，トリクロロエタン等のハロゲン炭化化合物の液状物の分解が可能である。本実施形態によるトリクロロエタン（ＣＨ_３・ＣＣｌ_３）及びベンゼン核を持つ有機物であるクロロベンゼン（Ｃ_６Ｈ_５Ｃｌ）の分解反応を説明する。
【００５６】
先ずトリクロロエタン（ＣＨ_３・ＣＣｌ_３）を分解する場合は以下のように反応が進行する。
ＣＨ_３・ＣＣｌ_３＋２Ｏ_２ → ２ＣＯ_２＋３ＨＣｌ
【００５７】
次にクロロベンゼン（Ｃ_６Ｈ_５Ｃｌ）を分解する場合は、以下のように分解が進行する。
Ｃ_６Ｈ_５Ｃｌ＋７Ｏ_２ → ６ＣＯ_２＋２Ｈ_２Ｏ＋ＨＣｌ
【００５８】
ここで活性化エネルギー注入機構３３の駆動原理を理論的に考察すると、一般に電子がエネルギーの最も低い状態にあるときは、原子が基底状態にあるといい、電子がエネルギー的に高い状態は、原子の内部にエネルギーが蓄積された励起状態と呼称される。励起が十分に高くなると、電子は原子核の束縛から逃れて自由電子となる。これが電離であり、自由電子は連続的なエネルギー状態を保っている。つまり電離は内部励起の一つの極限と考えることができる。
【００５９】
他方で化学反応を円滑に行うために、衝突によって反応系に加えなければならない最低限のエネルギーを活性化エネルギー（Ｅ_ａｃｔ）という。活性化エネルギーの源は動き回っている粒子の運動エネルギーであり、衝突で与えられるエネルギー量はほとんど最低限より少ないが、粒子の一方または両方が異常な早さで動き回っている場合には、粒子間で強烈な衝突が起こり、化学反応を起こすのに十分なエネルギーが与えられる。
【００６０】
従って化学反応を起こすためには、十分な活性化エネルギー（Ｅ_ａｃｔ）を持って粒子が衝突することが必要であり、前記活性化エネルギー注入機構３３を駆動することによって内部励起された自由電子の持つ連続的なエネルギー状態が有効利用され、加熱ヒータ等の熱エネルギー付与手段を用いなくても反応系のエネルギーレベルを上げて化学反応を円滑に進行させることが出来る。
【００６１】
また、本発明によれば、分解すべきガスを全て混合した状態で熱電子を注入することが可能であるから、全ての種類のガスに同時に活性化エネルギーが注入されて反応を効率的に行わせることが出来る。
【００６２】
表１は活性化エネルギー注入機構３３を駆動しないケースでのＲ２２（ＣＦＣ−２２）とＲ１２及びＲ１３４Ａの各フロンガスについて、分解率と温度の関係を測定した一覧表であり、図１０は表１の測定値をプロットしたグラフである。
【００６３】
【表１】

【００６４】
表１及び図１０によれば、Ｒ２２は８５０℃で分解率が９９．９％に達しているとともにＲ１２は９５０℃で分解率が９９．９％に達しており、Ｒ１３４Ａでは８００℃で分解率が９９．９％に達している。表２は各フロンガスの分解率が９９．９％に達してから以降の時間（分）と温度上昇の関係を測定した一覧表であり、図１１は表２の測定値をプロットしたグラフである。
【００６５】
【表２】

【００６６】
表２及び図１１によれば、Ｒ１２は分解率が９９．９％に達した後はほぼ９３０℃近辺にあり、Ｒ２２は分解率が９９．９％に達して１８分後に１０８０℃に達して、以降はほぼ温度が変化しない。これに対してＲ１３４Ａでは分解率が９９．９％に達して１８分後に１２４１℃に達してから以後は、ほぼ１２４０℃前後にある。
【００６７】
表３は前記活性化エネルギー注入機構３３を駆動したケースでのＲ１２（ＣＦＣ−１２）とＲ２２及びＲ１３４Ａの各フロンガスについて、同様に分解率と温度の関係を測定した一覧表であり、図１２は表３の測定値をプロットしたグラフである。尚、図３に示すカソードＨ_１，Ｈ_２，Ｈ_３とアノードＰ_１，Ｐ_２，Ｐ_３の各電極表面積を３．７ｃｍ^２，材質はタングステン＋トリウム，電流は３Ａ，電極表面温度を約１５００℃，加速電圧は１ｋＶとした。
【００６８】
【表３】

【００６９】
表３及び図１２によれば、Ｒ１２は５００℃で分解率が９９．９％に達しているとともにＲ２２は４５０℃で分解率が９９．９％に達しており、Ｒ１３４Ａでは４００℃で分解率が９９．９％に達している。従って前記表１及び図１０のデータよりも４００℃〜４５０℃も低温度の領域でフロンの分解率が９９．９％に達していることが分かる。
【００７０】
表４は各フロンガスについて自由電子注入時の時間（分）と温度上昇の関係を測定した一覧表であり、図１３は表４の測定値をプロットしたグラフである。
【００７１】
【表４】

【００７２】
表４及び図１３によれば、Ｒ１２は電子注入時に時間の経過とともに温度は６００℃〜６１４℃と変化が少なく、Ｒ２２は当初５５０℃の温度が１０分経過後に７２１℃に達し、以降は７３３℃〜７３５℃近辺にある。Ｒ１３４Ａは当初５００℃の温度が１２分経過後に８５４℃に達し、以降は８５５℃近辺にある。従って何れのケースでも温度の上昇範囲は１０００℃以下にあることが分かる。
【００７３】
表５は前記活性化エネルギー注入機構３３を駆動したケースでの各フロンガスについて、同様に分解率と温度の関係を測定した一覧表であり、図１４は表５の測定値をプロットしたグラフである。尚、図３に示すカソードＨ_１，Ｈ_２，Ｈ_３とアノードＰ_１，Ｐ_２，Ｐ_３間の電流を１．５Ａとした以外の測定条件は表３における測定条件と同一とした。
【００７４】
【表５】

【００７５】
表５及び図１４によれば、Ｒ１２は６５０℃で分解率が９９．９％に達しているとともにＲ２２は６００℃で分解率が９９．９％に達しており、Ｒ１３４Ａでは５５０℃で分解率が９９．９％に達している。従って前記表１及び図１０のデータよりも２５０℃〜３００℃も低温度の領域でフロンの分解率が９９．９％に達していることが分かる。
【００７６】
【表６】

【００７７】
表６の（１）は混合フロンについて活性化エネルギー注入機構３３を駆動しないケースでＲ４０４（ＣＦＣ−４０４）の１０（ｋｇ／ｈ）を、分解率が９９．９％まで分解処理した後の温度の変化を測定したデータであり、（２）は同一条件でＲ４０４の６（ｋｇ／ｈ）を分解処理した後の温度の変化を測定したデータである。（１）では分解処理終了時に８００℃に達しており、１６分経過後に１０００℃を越えて３０分経過後には１２８３℃まで温度が上昇し、（２）では３０分経過後の温度が８６４℃となっている。従ってＲ４０４を１度に１０（ｋｇ／ｈ）分解処理することは高温度により装置の劣化を招来するため好ましくなく、（２）の６（ｋｇ／ｈ）程度まで分解処理量を低減させなければならず、作業効率が低下するという難点が生じる。
【００７８】
表６の（３）は前記活性化エネルギー注入機構３３を駆動して自由電子を注入しながらＲ４０４の１０（ｋｇ／ｈ）を、分解率が９９．９％まで分解処理した後の温度の変化を測定したデータであり、図１５に前記（１）（２）のデータとともに（３）のデータをプロットしてある。表６の（３）によれば、分解処理終了時に５００℃であり、１６分経過後に８７２℃に達し、以後３０分まで温度が８７３℃前後に保たれている。従って本発明によれば、Ｒ４０４を１度に１０（ｋｇ／ｈ）分解処理しても高温度により装置が劣化する惧れはなく、分解処理量を高く維持して作業効率をアップさせることができる。
【００７９】
【発明の効果】
以上詳細に説明したように、本発明によればフロンガスとか有機化合物及びその他の産業廃棄物等の難分解物質を、酸素、又は酸素と水、若しくは溶媒としての水のみを供給し、反応器内に配備された活性化エネルギー注入機構を駆動することによってカソードからアノードに向けて熱電子が加速しながら放出され、該熱電子が被分解処理物の分子や原子に衝突して励起することによって活性化エネルギーが注入され、ヒータ等の熱エネルギーによって反応器内を高温に加熱しなくても分解反応が効率的に行わせることができる。特に反応器内の温度上昇を防止するために別途に冷却装置を設ける必要がなく、装置のコストが低廉化されるとともに稼働時に被分解処理物の処理量を犠牲にする惧れがない。
【００８０】
そして反応器内で所定の反応を行わせることにより、溶媒としての水の過熱蒸気により加水分解される形態と、酸素による酸化分解の形態及び水と酸素の添加による加水酸化分解の何れかの形態によって難分解物質を分解処理することができる。特に本発明は水熱反応を利用した分解手段のように反応器内を高温高圧に維持する必要がないため、反応器及びその他の圧力調整弁等を不要とし、操作上のコントロールも容易となる利点がある。
【００８１】
また、反応形態は一律であって酸化分解、加水酸化分解、加水分解の３種の分解形態が明らかであり、しかも鉄とか炭素鋼等の反応助材を用いていないため、一酸化炭素等の有毒ガスとか水素ガス等の爆発性を有する可燃性ガスは生成しないか、生成しても直ちに無害化処理することが可能となる。更に反応生成物に起因する配管の詰まりとか、途中の配管内で反応が開始されることによる配管の腐食現象を防止することができる。
【００８２】
分解の終了したガス成分は冷却することにより液化して排出することが可能であり、常圧下での加熱が主工程となっているため高圧ポンプは不要であり、排出弁とか配管が破損する懸念はない。更に反応は全て反応器の中で起こるクローズドシステムであるので二次汚染がないという効果が得られる。しかもフロンのみならず他の産業廃棄物とかベンゼン核を持つ有機物にも適用可能である。
【００８３】
更に本発明によれば、低圧で工程が進行するとともに反応器が１０００℃以上の高温に達することが回避されるため、耐食性が格段に向上するとともに反応器自体の材質は任意に選択することが出来る上、機械的な強度及び耐食性、引張応力とか熱応力に耐えるための設計は要求されないという利点があり、各種機器の破損に対する対策は容易であるとともに装置自体の自動化も容易であり、安全性が高いという効果がある。
【図面の簡単な説明】
【図１】本発明を適用した反応器の構成を示す断面図。
【図２】図１の要部拡大図。
【図３】図１のＡ−Ａ線に沿う断面図。
【図４】反応器の他の実施形態を示す断面図。
【図５】図４のＢ−Ｂ線に沿う断面図。
【図６】活性化エネルギー注入機構の他例を示す要部断面図。
【図７】図６の左側面図。
【図８】図６のＣ−Ｃ線に沿う断面図。
【図９】本発明にかかる難分解物質の分解処理方法と装置の基本的実施形態を示すシステム図。
【図１０】活性化エネルギー注入機構を駆動しないケースでの各フロンガスの分解率と温度の関係を示すグラフ。
【図１１】フロンガスの分解率が９９．９％に達した以降の時間と温度上昇の関係を示すグラフ。
【図１２】活性化エネルギー注入機構を駆動したケースでの各フロンガスの分解率と温度の関係を示すグラフ。
【図１３】自由電子注入時の時間と温度上昇の関係を示すグラフ。
【図１４】活性化エネルギー注入機構を駆動したケースでの各フロンガスの分解率と温度の関係を示すグラフ。
【図１５】活性化エネルギー注入機構を駆動したケースと駆動しないケースについて、フロンを９９．９％まで分解処理した後の温度の変化を示すグラフ。
【符号の説明】
１…被分解物タンク
２，４，３０…流量調整弁
３，２９…エアコンプレッサ
５…水タンク
６…定量ポンプ
７…反応器
１１，１２，１３…予備加熱ヒータ
１４，１５，１６…加熱ヒータ
１７，１８，１９…シャワリング塔
１７ａ，１８ａ，１９ａ…テラレット
２０…中和冷却器
２１…シャワリング用ポンプ
２２…ヘッダ
２３…冷却器
２４…吸引ブロワ
３１…保温材
３２，３５…パイプ
３３…活性化エネルギー注入機構
３４…絶縁用部材
整理番号 Ｐ３０７０[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method and apparatus for decomposing a hardly decomposable substance such as an environmental pollutant, and in particular, an organic compound having Freon gas, SF6, halon, benzene nuclei and other industrial wastes that contaminate the environment. When oxygen is reacted in an atmosphere of oxygen, oxygen and water, or water vapor as a solvent, thermal electrons are injected into the reaction apparatus to give activation energy, thereby lowering the decomposition start temperature of the object to be decomposed. In particular, the present invention relates to a treatment method and an apparatus for decomposing by oxidative degradation, hydrolytic degradation, hydrolysis and combinations thereof.
[0002]
[Prior art]
Conventionally, it has been pointed out that chlorofluorocarbon gas used as a refrigerant or spray agent and halon gas used as a digestive agent are environmental pollutants, and chlorofluorocarbon gas is a substance that destroys the ozone layer. Detoxification treatment has become a global concern from the viewpoint of protecting the global environment, and various countermeasures have been proposed. For example, hydrothermal reaction methods, incineration methods, explosion reaction decomposition methods, microbial decomposition methods, ultrasonic decomposition methods, plasma reaction methods, and the like have been proposed for chlorofluorocarbon gas treatment methods.
[0003]
Among these treatment methods, the hydrothermal reaction method is not limited to chlorofluorocarbons, but is versatile for all degradable substances mainly composed of organic solvents such as trichlene, waste oil, dioxin, PCB, manure, etc. It is attracting attention as a certain processing method. In this hydrothermal reaction method, for example, Freon gas can be decomposed into safe substances such as sodium chloride and carbon dioxide.
[0004]
Regarding equipment for realizing the hydrothermal reaction method, processing experiments using an autoclave in the laboratory, for example, the mixing ratio of caustic soda solution, ethanol, chlorofluorocarbon solution, temperature setting value, pressure setting value and reaction time setting Experiments on values have been conducted, but the normal hydrothermal reaction is 100 to 250 kg / cm at 300 to 450 ° C.²) Under the high temperature and high pressure conditions.
[0005]
According to Japanese Patent Application No. 11-276181, the applicant of the present application previously supplied oxygen, oxygen and water, or water as a solvent together with the object to be decomposed, and heated to a predetermined temperature at a normal pressure reactor. The present invention relates to a processing method and apparatus for decomposing a hardly decomposable substance on the basis of any one of the three decomposition principles of oxidative decomposition, hydrolytic decomposition, and hydrolysis, or a combination thereof by passing through a predetermined reaction time. Proposed. In this processing method, the steam of the decomposition target after the decomposition process is liquefied and discharged by cooling with a neutralization cooler.
[0006]
In addition, one or a plurality of showering towers for separating the liquid component in the vapor of the material to be decomposed into the reactor, a neutralization cooler for cooling the obtained liquid component, and the liquid component for the showering tower A circulation mechanism for spraying inside is attached.
[0007]
According to such a decomposition treatment method and apparatus, refractory substances such as chlorofluorocarbons or organic compounds having a benzene nucleus and other industrial wastes are supplied by supplying only oxygen or oxygen and water, or water as a solvent, at normal pressure. By passing through the reactor in which only the temperature has increased for a predetermined reaction time, it is hydrolyzed by the superheated steam of water as a solvent, the form of oxidative decomposition by oxygen and the addition of water and oxygen The hardly decomposable substance is decomposed by any form of hydrolytic decomposition, and the vapor after the decomposition is dissipated as a detoxified gas, or it can be liquefied and discharged.
[0008]
[Problems to be solved by the invention]
As described above, the decomposition means using the hydrothermal reaction must maintain the high-temperature and high-pressure conditions in the reactor, so that the structure of the reactor and the pressure regulating valve becomes complicated and mechanical strength, for example, tensile It is difficult to design to withstand stress and thermal stress, and there is a problem that the material to be used is limited. In addition, the mechanism for pumping and discharging the solid-liquid mixture under high temperature and high pressure is complicated, and it is necessary to change the structure depending on the type of substance to be decomposed. A piping damage accident may occur during operation due to high pressure, and there are still difficulties from the viewpoint of ensuring safety.
[0009]
Further, according to the previously proposed Japanese Patent Application No. 11-276181, oxygen, oxygen and water, or water as a solvent alone is supplied together with the material to be decomposed, and a normal pressure heated to a predetermined temperature is obtained. By passing through the reactor after a predetermined reaction time, it is possible to decompose difficult-to-decompose substances based on any of the three decomposition principles of oxidative decomposition, hydrolytic decomposition, and hydrolysis, or a combination thereof. In addition, the vapor of the material to be decomposed after being decomposed can be liquefied and discharged by cooling with a neutralization cooler. For example, the decomposition can be performed with a decomposition rate of 99.9% or more. When started, the temperature inside the reactor rises due to the exothermic reaction, and the temperature inside the reactor becomes 1200 ° C. or higher depending on the amount and type of the decomposing treatment material such as chlorofluorocarbon, so that the temperature control is difficult. To have.
[0010]
In particular, when the temperature in the reactor rises to 1000 ° C. or more, the limit of the corrosion resistance of the reactor is reached, causing a problem that the apparatus deteriorates. When ceramic with high heat resistance is used as the material of the reactor, it can withstand up to about 1800 ° C. For example, hydrofluoric acid even when silicon carbide (SiC), which has corrosion resistance to hydrofluoric acid (HF) and hydrochloric acid (HCl), is used. And oxygen at the same time,
SiC + 2O₂→ SiO₂+ CO₂
SiO₂+ 4HF → SiF₄+ 2H₂O
There is a problem that the corrosion resistance is rapidly reduced. Alumina has high corrosion resistance to hydrochloric acid, but has low corrosion resistance to hydrofluoric acid. As a result of conducting a corrosion resistance test at 1000 ° C. or higher under conditions where hydrofluoric acid and oxygen are simultaneously present using silicon carbide (SiC) having a thickness of 6 mm and alumina as a sample, 170 to 200 hours for silicon carbide (SiC), alumina In this case, it is observed that the sample is damaged or corroded in 250 to 300 hours, and even when Hastelloy, Inconel, or stainless steel 310s is used as another material, the corrosion rate increases rapidly near the transformation point when it exceeds 1200 ° C. Therefore, the reactor is required to be kept at 1000 ° C. or lower practically.
[0011]
In order to prevent the temperature inside the reactor from rising, it is necessary to reduce the processing amount of the material to be decomposed or to provide a separate cooling device. However, this reduces the efficiency of the decomposition treatment and increases the cost of the device itself. There is a difficulty of being invited.
[0012]
Furthermore, when chlorofluorocarbon is assumed as a material to be decomposed, the decomposition start temperature differs depending on the type of chlorofluorocarbon. Therefore, the set temperature for decomposition must be changed corresponding to each chlorofluorocarbon. For example, when decomposing recovered CFCs whose types and ratios are unknown, or R12 (CFC-12), R134, R134a, R410, R407, R404 and other mixed CFCs, the decomposition temperature is the highest at the set temperature of R12. When the decomposition is attempted, in the case where R134a is contained in the chlorofluorocarbon, the temperature in the reactor may exceed 1300 ° C., resulting in a problem that the lifetime of the reactor itself is extremely reduced. The set temperature for decomposing these chlorofluorocarbons must be determined after examining the type and ratio of chlorofluorocarbons by gas analysis.
[0013]
In addition, in order to stably decompose mixed CFCs in which various CFCs are arbitrarily mixed, it is important to lower the decomposition start temperature. Even if the amount of heat generated in the reactor is high, the decomposition start temperature must be low. Can be within the allowable temperature range. Even if the temperature in the reactor is slightly over, it can be dealt with by simple cooling means such as opening the lid of the reactor or air-cooling, so that the processing efficiency can be achieved without sacrificing the throughput of the material to be decomposed. Is considered to be able to maintain high.
[0014]
In JP-A-10-249161, a plasma constraining nozzle having a through hole for allowing plasma gas to flow into the outer periphery of the electrode and allowing the plasma arc to pass therethrough is disposed on the outer periphery of the plasma arc and compressed air. Disclosed is a method and an apparatus for decomposing a freon plasma arc in which an anode nozzle that allows a plasma jet to pass through is disposed, and a freon to be reacted is introduced from a swivel introduction hole and the flon is decomposed by contact between the freon and the plasma jet. . However, the reaction by plasma is a method in which the gas to be decomposed is brought into contact with the high temperature part after the plasma is generated and thermally decomposed, and the gas necessary for the reaction is mixed. Therefore, all the gases to be decomposed are mixed. It is not possible to cause the reaction to be efficiently performed by simultaneously contacting a gas of this kind with a plasma jet.
[0015]
The present invention eliminates the above problems in a system that decomposes environmentally hazardous substances such as chlorofluorocarbons, SF6, halon, organic compounds having benzene nuclei and other industrially degradable substances such as industrial waste, and provides a reaction form. It can be made uniform, and the thermal decomposition of the reactor can efficiently perform the decomposition reaction without heating the reactor to a high temperature, improving the corrosion resistance of the device, and no toxic gas or explosive combustible gas is generated during the reaction. An object of the present invention is to provide a method and apparatus for decomposing a hardly decomposable substance that does not cause clogging or corrosion of piping.
[0016]
[Means for Solving the Problems]
In order to achieve the above object, the present invention supplies oxygen, oxygen and water, or water as a solvent together with a substance to be decomposed to the reactor, and is placed in the reactor heated to a predetermined temperature. By releasing thermoelectrons from the cathode toward the anode, the thermoelectrons collide with oxygen, oxygen and water, or water molecules or atoms as a solvent together with the object to be decomposed, thereby causing the molecules and atoms to collide. Excitation and activation energy is injected, and oxygen or oxygen and water, or water as a solvent is allowed to pass through the reactor under normal pressure after passing through a predetermined reaction time. Provided as a basic means is a method and apparatus for decomposing a hardly decomposable substance that decomposes the hardly decomposable substance based on one of the three decomposition principles of hydrolytic decomposition and hydrolysis, or a combination thereof. .
[0017]
  Furthermore, by releasing thermoelectrons to oxygen or oxygen and water or water as a solvent together with the object to be decomposed, these thermoelectrons together with the object to be decomposed are oxygen or oxygen and water or a solvent. The molecules and atoms are excited to collide with water molecules and atoms to inject activation energy and then supplied to the reactor, and oxygen, oxygen and water, or water as a solvent is usually supplied with the substance to be decomposed. A structure in which a hardly decomposed substance is decomposed on the basis of any one of the three decomposition principles of oxidative decomposition, hydrolytic decomposition, and hydrolysis, or a combination thereof, by passing through a pressure reactor through a predetermined reaction time. And one or more selected from the substance to be decomposed, oxygen, oxygen and water, or water as a solventofA configuration for emitting thermal electrons is provided.
[0018]
The method using air instead of oxygen, by supplying air from the middle of the reactor, promotes the oxidation reaction by oxygen in the supplied air, and cools the reactor by nitrogen in the supplied air And a method of liquefying and discharging the vapor of the material to be decomposed after being decomposed by cooling with a neutralization cooler.
[0019]
Further, the reactor includes one or a plurality of showering towers for separating liquid components in the vapor of the substance to be decomposed, a neutralization cooler for cooling the obtained liquid components, and the liquid components for the showering tower. A circulation mechanism for spraying inside is attached.
[0020]
According to such a decomposition treatment method and apparatus, oxygen, or oxygen and water, or water as a solvent is supplied by supplying chlorofluorocarbon or an organic compound having a benzene nucleus and other industrial waste, or water at a normal pressure. By driving the activation energy injection mechanism provided in the reactor when passing through the reactor after a predetermined reaction time, the thermal electrons are discharged from each cathode toward the anode while accelerating. Alternatively, before being supplied to the reactor, oxygen is released together with the substance to be decomposed, or oxygen and water, or water as a solvent, respectively. Activation energy by colliding with molecules and atoms of oxygen and water or water as a solvent to excite them and ionizing or dissociating them into radicals or ions It is injected. Accordingly, the decomposition reaction is efficiently performed without heating the reactor to a high temperature by heat energy, the reaction form can be made uniform, and the form hydrolyzed by the superheated steam of water as a solvent, and oxygen The hardly decomposable substance is decomposed in any form of oxidative decomposition and hydrolytic decomposition by addition of water and oxygen. Thereafter, the vapor that has been decomposed is either dissipated as a detoxified gas or liquefied and discharged.
[0021]
DETAILED DESCRIPTION OF THE INVENTION
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Specific embodiments of a method for decomposing a hardly decomposable substance and its apparatus according to the present invention will be described below with reference to the drawings. In the present invention, a hardly decomposable substance including an environmental pollutant such as chlorofluorocarbon gas is decomposed at normal pressure, and the target hardly decomposed substance is an organic compound that is stable, but there is no particular limitation. As long as it can be gasified such as organic solvents such as chlorofluorocarbon, trichrene, waste oil, dioxin, PCB, etc., the state is not particularly limited regardless of whether it is solid, liquid or gas. It is mainly organic compounds that are useful but difficult to treat after use or harmful ones such as chlorobenzene, chlorofluorocarbon (halogen carbon compound), dioxins in question.
[0022]
As a result of trying various improvement experiments, the inventor of the present application supplied oxygen, oxygen and water, or water as a solvent alone together with a substance to be decomposed such as chlorofluorocarbon in the reactor, and injected thermal energy. It is possible to decompose a hardly decomposable substance based on any one of the three decomposition principles of oxidative decomposition, hydrolytic decomposition, and hydrolysis, or a combination thereof, and to provide activation energy to the material to be decomposed by a method other than heating. It was found that the reaction proceeds efficiently if injected.
[0023]
In general, activation energy must be injected in order to perform a chemical reaction smoothly. It is common practice to raise the temperature of the reaction system by applying thermal energy as an activation energy injection means, but the activation energy has a specific value depending on the chemical substance, and the temperature at which the reaction starts is also It depends on the substance. Therefore, if activation energy is applied to the substance by a method other than heating, the chemical reaction is considered to proceed smoothly if the free energy (ΔG) is (−).
[0024]
In addition, when water is added without causing the reactor to be in a high-pressure state during the reaction, the decomposition target in the superheated steam can be decomposed by maintaining the atmosphere of the superheated steam, and toxic gas, etc. No combustible gas is generated. Air may be used instead of oxygen.
[0025]
Note that either oxygen or air may be used. However, if air is used instead of oxygen, nitrogen is supplied four times as much as the required amount of oxygen simultaneously with oxygen, increasing the amount of gas. However, there is a cooling effect of the reactor. In the oxidative decomposition, heat of oxidation is generated, and this heat of oxidation raises the temperature in the reactor. However, a very high temperature rise in the reactor is not preferable from the viewpoint of safety of the apparatus. Thus, the overall temperature in the reactor can be lowered by the presence of nitrogen that is not involved in the reaction at all.
[0026]
According to the present invention, it is possible to open a benzene ring, and the benzene to be decomposed by the present invention is a basic compound of an aromatic hydrocarbon, and C₆H₆Monochlorobenzene is C₆H₅It is represented by Cl. Examples of organic compounds having a benzene nucleus include phenols. These phenols are a general term for organic compounds in which an OH group is bonded to a benzene nucleus.₆H₅Expressed as OH. In addition, according to the present invention, dioxins, PCBs and the like having a benzene ring as a skeleton structure can be decomposed and rendered harmless.
[0027]
FIG. 9 is a system diagram showing a basic embodiment of a method and apparatus for decomposing a hardly decomposed material to which the present invention is applied. Compressor, 4 is a flow control valve, 5 is a water tank as a solvent, 6 is a metering pump, 7 is a reactor, and other than the flow control valves 4, 2 and pipes 8, 9, 10 derived from the metering pump 6 The end is introduced into the reactor 7. Preliminary heaters 11, 12, and 13 are provided in the pipes 8, 9, and 10. The reactor 7 is also provided with a plurality of heaters 14, 15, 16, and the temperature distribution T in the reactor₁, T₂, T₃Is controlled to obtain freely. The reactor 7 is an apparatus for performing a decomposition treatment by reacting a material to be decomposed with water in a solvent and oxygen in the air while maintaining a predetermined temperature. 29 is an air compressor for supplying air to the reactor 7 from the middle, and 30 is a flow rate adjusting valve thereof.
[0028]
Reference numerals 17, 18, and 19 denote showering towers, and reference numeral 20 denotes a neutralization cooler. The lower ends of the showering towers 17, 18, and 19 are inserted into the neutralization cooler 20. In each showering tower 17, 18, 19, terrarets 17 a, 18 a, 19 a that allow only reaction gas to pass are arranged. 21 is a showering pump, 22 is a header, 23 is a cooler, and 24 is a suction blower. Pipes 20 a and 20 b led out from the neutralization cooler 20 are connected to the cooler 23. 23a is an inlet of the cooling water, and 23b is an outlet of the cooling water. A pipe 25 led out from the reactor 7 is connected to an intermediate portion of the showering tower 17, flows in the showering towers 18 and 19 through the pipes 26 and 27, and is exhausted to the outside through the suction blower 24. It has become.
[0029]
The showering towers 17, 18, and 19 are devices for separating liquid components in the vapor of the object to be decomposed, and are not limited to the three illustrated, but a single or a plurality of showering towers are provided. . The neutralization cooler 20 cools the obtained liquid component, and the showering pump 21 and the header 22 have a circulation mechanism for spraying the obtained liquid component into the showering towers 17, 18, 19 to promote liquefaction. It is composed.
[0030]
The inside of the reactor 7 is not pressurized and is at a normal pressure with the discharge port side opened. In other words, the pressure of the piping on the inlet side is a pressure gradient with only pressure loss due to the pipeline. As described above, it is one of the features of the present invention that the reactor 7 can decompose the substance to be decomposed by using an open type apparatus that does not forcibly pressurize unlike the conventional high pressure hydrothermal reactor. . A slight pressure is naturally generated in the reactor 7 due to the superheated steam, and a pressure gradient is formed to transfer the substance to be decomposed. In the present invention, the normal pressure means that the outlet is opened without forcibly pressurizing to a high pressure as in the conventional hydrothermal reactor.
[0031]
1 is a cross-sectional view showing a configuration of the reactor 7, FIG. 2 is an enlarged view of a main part of FIG. 1, and FIG. 3 is a cross-sectional view taken along line AA of FIG. The outer periphery of the reactor 7 is covered with a heat insulating material 31, and a stainless steel pipe 32 is provided through the inside along the longitudinal direction. The other ends of the pipes 8, 9, 10 are introduced into the pipe 32, and the plurality of heaters 14, 15, 16,. In the reactor 7, the material to be decomposed, the solvent water and oxygen in the air react with each other while maintaining a predetermined temperature.
[0032]
In the middle of the pipe 32, an activation energy injection mechanism 33, which is a characteristic component of the present invention, is provided. As shown in FIGS. 2 and 3, the activation energy injection mechanism 33 has three cathodes H that emit thermal electrons into the pipe 32.₁, H₂, H₃And three anodes P receiving these thermoelectrons₁, P₂, P₃Is the main constituent. 3 cathodes H₁, H₂, H₃Also serves as a coil heater, and each of these cathodes H₁, H₂, H₃Anode P at a position opposite to₁, P₂, P₃Is arranged. Each anode P₁, P₂, P₃Is power E₁Connected to the positive side of each cathode H that also serves as a coil heater₁, H₂, H₃One terminal of the power supply E₁, E₂And the other terminal is connected to the power supply E.₂It is connected to the positive side. Reference numeral 34 denotes an insulating member made of alumina.
[0033]
The operation mode of this embodiment will be described. First, taking as an example the case of decomposing chlorofluorocarbon gas, which is an environmental pollutant, by hydrolytic decomposition, chlorofluorocarbon is introduced into the decomposition target tank 1 and the air compressor 3 and metering pump 6 are activated to generate air and chlorofluorocarbon. It is sent to the pipe 32 in the reactor 7 through the flow rate adjusting valves 4, 2 and the pipes 8, 9, and at the same time, a certain amount of water as a solvent is similarly fed into the pipe 32 through the pipe 10 at an appropriate ratio. Mixed. At this time, the preheating heaters 11, 12, and 13 provided in the pipes 8, 9, and 10 are driven to perform preheating, and the three heating heaters 14, 15, and 16 provided in the reactor 7 are driven. By doing so, the temperature distribution T in the pipe 32₁, T₂, T₃To control.
[0034]
Superheated steam is generated by heating the inside of the pipe 32 of the reactor 7 to a predetermined temperature range. Since the temperature of the superheated steam necessary for the decomposition treatment varies depending on the object to be decomposed, it is set according to the object to be decomposed. Then, in the pipe 32 of the reactor 7, CFC-22, which is an object to be decomposed, reacts with water in the solvent and oxygen in the air while maintaining a predetermined temperature to perform the hydrolytic decomposition treatment. You may supply air in the pipe 32 of the reactor 7 using the air compressor 29 and the flow regulating valve 30 from the middle of reaction.
[0035]
During the above-described decomposition process, the activation energy injection mechanism 33 provided in the middle of the pipe 32 in the reactor 7 is driven, and thermionic electrons (e⁻The main feature of the present invention is that the activation energy is injected into the object to be decomposed. That is, as indicated by the broken line in FIG.₁, H₂, H₃To anode P₁, P₂, P₃Thermionic electrons are emitted while being accelerated toward the surface, and in the course of emission, the thermal electrons collide with the molecules and atoms of the object to be decomposed to excite the molecules and atoms, and the molecules and atoms are ionized and dissociated. Activation energy is injected by using radicals or ions.
[0036]
Since the excited molecules and atoms are a group of highly reactive particles that release excessive energy and become stable, the decomposition treatment can be performed without particularly increasing the temperature in the reactor 7. Things can be decomposed. Then, a predetermined reaction time elapses while the superheated steam passes through the reactor 7, and the material to be decomposed in the superheated steam is decomposed and sent into the next-stage showering tower 17.
[0037]
In the showering tower 17, only the reaction gas in the material to be decomposed flows from the terrarette 17 a through the pipe 26, the terralet 18 a, the pipe 27, and the terralet 19 a, and is exhausted to the outside through the suction blower 24. The liquid component in the material to be decomposed flows into the neutralization cooler 20 from each showering tower 17, 18, 19 and a part flows into the cooler 23 from the pipe 20a. By supplying the cooling water from the cooling water inlet 23a of this cooler 23 and letting it flow out from the outlet 23b, the gas component of the decomposition product is cooled and completely liquefied. The temperature in the cooler 23 should just be the temperature which can liquefy the gas component of a decomposition product, and is set to about 25 degreeC in the case of Freon gas.
[0038]
The liquefied decomposition product is sent from the showering pump 21 to the header 22 and sprayed into the showering towers 17, 18, 19, thereby cooling the gas component and promoting liquefaction. By rapidly cooling the decomposition product and liquefying in this way, generation of by-products is prevented, and there is no concern about secondary contamination due to release in the gaseous state and scattering into the atmosphere. The reason for quenching is to prevent the formation of harmful by-products because slow by-products such as dioxins are formed when cooled slowly from a high temperature to a low temperature. The decomposition product stored in the neutralization cooler 20 is periodically discharged through the pipe 28 and sent into a drainage tank (not shown).
[0039]
FIG. 4 is a cross-sectional view showing another embodiment of the reactor 7, and FIG. 5 is a cross-sectional view taken along the line BB of FIG. The reactor 7 is mainly composed of a stainless steel pipe 35, and the other ends of the pipes 8, 9, 10 are introduced through the front wall 35 a of the pipe 35. Preliminary heaters 11, 12, and 13 are disposed in the pipes 8, 9, and 10, and a plurality of heaters 14, 15, and 16 are also disposed in the reactor 7. And the cathode H which discharge | releases a thermoelectron to the position which penetrates the center part of the front wall 35a.₄Are arranged, and three anodes P receiving the thermal electrons at the inner wall intermediate portion of the pipe 35₄, P₅, P₆Is arranged. Therefore cathode H₄And three anodes P₄, P₅, P₆Are arranged apart from each other in the longitudinal direction of the reactor 7, that is, in the flow direction of the material to be decomposed.₄And anode P₄, P₅, P₆The activation energy injection mechanism is configured by.
[0040]
Cathode H that doubles as coil heater₄The one side terminal is connected to the positive side of the high-voltage power source E, and the other side terminal is connected to the negative side of the high-voltage power source E.₄, P₅, P₆Is connected to the positive side of the high-voltage power supply E.
[0041]
Such a configuration of the reactor 7 has a feature that the apparatus itself can be miniaturized. The operation mode of the reactor 7 is substantially the same as that of the embodiment shown in FIG.₄To anode P₄, P₅, P₆The electrons are emitted while accelerating toward the surface, and in the middle of the emission, the thermoelectrons collide with the molecules and atoms of the object to be decomposed to excite the molecules and atoms, and the molecules and atoms are ionized and dissociated. Activation energy is injected by using radicals or ions.
[0042]
In the example shown in FIGS. 1 to 4 described above, oxygen, oxygen and water, or water as a solvent is supplied to the reactor 7 together with the object to be decomposed, and then excited by releasing thermal electrons. By releasing thermionic electrons to the object to be decomposed, oxygen and water before being supplied to the reactor 7, the thermoelectrons collide with molecules and atoms to be decomposed, oxygen and water. The molecule or atom may be excited to inject activation energy. Or you may make it discharge | release a thermoelectron only to the one or more selected from the to-be-decomposed processed material, oxygen, and water.
[0043]
An example of the configuration of the activation energy injection mechanism 33 that emits and excites thermal electrons before supplying the object to be decomposed or the like to the reactor 7 is shown in FIGS. 6 is a cross-sectional view of the main part showing another example of the activation energy injection mechanism 33, FIG. 7 is a left side view thereof, and FIG. 8 is a cross-sectional view taken along the line CC. The activation energy injection mechanism 33 shown in FIG. 6 is connected to the reactor 7, and three sets are appropriately arranged as shown in FIG. These are for exciting the object to be decomposed, oxygen and water, respectively.
[0044]
A stainless steel pipe 32 is provided in the reactor 7 along the longitudinal direction via an insulating member 34, and a cathode H that emits thermoelectrons to the end of the pipe 32.₄And the cathode H₄Are connected to a heater 36 for generating thermoelectrons, and a cylinder 37 for accelerating electrons is provided around the heater 36. Further, the end of the pipe 32 on the reactor side and the end of the reactor are anodes P for receiving thermoelectrons.₇It is configured as. In the middle of the pipe 32, an input port 39 for supplying an object to be decomposed (oxygen or water) is opened. Anode P₇Is power E₁Connected to the positive side of the cathode H₄One terminal of the power supply E₁, E₂And the other terminal is connected to the power supply E.₂It is connected to the positive side.
[0045]
According to the above apparatus, the activation energy injection mechanism 33 is driven so that the thermal electrons (e⁻), The activation energy can be injected by releasing thermal electrons to the material to be decomposed, oxygen, and water, respectively, or selectively before being supplied to the reactor 7. That is, the cathode H in FIG.₄To anode P₇The thermoelectrons are heated by the heater 36 and emitted while being accelerated by the electron accelerating cylinder 37, and the thermoelectrons are decomposed in the reaction field 38 in the middle of the emission, molecules of oxygen, water, The molecules and atoms are excited by colliding with the atoms, and the molecules and atoms are ionized or dissociated to form radicals or ions. Then, activation energy is injected and then supplied to the reactor 7.
[0046]
The total length of the reactor 7 in this embodiment is 1900 mm, the output of the three heaters 14, 15, 16 is 11 kW, the flow rate of Freon is 10 (kg / h), the amount of water is 10 (kg / h), and the amount of air is R12 was 0 (l / min), R22 was 120 (l / min), and R134A was 300 (l / min). The calorific value of main CFCs is

It is.
[0047]
When the substance to be decomposed is R12, that is, CFC-12, the hydrolysis of the following formula (1) proceeds by adding only water as a solvent for reaction.
CCl₂F₂+ 2H₂O → CO₂+ 2HCl + 2HF (1)
[0048]
When the activation energy injection mechanism 33 is driven during the reaction of the above formula (1), thermionic electrons (e⁻) Collide with CFC-12 molecules and atoms to form molecular ions and radicals and radical ions accompanied by dissociation.

[0049]
These molecular ions, radicals and radical ions are excited with high energy and are highly reactive particles, so the excited molecules and atoms release excess energy and are in the most stable state. That is, the -directional reaction proceeds and decomposes so that the binding energy becomes the lowest. Then, the reaction time elapses and the decomposition process is almost complete, and the reaction product is fed into the next showering tower 17.
[0050]
Hydrolysis of CFC-22 is carried out according to the following formulas (3) to (5).
CHClF₂+ 2H₂O → CO₂+ HCl + 2HF + H₂……… (3)
CHClF₂+ H₂O → HCl + 2HF + CO (4)
4CHClF₂+ 6H₂O → 3CO₂+ 8HF + 4HCl + CH₄......... (5)
According to equations (3), (4) and (5), H₂Gas, CO gas, CH₄There is a problem of generating harmful or flammable gas called gas. Therefore, when air or oxygen is added together with water to cause oxidative decomposition, the following equation (6) proceeds.
CHClF₂+ 2H₂O + O₂ → 2CO₂+ 2HCl + 4HF (6)
Therefore, carbon monoxide CO
2CO + O₂= 2CO₂
And hydrogen gas H₂Is
2H₂+ O₂= 2H₂O
Methane gas CH₄Is
CH₄+ 3O₂= CO₂+ 2H₂O
It becomes. Therefore, harmful or flammable gas is detoxified as carbon dioxide or converted into moisture, resulting in the result shown in equation (6).
[0051]
Hydrocarbon CFC-134a is hydrolyzed by the following formulas (7) to (9).
C₂H₂F₄+ 2H₂O → 4HF + 2CO + 2H₂………………… (7)
C₂H₂F₄+ 4H₂O → 4HF + 2CO₂+ 3H₂……………… (8)
C₂H₂F₄+ 3H₂O → 4HF + CO + 2H₂+ CO₂............ (9)
(7) Even in the case of (8) and (9), H₂Although harmful or flammable gases such as gas and CO gas are generated, the above equation (6) proceeds by adding air or oxygen together with water to cause the reaction to be hydrolyzed.
[0052]
Hydrocarbon CFC-141b is hydrolyzed by the following formulas (10) to (11).
C₂H₃Cl₂F + 2H₂O → 2CO + HF + 2HCl + 2H₂...... (10)
C₂H₃Cl₂F + 4H₂O → 2CO₂+ HF + 2HCl + 4H₂...... (11)
(10) Equation (11) is carbon monoxide, H₂Since gas is generated, it is not suitable. Therefore, when air or oxygen is added together with water to cause the reaction, the following formulas (12) and (13) advance, and hydrolytic decomposition is performed.

In this case, when water and oxygen are added, CO, H as shown in equations (12) and (13)₂Is unsuitable. In this case, the following equations (14) and (15) proceed in the case of oxidative decomposition with only oxygen added.
C₂H₃Cl₂F + 2O₂ → 2CO₂+ 2HCl + HF …… (14)
C₂H₃Cl₂F + O₂ → 2CO + 2HCl + HF (15)
In this case as well, CO gas is generated as shown in the equation (15). However, since the equation (14) is preferentially generated in an oxygen-excess state, an atmosphere in which oxygen is sufficiently excessive is created. Regardless of the decomposition of any process, the equation (14) can be finally obtained. When only oxygen is added, oxidative decomposition proceeds, but an unexpected by-product may be formed. Therefore, the presence of superheated steam generated by adding an appropriate amount of water is important. Therefore, hydrolytic decomposition is the most suitable decomposition method.
[0053]
When CFC gas was used as the decomposition target, the following products were confirmed. First, the gas is CO₂, HCl and HF, and after cooling, HCl and HF dissolve in water and become strong acids.
[0054]
As shown in the following equation (16), caustic soda NaOH is added according to the concentration of chlorofluorocarbon, and carbon dioxide gas is converted to sodium bicarbonate NaHCO 3.₃In some cases, sodium chloride is generated by the reaction of caustic soda and hydrochloric acid as in the formula (17), and sodium fluoride NaF is generated in the reaction of the caustic soda and hydrofluoric acid as in the formula (18). . When neutralizing the strongly acidic liquid after liquefaction with NaOH, the equations (17) and (18) must be₂Therefore, a method in which the equation (16) also occurs and carbon dioxide gas is not released becomes possible.
NaOH + CO₂   → NaHCO₃ ………………………… (16)
NaOH + HCl → NaCl + H₂O ………………………… (17)
NaOH + HF → NaF + H₂O ………………………… (18)
[0055]
The embodiment described above is for decomposing a fluid or gaseous object to be decomposed, and in addition to chlorofluorocarbon, trichloroethane and other halogenated carbon compounds as an environmental pollutant are decomposed. Is possible. Trichloroethane (CH) according to this embodiment₃・ CCl₃) And chlorobenzene (C₆H₅The decomposition reaction of Cl) will be described.
[0056]
First, trichloroethane (CH₃・ CCl₃), The reaction proceeds as follows.
CH₃・ CCl₃+ 2O₂ → 2CO₂+ 3HCl
[0057]
Next, chlorobenzene (C₆H₅When decomposing Cl), the decomposition proceeds as follows.
C₆H₅Cl + 7O₂ → 6CO₂+ 2H₂O + HCl
[0058]
Here, theoretically considering the driving principle of the activation energy injection mechanism 33, it is generally said that when an electron is in the lowest energy state, the atom is in a ground state, and the electron is in an energy high state. This is called an excited state in which energy is stored inside. When the excitation is high enough, the electrons escape from the nuclear constraints and become free electrons. This is ionization, and free electrons maintain a continuous energy state. In other words, ionization can be considered as one limit of internal excitation.
[0059]
On the other hand, the minimum energy that must be added to the reaction system by collision is the activation energy (E_act). The source of activation energy is the kinetic energy of the moving particles, and the amount of energy given in the collision is almost less than the minimum, but if one or both of the particles are moving around at an unusually fast rate, A strong collision takes place and gives enough energy to cause a chemical reaction.
[0060]
Therefore, sufficient activation energy (E_act), The continuous energy state of the free electrons internally excited by driving the activation energy injection mechanism 33 is effectively used, and the heat energy of the heater or the like Even without using an imparting means, the energy level of the reaction system can be increased to allow the chemical reaction to proceed smoothly.
[0061]
In addition, according to the present invention, it is possible to inject thermoelectrons in a state where all the gases to be decomposed are mixed, so that activation energy is simultaneously injected into all kinds of gases to perform the reaction efficiently. It can be made.
[0062]
Table 1 is a list of the R22 (CFC-22), R12, and R134A freon gases in the case where the activation energy injection mechanism 33 is not driven, and the relationship between the decomposition rate and the temperature, and FIG. It is the graph which plotted the measured value.
[0063]
[Table 1]

[0064]
According to Table 1 and FIG. 10, R22 has a decomposition rate of 99.9% at 850 ° C. and R12 has a decomposition rate of 99.9% at 950 ° C., and R134A has a decomposition rate of 800 ° C. Has reached 99.9%. Table 2 is a table in which the relationship between the time (minutes) and the temperature rise after the decomposition rate of each chlorofluorocarbon gas reaches 99.9%, and FIG. 11 is a graph in which the measured values in Table 2 are plotted. .
[0065]
[Table 2]

[0066]
According to Table 2 and FIG. 11, R12 is in the vicinity of 930 ° C. after the decomposition rate reaches 99.9%, and R22 reaches 1080 ° C. 18 minutes after the decomposition rate reaches 99.9%. After that, the temperature hardly changes. On the other hand, in R134A, the decomposition rate reaches 99.9%, reaches 1241 ° C. 18 minutes later, and thereafter is approximately 1240 ° C.
[0067]
Table 3 is a table in which the relationship between the decomposition rate and the temperature is similarly measured for each of the fluorocarbon gases of R12 (CFC-12), R22, and R134A in the case where the activation energy injection mechanism 33 is driven. It is the graph which plotted the measured value of Table 3. FIG. The cathode H shown in FIG.₁, H₂, H₃And anode P₁, P₂, P₃Each electrode surface area of 3.7cm²The material was tungsten + thorium, the current was 3 A, the electrode surface temperature was about 1500 ° C., and the acceleration voltage was 1 kV.
[0068]
[Table 3]

[0069]
According to Table 3 and FIG. 12, R12 has a decomposition rate of 99.9% at 500 ° C., R22 has a decomposition rate of 99.9% at 450 ° C., and R134A has a decomposition rate of 400 ° C. Has reached 99.9%. Therefore, it can be seen from the data in Table 1 and FIG. 10 that the decomposition rate of CFCs reaches 99.9% in a region as low as 400 ° C. to 450 ° C.
[0070]
Table 4 is a table in which the relationship between the time (min) at the time of free electron injection and the temperature rise is measured for each Freon gas, and FIG. 13 is a graph in which the measured values in Table 4 are plotted.
[0071]
[Table 4]

[0072]
According to Table 4 and FIG. 13, the temperature of R12 hardly changes with time as 600 ° C. to 614 ° C. at the time of electron injection, and R22 reaches 721 ° C. after the temperature of 550 ° C. has elapsed for 10 minutes. It is in the vicinity of ° C-735 ° C. R134A initially reaches 854 ° C. after 12 minutes at a temperature of 500 ° C., and thereafter is around 855 ° C. Therefore, it can be seen that the temperature increase range is 1000 ° C. or lower in any case.
[0073]
Table 5 is a table in which the relationship between the decomposition rate and the temperature is similarly measured for each of the CFCs in the case where the activation energy injection mechanism 33 is driven, and FIG. 14 is a graph in which the measured values in Table 5 are plotted. . The cathode H shown in FIG.₁, H₂, H₃And anode P₁, P₂, P₃The measurement conditions except that the current between them was 1.5 A were the same as those in Table 3.
[0074]
[Table 5]

[0075]
According to Table 5 and FIG. 14, R12 has a decomposition rate of 99.9% at 650 ° C., R22 has a decomposition rate of 99.9% at 600 ° C., and R134A has a decomposition rate of 550 ° C. Has reached 99.9%. Therefore, it can be seen from the data in Table 1 and FIG. 10 that the decomposition rate of chlorofluorocarbon reaches 99.9% in the low temperature region of 250 ° C. to 300 ° C.
[0076]
[Table 6]

[0077]
(1) in Table 6 shows a case where 10 (kg / h) of R404 (CFC-404) is decomposed to a decomposition rate of 99.9% in the case where the activation energy injection mechanism 33 is not driven for mixed CFCs. (2) is data obtained by measuring a change in temperature after 6 (kg / h) of R404 was decomposed under the same conditions. In (1), the temperature reached 800 ° C. at the end of the decomposition treatment, and after 16 minutes, the temperature rose to over 1000 ° C. and after 30 minutes, the temperature rose to 1283 ° C., and in (2) the temperature after 30 minutes passed was 864 ° C. It has become. Therefore, it is not preferable to decompose R404 at 10 (kg / h) at a time because it causes deterioration of the device due to high temperature, and unless the amount of decomposition treatment is reduced to about 6 (kg / h) in (2). In other words, there is a problem that work efficiency is lowered.
[0078]
Table 3 (3) shows the change in temperature after decomposing 10 (kg / h) of R404 to a decomposition rate of 99.9% while driving the activation energy injection mechanism 33 and injecting free electrons. FIG. 15 plots the data (3) together with the data (1) and (2). According to (3) of Table 6, the temperature is 500 ° C. at the end of the decomposition treatment, reaches 872 ° C. after 16 minutes, and is kept at around 873 ° C. until 30 minutes thereafter. Therefore, according to the present invention, even if R404 is decomposed at 10 (kg / h) at a time, there is no possibility that the apparatus will be deteriorated due to high temperature, and it is possible to maintain a high amount of decomposition processing and increase work efficiency. it can.
[0079]
【The invention's effect】
As described above in detail, according to the present invention, refractory substances such as chlorofluorocarbons, organic compounds, and other industrial waste are supplied by supplying only oxygen or oxygen and water, or water as a solvent. By driving the activation energy injection mechanism installed in the thermal energy, thermal electrons are emitted from the cathode toward the anode while accelerating, and the thermal electrons are activated by colliding with molecules and atoms of the object to be decomposed and being excited. Thus, the decomposition reaction can be efficiently performed without heating the inside of the reactor to a high temperature by the heat energy of a heater or the like. In particular, it is not necessary to provide a separate cooling device in order to prevent the temperature in the reactor from rising, so that the cost of the device is reduced and there is no risk of sacrificing the throughput of the decomposition target during operation.
[0080]
And by carrying out a predetermined reaction in the reactor, a form hydrolyzed by superheated steam of water as a solvent, a form of oxidative decomposition by oxygen and a form of hydrolytic decomposition by addition of water and oxygen By this, it is possible to decompose the hardly decomposable substance. In particular, the present invention eliminates the need for maintaining the reactor at a high temperature and high pressure unlike the decomposition means utilizing hydrothermal reaction, thus eliminating the need for a reactor and other pressure regulating valves, and facilitating operational control. There are advantages.
[0081]
Moreover, the reaction form is uniform, and three kinds of decomposition forms of oxidative decomposition, hydro-oxidative decomposition, and hydrolysis are obvious, and since reaction aids such as iron and carbon steel are not used, carbon monoxide or the like An explosive combustible gas such as a toxic gas or hydrogen gas is not generated or can be immediately rendered harmless even if generated. Further, it is possible to prevent clogging of the piping due to clogging of the piping due to the reaction product or the start of the reaction in the piping on the way.
[0082]
The gas components that have been decomposed can be liquefied and discharged by cooling, and heating under normal pressure is the main process, so a high-pressure pump is not necessary and the discharge valve or piping may be damaged. There is no. Furthermore, since all the reactions are closed systems that take place in the reactor, the effect is obtained that there is no secondary contamination. Moreover, it can be applied not only to CFCs but also to other industrial wastes and organic substances having a benzene nucleus.
[0083]
Furthermore, according to the present invention, since the process proceeds at a low pressure and the reactor is prevented from reaching a high temperature of 1000 ° C. or higher, the corrosion resistance is remarkably improved and the material of the reactor itself can be arbitrarily selected. In addition, it has the advantage that mechanical strength and corrosion resistance, design to withstand tensile stress or thermal stress is not required, measures against damage to various devices are easy and automation of the device itself is also easy, safety Is effective.
[Brief description of the drawings]
FIG. 1 is a cross-sectional view showing a configuration of a reactor to which the present invention is applied.
FIG. 2 is an enlarged view of a main part of FIG.
3 is a cross-sectional view taken along line AA in FIG.
FIG. 4 is a cross-sectional view showing another embodiment of a reactor.
5 is a cross-sectional view taken along line BB in FIG.
FIG. 6 is a cross-sectional view of a main part showing another example of the activation energy injection mechanism.
7 is a left side view of FIG.
8 is a cross-sectional view taken along the line CC in FIG.
FIG. 9 is a system diagram showing a basic embodiment of a method and apparatus for decomposing a hardly decomposable substance according to the present invention.
FIG. 10 is a graph showing the relationship between the decomposition rate of each chlorofluorocarbon gas and the temperature when the activation energy injection mechanism is not driven.
FIG. 11 is a graph showing the relationship between the time after the decomposition rate of Freon gas reaches 99.9% and the temperature rise.
FIG. 12 is a graph showing the relationship between the decomposition rate of each chlorofluorocarbon gas and the temperature in the case where the activation energy injection mechanism is driven.
FIG. 13 is a graph showing the relationship between time and temperature rise during free electron injection.
FIG. 14 is a graph showing the relationship between the decomposition rate of each chlorofluorocarbon gas and the temperature in the case where the activation energy injection mechanism is driven.
FIG. 15 is a graph showing a change in temperature after decomposing chlorofluorocarbon to 99.9% for a case where the activation energy injection mechanism is driven and a case where the activation energy injection mechanism is not driven.
[Explanation of symbols]
1 ... Decomposed object tank
2, 4, 30 ... Flow control valve
3, 29 ... Air compressor
5 ... Water tank
6 ... Metering pump
7 ... Reactor
11, 12, 13 ... Preheating heater
14, 15, 16 ... heater
17, 18, 19 ... Showering tower
17a, 18a, 19a ... Terralet
20 ... Neutralization cooler
21 ... Showering pump
22 ... Header
23 ... Cooler
24 ... Suction blower
31. Insulation material
32, 35 ... pipe
33 ... Activation energy injection mechanism
34. Insulating member
Reference number P3070

Claims (9)

Oxygen, oxygen and water, or water as a solvent is supplied to the reactor together with the material to be decomposed, and thermionic electrons are emitted from the cathode arranged in the reactor heated to a predetermined temperature toward the anode. Thus, the thermal electrons collide with oxygen or oxygen and water or water molecules or atoms as a solvent together with the object to be decomposed to excite the molecules and atoms to inject activation energy, Oxygen, oxygen and water, or water as a solvent is allowed to pass through a reactor under atmospheric pressure with a predetermined reaction time along with the decomposed product, so that three types of decomposition, oxidative decomposition, hydrolytic decomposition, and hydrolysis are performed. A method for decomposing a hardly decomposable substance, comprising decomposing the hardly decomposable substance based on any one of the principles or a combination thereof. By releasing thermoelectrons to oxygen or oxygen and water or water as a solvent together with the material to be decomposed, the thermoelectrons together with the material to be decomposed are oxygen, oxygen and water, or water as a solvent. After the molecules and atoms collide with the molecules and atoms to activate and inject activation energy, they are supplied to the reactor, and oxygen, oxygen and water, or water as a solvent is added to the substance to be decomposed at normal pressure. It is characterized by decomposing a hardly decomposable substance on the basis of one of the three decomposition principles of oxidative decomposition, hydrolytic decomposition, hydrolysis, or a combination thereof by passing it through the reactor after a predetermined reaction time. A method for decomposing a difficult-to-decompose substance. The decomposition products, oxygen, or oxygen and water, or cracking process of hardly decomposable substance according to claim 2, wherein releasing one or more of the thermal electrons to be selected from water as a solvent. The method for decomposing a hardly decomposable substance according to claim 1, 2 or 3, wherein air is used instead of oxygen. 2. The air is supplied from the middle of the reactor to promote the oxidation reaction with oxygen in the supplied air, and the reactor is cooled with nitrogen in the supplied air. , 2, 3 or 4. 6. The decomposition of a hardly decomposable substance according to claim 1, 2, 3, 4 or 5, characterized in that the vapor of the object to be decomposed after being decomposed is liquefied and discharged by cooling with a neutralization cooler. Processing method. A mechanism for supplying oxygen, oxygen and water, or water as a solvent to the reactor together with the object to be decomposed, and thermoelectrons released from the cathode disposed in the reactor toward the anode And an activation energy injection mechanism that excites molecules or atoms of oxygen, oxygen and water, or water as a solvent, and the inside of the reactor as an object to be decomposed and oxygen, or oxygen and water, or a solvent. Characterized in that the hardly decomposed substance is decomposed on the basis of any one of the three decomposition principles of oxidative decomposition, hydrolytic decomposition, hydrolysis, or a combination thereof by passing water of a predetermined temperature and reaction time. Decomposition processing equipment for difficult-to-decompose substances. A thermal electron is individually emitted to one or more selected from oxygen, oxygen and water, or water as a solvent together with the object to be decomposed, and the object to be decomposed, oxygen, or oxygen and water, or a solvent And an activation energy injection mechanism for exciting water molecules and atoms as a mechanism, and a mechanism for supplying the activated substance to be decomposed and oxygen, or oxygen and water, or water as a solvent to a reactor. By passing a substance to be decomposed and oxygen, or oxygen and water, or water as a solvent for a predetermined temperature and reaction time through the reactor, three kinds of oxidation decomposition, hydrolysis decomposition, and hydrolysis are performed. An apparatus for decomposing a hardly decomposable substance, which decomposes the hardly decomposable substance based on any one of the decomposition principles or a combination thereof. In the reactor, one or more showering towers for separating the liquid component in the vapor of the material to be decomposed, a neutralization cooler for cooling the obtained liquid component, and the liquid component in the showering tower The decomposition processing apparatus for hardly decomposed substances according to claim 7 or 8, wherein a circulation mechanism for spraying is attached.

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